CN107069091A - Lithium secondary battery and the nonaqueous electrolytic solution wherein used - Google Patents

Lithium secondary battery and the nonaqueous electrolytic solution wherein used Download PDF

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Publication number
CN107069091A
CN107069091A CN201710119547.7A CN201710119547A CN107069091A CN 107069091 A CN107069091 A CN 107069091A CN 201710119547 A CN201710119547 A CN 201710119547A CN 107069091 A CN107069091 A CN 107069091A
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active material
negative pole
electrolyte
positive
lithium
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Inventor
宫城秀和
加藤竜
加藤竜一
横沟正和
宇尾野宏之
松本志
松本一志
佐藤智洋
古田土稔
中岛孝之
铃木仁
大岛裕之
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Mu Electrolyte Co ltd
Mitsubishi Chemical Corp
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Mitsubishi Kasei Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Physics & Mathematics (AREA)
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  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of lithium secondary battery, and it includes positive pole and negative pole and nonaqueous electrolytic solution with specific composition and physical property, and the nonaqueous electrolytic solution contains selected from least one of following substances compound, and its content is more than 10ppm, and the material includes：Compound, the intramolecular that the cyclic siloxane compound of formula (1) expression, the fluorosilane compounds of formula (2) expression, formula (3) are represented have compound, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and the propionate of S F keys.The lithium secondary battery has high power capacity, long-life, high-output power.In formula (1), R1And R2It is the organic group of carbon number 1~12, n is 3~10 integer；In formula (2), R3~R5It is the organic group of carbon number 1~12, x is 1~3 integer, p, q and r are 0~3 integer respectively, and 1≤p+q+r≤3；In formula (3), R6~R8It is the organic group of carbon number 1~12, A is the group being made up of H, C, N, O, F, S, Si and/or P.

Description

Lithium secondary battery and the nonaqueous electrolytic solution wherein used
It is on October 19th, 2006, Application No. 201410514981.1, entitled " lithium two applying date that the application, which is, The divisional application of the application of primary cell and the nonaqueous electrolytic solution wherein used ".
Technical field
The nonaqueous electrolytic solution the present invention relates to lithium secondary battery and wherein used, in more detail, is related to containing The non-aqueous electrolytic solution used for lithium secondary batteries of special component and energy occlusion with specific composition and physical property and release lithium positive pole and Negative pole, and particularly cryogenic discharging characteristic is excellent and capacity is high, the long-life, the lithium secondary battery of height output and wherein use Nonaqueous electrolytic solution.
Background technology
In recent years, along with the miniaturization of electronic equipment, the requirement to the high capacity of secondary cell is improved constantly, energy Density ratio nickel-cadmium cell and the high lithium secondary battery of Ni-MH battery attract attention.
Lithium secondary battery can use in a variety of applications where due to being the secondary cell of high power capacity, but it is mainly used in Mobile phone etc. compares in small-sized battery, and expectation expands its application in the large-sized battery of mobile applications etc. from now on.In large-sized battery In particularly output is required, conventional compact battery is simply become merely to big in performance and insufficient.In addition, it is proposed that The various modification methods for being used to improve the battery material of output (for example, referring to patent document 1~25, non-patent literature 1 etc.).Can It is that still can not obtain enough output, it is desirable to further improve.
Patent document 1：JP 2005-071749 publications
Patent document 2：JP 2005-123180 publications
Patent document 3：JP 2001-206722 publications
Patent document 4：JP 2003-267732 publications
Patent document 5：JP 2001-015108 publications
Patent document 6：WO2003/34518 publications
Patent document 7：Unexamined Patent 11-067270 publications
Patent document 8：JP 61-168512 publications
Patent document 9：Unexamined Patent 6-275263 publications
Patent document 10：JP 2000-340232 publications
Patent document 11：JP 2005-235397 publications
Patent document 12：Unexamined Patent 11-031509 publications
Patent document 13：Unexamined Patent 3-055770 publications
Patent document 14：JP 2004-071458 publications
Patent document 15：JP 2004-087459 publications
Patent document 16：Unexamined Patent 10-270074 publications
Patent document 17：JP 2002-075440 publications
Patent document 18：Unexamined Patent 10-270075 publications
Patent document 19：Unexamined Patent 8-045545 publications
Patent document 20：JP 2001-006729 publications
Patent document 21：Unexamined Patent 10-050342 publications
Patent document 22：Unexamined Patent 9-106835 publications
Patent document 23：JP 2000-058116 publications
Patent document 24：JP 2001-015158 publications
Patent document 25：JP 2005-306619 publications
Non-patent literature 1：J.Electrochem.soc.,145,L1(1998)
The content of the invention
The invention problem to be solved
The present invention in view of such background technology and be made, its problem is to provide a kind of when being made larger It is also high power capacity, long-life and the lithium secondary battery with height output.
The method for solving problem
The present inventor etc. has made intensive studies to above-mentioned problem, as a result finds, by using with specific composition and The positive pole and negative pole of physical property and the nonaqueous electrolytic solution containing the compound selected from specific group, can obtain high power capacity, length Life-span and the lithium secondary battery of height output, so as to complete the present invention.
That is, the present invention provides a kind of lithium secondary battery, and the lithium secondary battery is comprised at least：Clipped between positive pole and negative pole micro- Perforated membrane dividing plate and the electrode group that constitutes and contain nonaqueous electrolytic solution formed by lithium salts in nonaqueous solvents, and by it Be mounted in battery case in, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, and the active material layer, which contains, to be inhaled Stay and release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions Content is more than 10ppm, and the material includes：
The cyclic siloxane compound of following formulas (1) expressions,
[chemical formula 1]
[in formula (1), R1And R2It can be the same or different, represent the organic group of carbon number 1~12, n represents 3 ~10 integer.]
The fluorosilane compounds of following formulas (2) expressions,
[chemical formula 2]
SiFxR3 pR4 qR5 r (2)
[in formula (2), R3~R5It can be the same or different, represent the organic group of carbon number 1~12, x represents 1 ~3 integer, p, q and r represent 0~3 integer, and 1≤p+q+r≤3 respectively.]
The compound of following formulas (3) expressions,
[chemical formula 3]
[in formula (3), R6~R8It can be the same or different, represent the organic group of carbon number 1~12, A is represented The group being made up of H, C, N, O, F, S, Si and/or P.], and
Intramolecular has the compounds of S-F keys, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate And propionate；
Also, the positive pole is any one positive pole being selected from following positive poles [1]~positive pole [5]：
Positive pole [1]：Positive pole comprising positive active material, the positive active material contains manganese；
Positive pole [2]：Positive pole comprising positive active material, the positive active material has what following composition formulas (4) were represented Composition,
LixNi(1-y-z)CoyMzO2Composition formula (4)
[in composition formula (4), M is represented selected from least one of Mn, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb element, X represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.5, and z represents the number of satisfaction 0.01≤z≤0.5.]；
Positive pole [3]：Comprising the positive pole selected from any of following (a)~(d) positive active materials,
(a) BET specific surface area is 0.4m2/ g~2m2/ g positive active material
(b) average primary particle diameter is 0.1 μm~2 μm of positive active material
(c) median particle diameter d50For 1 μm~20 μm of positive active material
(d) tap density is 1.3g/cm3~2.7g/cm3Positive active material；
Positive pole [4]：The positive pole for any one condition being selected from following (e)~(f) is met,
(e) form the positive electrode active material layer containing positive active material, conductive material and adhesive on the current collector and The positive pole of making, wherein, the content of the conductive material in positive electrode active material layer for the mass % of 6 mass %~20 scope
(f) positive electrode active material layer containing positive active material and adhesive is formed on the current collector and is made just Pole, wherein, the density of positive electrode active material layer is 1.7g/cm3~3.5g/cm3Scope
(g) positive electrode active material layer containing positive active material and adhesive is formed on the current collector and is made just Pole, wherein, the ratio between thickness of positive electrode active material layer and collector (side active material layer before injection nonaqueous electrolytic solution Thickness)/the value of (thickness of collector) is 1.6~20；
Positive pole [5]：Contain the positive pole for constituting two or more different positive active materials.
In addition, the present invention provides a kind of lithium secondary battery, the lithium secondary battery is comprised at least：Clipped between positive pole and negative pole Micro-porous film dividing plate and the electrode group that constitutes and contain nonaqueous electrolytic solution formed by lithium salts in nonaqueous solvents, and will They are mounted in battery case, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, and the active material layer, which contains, to be inhaled Stay and release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions In content be more than 10ppm, the material includes：Cyclic siloxane compound, the above-mentioned formula of above-mentioned formula (1) expression (2) compound, the intramolecular that the fluorosilane compounds that represent, above-mentioned formula (3) are represented have the compounds of S-F keys, nitrate, Nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate；
Also, the negative pole is any one negative pole being selected from following negative poles [1]~negative pole [10]：
Negative pole [1]：Contain the different carbonaceous material of two or more crystallinity as the negative pole of negative electrode active material；
Negative pole [2]：Contain amorphous carbonaceous as the negative pole of negative electrode active material, the amorphous carbonaceous passes through wide-angle X The interplanar distance (d002) in (002) face that ray diffraction method is determined is more than 0.337nm, and crystallite size (Lc) is below 80nm, is adopted With argon laser Raman spectroscopy measure with 1360cm-1Peak intensity relative to 1580cm-1The ratio between peak intensity definition Raman R value is more than 0.2；
Negative pole [3]：Contain metal oxide as the negative pole of negative electrode active material, the metal oxide, which contains, to be inhaled Stay and release the titanium of lithium；
Negative pole [4]：Contain carbonaceous material as the negative pole of negative electrode active material, the circularity of the carbonaceous material is 0.85 More than, surface functional group amount O/C values are 0~0.01；
Negative pole [5]：Contain different orientation carbon complex as the negative pole of negative electrode active material, the different orientation carbon is combined Thing contains the different carbonaceous material of two or more orientation；
Negative pole [6]：Contain graphite carbon particle as the negative pole of negative electrode active material, the circle of the graphite carbon particle Spend for more than 0.85, the interplanar distance (d002) in (002) face determined by wide-angle x-ray diffraction is less than 0.337nm, using argon Ion laser Raman spectroscopy determine with 1360cm-1Peak intensity relative to 1580cm-1The definition of the ratio between peak intensity Raman R values are 0.12~0.8；
Negative pole [7]：Containing negative pole of following negative electrode active materials (C) comprising multielement as negative electrode active material, The negative electrode active material (C) comprising multielement contain selected from Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, At least one of Pt, Pd and Sb lithium occlusion metal (A) and/or lithium occlusion alloy (B), and contain C and/or N as member Plain Z；
Negative pole [8]：Contain the different negative electrode active material of more than two kinds of property as the negative pole of negative electrode active material；
Negative pole [9]：It is 0.1g/cm containing tap density3More than, and using mercury, Hg porosimeter measure equivalent to straight The micropore volume of the particle of the μ m of footpath 0.01 μm~1 is the negative pole of more than 0.01mL/g negative electrode active material；
Negative pole [10]：Be charged to the negative pole nominal capacity 60% when, by negative pole opposed battery produce reaction electricity Hinder for 500 below Ω negative pole.
In addition, the present invention provides a kind of lithium secondary battery, the lithium secondary battery is comprised at least：Positive pole and negative pole are clipped micro- Perforated membrane dividing plate and the electrode group that constitutes and contain nonaqueous electrolytic solution formed by lithium salts in nonaqueous solvents, and by it Be mounted in battery case in, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, and the active material layer, which contains, to be inhaled Stay and release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions In content be more than 10ppm, the material includes：Cyclic siloxane compound, the above-mentioned formula of above-mentioned formula (1) expression (2) compound, the intramolecular that the fluorosilane compounds that represent, above-mentioned formula (3) are represented have the compounds of S-F keys, nitrate, Nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate；
Also, the nonaqueous electrolytic solution is the electricity for meeting the either condition being selected from following electrolyte [1]~electrolyte [9] Solve liquid：
Electrolyte [1]：The nonaqueous solvents for constituting electrolyte is at least mixed solvent containing ethylene carbonate, and carbonic acid Ethyl is the capacity % of 1 capacity %~25 relative to the ratio of nonaqueous solvents total amount；
Electrolyte [2]：The nonaqueous solvents for constituting electrolyte contains at least one asymmetric linear carbonate, and this is not right Linear carbonate content ratio shared in whole nonaqueous solvents is called the volume % of 5 volume %~90；
Electrolyte [3]：The nonaqueous solvents for constituting electrolyte contains at least one chain carboxylate；
Electrolyte [4]：The nonaqueous solvents for constituting electrolyte contains the solvent that flash-point is more than 70 DEG C, and its content is all non- More than the 60 capacity % of aqueous solvent；
Electrolyte [5]：Contain LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) boric acid Lithium is used as the lithium salts for constituting electrolyte；
Electrolyte [6]：The lithium salts for constituting electrolyte is fluorine-containing lithium salts, and contains 10ppm in whole nonaqueous electrolytic solutions ~300ppm hydrogen fluoride (HF)；
Electrolyte [7]：Contain vinylene carbonate in the electrolytic solution, the content of the vinylene carbonate is the total matter of electrolyte The mass % of 0.001 mass %~3 of amount scope；
Electrolyte [8]：Also contain in the electrolytic solution represented selected from following formulas (4) compound, containing nitrogen and/or sulphur At least one of heterocyclic compound, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound, it is in whole nonaqueous electrolytic solutions Content is the mass % of 0.001 mass %~5 scope,
[chemical formula 4]
[in formula (4), R9~R12Can be the same or different, represent by H, C, N, O, F, S and P at least The group that a kind of element is constituted.]；
Electrolyte [9]：In the electrolytic solution, overcharge preventing agent is also contained.
In above-mentioned secondary cell, particularly preferably there is the secondary cell for being selected from any property in following (1)~(3),
(1) the area ratio of surface area of the electrode area summation relative to the shell of secondary cell of positive pole is more than 20 times；
(2) DC resistance component of secondary cell be 20 milliohms (m Ω) below；
(3) electric capacity that the battery element in a battery case of secondary cell has is 3 ampere-hours (Ah) More than.
In addition, the present invention provides a kind of lithium secondary battery, the lithium secondary battery is comprised at least：Positive pole and negative pole are clipped micro- Perforated membrane dividing plate and the electrode group that constitutes and contain nonaqueous electrolytic solution formed by lithium salts in nonaqueous solvents, and by it Be mounted in battery case in, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, and the active material layer, which contains, to be inhaled Stay and release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions In content be more than 10ppm, the material includes：Cyclic siloxane compound, the above-mentioned formula of above-mentioned formula (1) expression (2) compound, the intramolecular that the fluorosilane compounds that represent, above-mentioned formula (3) are represented have the compounds of S-F keys, nitrate, Nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate；
Also, the secondary cell has selected from any of following structures [1]~structure [6] property：
Structure [1]：The area of the surface area of shell of the electrode area summation relative to the secondary cell of the positive pole Than for more than 20 times；
Structure [2]：The DC resistance component of the secondary cell be 20 milliohms (m Ω) below；
Structure [3]：The electric capacity that battery element in a battery case of the secondary cell has is 3 amperes It is more than hour (Ah)；
Structure [4]：The positive pole of the secondary cell and the collector of negative pole are made up of metal material respectively, and the collection The metal material of electric body and for by electric current be fetched into outside electric conductor pass through in slot welding, high-frequency welding or ultrasonic bonding Any method is welded；
Structure [5]：The shell of the secondary cell is aluminum or aluminum alloy；
Structure [6]：The sheathing material of the above-mentioned battery case of formation of the secondary cell is following sheathing material：Battery At least a portion of inner face side include using sheet material formed by thermoplastic resin, while the battery pack is accommodated, also The battery pack can be sealed by making the thermoplastic resin layer heat-sealed with one another.
In addition, the present invention also provides a kind of non-aqueous electrolyte for secondary battery, the nonaqueous electrolytic solution comprises at least non-aqueous Agent and lithium salts, wherein,
The nonaqueous electrolytic solution contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions In content be more than 10ppm, the material includes：Cyclic siloxane compound, the above-mentioned formula of above-mentioned formula (1) expression (2) compound, the intramolecular that the fluorosilane compounds that represent, above-mentioned formula (3) are represented have the compounds of S-F keys, nitrate, Nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate；
Also, the nonaqueous electrolytic solution meets the either condition being selected from following electrolyte [1]~electrolyte [9]：
Electrolyte [1]：The nonaqueous solvents for constituting electrolyte is at least mixed solvent containing ethylene carbonate, and carbonic acid Ethyl is the capacity % of 1 capacity %~25 relative to the ratio of nonaqueous solvents total amount；
Electrolyte [2]：The nonaqueous solvents for constituting electrolyte contains at least one asymmetric linear carbonate, and this is not right Linear carbonate content ratio shared in whole nonaqueous solvents is called the volume % of 5 volume %~90；
Electrolyte [3]：The nonaqueous solvents for constituting electrolyte contains at least one chain carboxylate；
Electrolyte [4]：The nonaqueous solvents for constituting electrolyte contains the solvent that flash-point is more than 70 DEG C, and its content is complete More than the 60 capacity % of portion's nonaqueous solvents；
Electrolyte [5]：Contain LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) boric acid Lithium is used as the lithium salts for constituting electrolyte；
Electrolyte [6]：The lithium salts for constituting electrolyte is fluorine-containing lithium salts, and contains 10ppm in whole nonaqueous electrolytic solutions ~300ppm hydrogen fluoride (HF)；
Electrolyte [7]：Contain vinylene carbonate in the electrolytic solution, and the content of the vinylene carbonate is electrolyte The mass % of 0.001 mass % of gross mass~3 scope；
Electrolyte [8]：Also contain in the electrolytic solution represented selected from above-mentioned formula (4) compound, containing nitrogen and/or sulphur At least one of heterocyclic compound, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound, and it is in whole nonaqueous electrolytic solutions In content for the mass % of 0.001 mass %~5 scope；
Electrolyte [9]：In the electrolytic solution, overcharge preventing agent is also contained.
The effect of invention
According to the present invention it is possible to provide particularly cryogenic discharging characteristic excellent lithium secondary battery, pass through what is described below The various modes of invention, can play effect for example as described below.
Positive pole [1]：
According to the present invention it is possible to obtain long-life, height output with less expensive material, therefore it can provide and be particularly suitable for use in The lithium secondary battery of large-sized battery such as mobile applications.
Positive pole [2]：
According to the present invention it is possible to provide high power capacity and with long-life, the lithium secondary battery of height output, spy can also be provided The lithium secondary battery of large-sized battery that Shi Yongyu be such as mobile applications.
Positive pole [3]：
According to the present invention it is possible to obtain long-life, the lithium secondary battery of height output, therefore it can provide and be particularly suitable for use in example The lithium secondary battery of the large-sized battery of such as mobile applications.
Positive pole [4]：
According to the present invention it is possible to obtain the lithium secondary battery of height output, therefore it can provide and be particularly suitable for use in such as automobile The lithium secondary battery of the large-sized battery of purposes etc..
Positive pole [5]：
According to the present invention it is possible to obtain high power capacity, long-life, height output, and inhibit because filling for battery is repeated The lithium secondary battery of the reduction (repeated charge characteristic (cycle characteristics) is excellent) of battery capacity caused by electric discharge and output, because This can provide the lithium secondary battery for being particularly suitable for use in the large-sized battery such as mobile applications.
Negative pole [1]：
According to the present invention it is possible to provide the lithium secondary battery for being particularly suitable as large-sized battery, the lithium secondary battery can be with The effect for keeping cycle characteristics to improve, while high output characteristics can all be kept at circulation initial stage to latter stage, even in progress After deterioration after charge and discharge cycles, can also keep it is high-power under output characteristics.
Negative pole [2]：
According to the present invention it is possible to provide short time high current density charge-discharge characteristic good lithium secondary battery.
Negative pole [3]：
According to the present invention it is possible to which it is small to provide output resistance, it is possible to effectively utilize the lithium secondary battery of energy.
Negative pole [4]：
According to the present invention it is possible to provide the lithium secondary battery that the High temperature storage patience under low depth of charge is improved.
Negative pole [5]：
According to the present invention it is possible to which formedness can also be kept when providing the discharge and recharge of long-time repeatedly under low depth of charge The lithium secondary battery of energy.
Negative pole [6]：
According to the present invention it is possible to recover the fast lithium secondary battery of output from low output state when providing low temperature.
Negative pole [7]：
According to the present invention it is possible to which it is also big to provide the capacity when being made larger, and the good lithium of the acceptance that charges is secondary Battery.
Negative pole [8]：
According to the present invention it is possible to provide cycle characteristics and low temperature output good lithium secondary battery.
Negative pole [9] [10]：
According to the present invention it is possible to provide, to circulate conservation rate when battery is made into larger also big, and can realize good Battery life, the lithium secondary battery that height output, or both has both can also be realized after charge and discharge cycles experiment.
Electrolyte [1]：
According to the present invention it is possible to greatly improve the low-temperature characteristics of rechargeable nonaqueous electrolytic battery, in more detail, it can not make Cycle characteristics and preservation characteristics deteriorate and improve low-temperature characteristics.
Electrolyte [2]：
According to the present invention it is possible to provide cycle characteristics and low-temperature characteristics while the secondary cell non-aqueous solution electrolysis greatly improved The secondary cell of the above-mentioned excellent performance of liquid and the use nonaqueous electrolytic solution.
Electrolyte [3]：
According to the present invention it is possible to provide non-aqueous electrolyte for secondary battery that low temperature output characteristics are largely increased and Secondary cell.
Electrolyte [4]：
According to the present invention it is possible to provide following non-aqueous electrolyte for secondary battery and secondary cell：Although this is secondary Nonaqueous electrolyte for battery be due to the evaporation of solvent and make to salt out or flash-point reduction, at high temperature internal pressure easily rise Deng few electrolyte composition the problem of generation when containing a large amount of low viscosity solvents, but still high low-temperature characteristics can be kept and defeated Go out characteristic.
Electrolyte [5]：
Greatly improved according to the present invention it is possible to provide output characteristics, and High temperature storage characteristic and cycle characteristics are excellent Non-aqueous electrolyte for secondary battery and secondary cell.
Electrolyte [6]：
According to the present invention it is possible to provide High temperature storage characteristic and cycle characteristics is excellent, and output characteristics is greatly improved Non-aqueous electrolyte for secondary battery.
Electrolyte [7]：
According to the present invention it is possible to provide cycle characteristics and low-temperature characteristics while the secondary cell greatly improved.
Electrolyte [8]：
Greatly improved according to the present invention it is possible to provide cryogenic discharging characteristic, and High temperature storage characteristic and cycle characteristics are excellent Different non-aqueous electrolyte for secondary battery and secondary cell.
Electrolyte [9]：
According to the present invention it is possible to provide while the secondary cell of security when meeting high speed characteristic and overcharge.
Structure [1]~[5]：
According to the present invention it is possible to obtain high power capacity, long-life, height output, and the security also high lithium in overcharge Secondary cell, it is, therefore, possible to provide the lithium secondary battery for the large-sized battery being particularly suitable for use in such as mobile applications.
Structure [6]：
According to the present invention it is possible to obtain high power capacity, long-life, height output, and it is few to produce gas, when overcharge Security also high lithium secondary battery, it is, therefore, possible to provide the lithium two for the large-sized battery being particularly suitable for use in such as mobile applications Primary cell.
Embodiment
The following detailed description of embodiments of the present invention, but the explanation for the constitutive requirements recorded below is the reality of the present invention An example (typical example) of mode is applied, without departing from its main points, then the present invention is not limited to these specific contents.
The lithium secondary battery of the present invention is comprised at least：The electrode that positive pole and negative pole are clipped into micro-porous film dividing plate and constituted Group and in nonaqueous solvents contain nonaqueous electrolytic solution formed by lithium salts, and by they be mounted in battery case in, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, and the active material layer, which contains, to be inhaled Stay and release the active material of lithium ion；
The nonaqueous electrolytic solution contains (to be below referred to as them " specific selected from least one of following substances compound Compound "), and its content in whole nonaqueous electrolytic solutions is more than 10ppm, and the material includes：Above-mentioned formula (1) table Compound that fluorosilane compounds that the cyclic siloxane compound that shows, above-mentioned formula (2) are represented, above-mentioned formula (3) are represented, point There is compound, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and the propionate of S-F keys in sub；
Also, the positive pole, negative pole, electrolyte or battery structure meet specific condition.
Below, the lithium secondary battery of the present invention is illustrated in more detail.
＜ positive poles ＞
The positive pole used in the lithium secondary battery of the present invention is illustrated below.
As long as the positive pole formation used in the present invention contains being capable of occlusion and the activity for the active material for releasing lithium ion The positive pole of material layer, is not particularly limited, and the positive pole is preferably selected from any one in following positive poles [1]~positive pole [5] Positive pole：
Positive pole [1]：Positive pole comprising positive active material, the positive active material contains manganese；
Positive pole [2]：Positive pole comprising positive active material, the positive active material has what following composition formulas (4) were represented Composition,
LixNi(1-y-z)CoyMzO2Composition formula (4)
[in composition formula (4), M is represented selected from least one of Mn, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb element, X represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents to meet the number of 0.05 ＜ y≤0.5, and z represents the number of satisfaction 0.01≤z≤0.5.]；
Positive pole [3]：Comprising the positive pole selected from any of following (a)~(d) positive active materials,
(a) BET specific surface area is 0.4m2/ g~2m2/ g positive active material
(b) average primary particle diameter is 0.1 μm~2 μm of positive active material
(c) median particle diameter d50For 1 μm~20 μm of positive active material
(d) tap density is 1.3g/cm3~2.7g/cm3Positive active material；
Positive pole [4]：The positive pole for any one condition being selected from following (e)~(f) is met,
(e) positive pole is to form the positive-active containing positive active material, conductive material and adhesive on the current collector Material layer and the positive pole made, wherein, the content of the conductive material in positive electrode active material layer is the mass %'s of 6 mass %~20 Scope
(f) positive pole is to form the positive electrode active material layer containing positive active material and adhesive on the current collector and make The positive pole of work, wherein, the density of positive electrode active material layer is 1.7g/cm3~3.5g/cm3Scope
(g) positive pole is to form the positive electrode active material layer containing positive active material and adhesive on the current collector and make The positive pole of work, wherein, the ratio between thickness of positive electrode active material layer and collector (side active matter before injection nonaqueous electrolytic solution The thickness of matter layer)/the value of (thickness of collector) be 1.6~20 scope；
Positive pole [5]：Contain the positive pole for constituting two or more different positive active materials.
Below, positive pole usually used in the lithium secondary battery of the present invention is illustrated first.
[positive active material]
Positive active material usually used in positive pole is illustrated below.
[[composition]]
As positive active material, as long as can electrochemically occlusion and release lithium ion material, do not have There is special limitation.The material of lithium and at least one transition metal is preferably comprised, for example, can enumerate lithium-transition metal combined oxidation Thing, the transition metal phosphate compound containing lithium.
As the transition metal of lithium-compound transition metal oxide, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc., as Specific example, can enumerate LiCoO2Deng lithium-cobalt composite oxide；LiNiO2Deng lithium-ni compound oxide；LiMnO2、LiMn2O4、 Li2MnO3Deng lithium-manganese composite oxide；With other gold such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si Belong to material obtained from the part to substitute the transition metal atoms to form these lithiums-compound transition metal oxide main body Deng.As the specific example of material obtained from replacement, for example, it can enumerate LiNi0.5Mn0.5O2、LiNi0.85Co0.10Al0.05O2、 LiNi0.33Co0.33Mn0.33O2、LiMn1.8Al0.2O4、LiMn1.5Ni0.5O4Deng.
It is used as the transition metal of the transition metal phosphate compound containing lithium, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu Deng as specific example, such as LiFePO can be enumerated4、Li3Fe2(PO4)3、LiFeP2O7Deng ferric phosphate class；LiCoPO4Deng phosphoric acid Cobalt class；With other metals such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si these are formed to substitute Material etc. obtained from a part for the transition metal atoms of transition metal phosphate compound main body containing lithium.
[[Surface coating]]
Additionally, it is preferred that the surface attachment in these positive active materials is made up of different things the positive active material from core Matter.As the material (hreinafter referred to as " surface attachment material ") for being attached to surface, for example, it can enumerate aluminum oxide, silica, oxygen Change the oxides such as titanium, zirconium oxide, magnesia, calcium oxide, boron oxide, antimony oxide, bismuth oxide；Lithium sulfate, sodium sulphate, potassium sulfate, The sulfate such as magnesium sulfate, calcium sulfate, aluminum sulfate；Carbonate such as lithium carbonate, calcium carbonate, magnesium carbonate etc..
These surface attachment materials can be attached to positive active material surface by following methods, and methods described includes： For example, making surface attachment material be dissolved or suspended in solvent, then it is impregnated with what is added in positive active material and be dried Method；Surface attachment material precursor is dissolved or suspended in solvent, then be impregnated with addition in positive active material, then pass through The method that heating etc. is allowed to reaction；Surface attachment material is added in positive active material precursor, while the side being sintered Method etc..
As the amount of surface attachment material, relative to positive active material in mass, its lower limit be preferably 0.1ppm with On, more preferably more than 1ppm, more preferably more than 10ppm；Its upper limit is preferably less than 20%, more preferably 10% with Under, more preferably less than 5%.Oxygen of the nonaqueous electrolytic solution on positive active material surface can be suppressed by surface attachment material Change reaction, so as to improve battery life, but its adhesion amount it is very few when, it is impossible to fully show its effect, and when excessive, by In hinder lithium ion discrepancy, therefore impedance sometimes increase.
[[shape]]
The bulk used in the past can be used in the shape of particle of positive active material in the present invention, polyhedral, spherical, ellipse Spherical shape, tabular, needle-like, column etc., wherein, preferably primary particle condenses and forms offspring, and the shape of the offspring Shape is spherical or oval spherical.Generally, electrochemical element is with its discharge and recharge, and the active mass expansion in electrode shrinks, therefore Easily occur due to the deterioration such as the destruction of active material caused by the stress or conductive path cut-out.Therefore, with being once grain The single particle active material of son is compared, and preferably primary particle condenses and formed the situation of offspring, because forming secondary grain Son can relax the stress of dilation, so as to prevent deterioration.In addition, compared with the particle of the isometric orientation of tabular, preferred ball Shape or oval spherical particle, because orientation of the spherical or oval spherical particle in electrode moulding is few, electricity during discharge and recharge The dilation of pole is also few, and when making electrode and conductive agent mixing when, also easily uniform mixing.
[[tap density]]
The tap density of positive active material is usually 1.3g/cm3More than, preferably 1.5g/cm3More than, more preferably 1.6g/cm3More than, most preferably 1.7g/cm3More than.If the tap density of positive active material is less than above-mentioned lower limit, Formed positive electrode active material layer when, it is necessary to decentralized medium amount increase, while conductive material or adhesive necessary amount increase, just Filling rate of the pole active material in positive electrode active material layer is restricted, and battery capacity is restricted sometimes.By using shaking The high composite oxide power of real density, can form highdensity positive electrode active material layer.In general, tap density is bigger It is more preferred, without the special upper limit, but if tap density is too big, then in positive electrode active material layer using nonaqueous electrolytic solution as be situated between The diffusion of the lithium ion of matter turns into the factor for determining speed, and part throttle characteristics is sometimes prone to reduction, and therefore, tap density is usually 2.9g/cm3Hereinafter, preferably 2.7g/cm3Hereinafter, more preferably 2.5g/cm3Below.
In the present invention, tap density is defined as below：Sample is set to fall on 20cm by the sieve in 300 μm of aperture3Jolt ramming In container (tapping cell), after vessel volume, using powder density determination device (for example, Seishin (セ イ シ Application) society of enterprise manufacture Tap densor (タ ッ プ デ ン サ ー)), carry out 1000 length of stroke 10mm vibration, will thus When volume and sample the density obtained of weight as tap density.
[[median particle diameter d50]]
The median particle diameter d of the particle of positive active material50(it is secondary grain when primary particle condenses and forms offspring Sub- diameter) it is usually more than 0.1 μm, preferably more than 0.5 μm, more preferably more than 1 μm, most preferably more than 3 μm, its upper limit Usually less than 20 μm, preferably less than 18 μm, most preferably more preferably less than 16 μm, less than 15 μm.If median particle diameter d50Less than above-mentioned lower limit, then the product of high-tap density can not be obtained sometimes, and if it exceeds the upper limit, then due to the lithium in particle Diffusion need the time, therefore produce battery performance reduction sometimes, or the positive pole of battery is made, namely by active matter Matter and conductive agent or adhesive etc. are slurried when being coated into film-form in a solvent, the problems such as producing striped.Here, by mixed Closing two or more has different median particle diameter d50Positive active material, can further improve make positive pole when fillibility.
In addition, the median particle diameter d in the present invention50Known laser diffraction/scattering formula particle size distribution dress can be utilized Put to determine.The LA-920 manufactured using HORIBA companies is as size distribution timing, as the decentralized medium used when determining, Using 0.1 mass % sodium hexametaphosphate solutions, after 5 minutes ultrasonic waves of progress are scattered, setting determines refractive index 1.24 and surveyed It is fixed.
[[average primary particle diameter]]
When primary particle condenses and forms offspring, as the average primary particle diameter of positive active material, it is usually More than 0.01 μm, preferably more than 0.05 μm, more preferably more than 0.08 μm, most preferably more than 0.1 μm, and usually 3 μm Hereinafter, preferably less than 2 μm, most preferably more preferably less than 1 μm, less than 0.6 μm.If average primary particle diameter exceedes above-mentioned The upper limit, then be difficult to the glomerate offspring of shape, bring harmful effect, or specific surface area to be greatly reduced powder fillibility, Therefore, the possibility of the battery performance such as output characteristics reduction is uprised sometimes.If on the contrary, average primary particle diameter is less than under above-mentioned Limit, then be typically due to that crystallization is incomplete, thus produce sometimes discharge and recharge it is poorly reversible the problems such as.
In addition, primary particle size can be determined by using the observation of SEM (SEM).Specifically, by such as Lower method is obtained：In the photo of 10000 times of multiplying power, arbitrary 50 primary particles are obtained on the straight line of horizontal direction by The greatest length for the section that the left bounding lines of primary particle are produced, and take its average value.
[[BET specific surface area]]
The BET specific surface area usually 0.2m of the positive active material for being supplied to lithium secondary battery of the present invention2/ more than g, Preferably 0.3m2/ more than g, more preferably 0.4m2/ more than g, its upper limit is usually 4.0m2/ below g, preferably 2.5m2/ g with Under, more preferably 1.5m2/ below g.If BET specific surface area is smaller than the scope, battery performance is easily reduced, and if BET Specific surface area is bigger than the scope, then tap density is difficult to improve, and is sometimes prone on the coating when forming positive active material Generation problem.
The value that BET specific surface area is defined as：Using surface area meter (for example, the full-automatic surface that big storehouse reason development is made Product determines device), at 150 DEG C sample is carried out under nitrogen circulation 30 minutes it is predrying, then to be adjusted to nitrogen relative using correct The nitrogen helium mixture for being 0.3 in the relative pressure of atmospheric pressure, 1 point of the N2 adsorption BET carried out by using gas flow method Method and the value determined.
[[autofrettage]]
As the autofrettage of positive active material, the usual way of the autofrettage as inorganic compound is used.Especially It is when making spherical or oval spherical active material, it is contemplated that various methods, for example, can be listed below method：By transition gold The transition metal such as genus nitrobacter, transition metal sulfate raw material and the raw material of the other elements used as needed are molten Solution or grinding dispersion adjust pH, make and obtain spherical precursor, be dried as needed while stirring in water equal solvent Afterwards, LiOH, Li are added2CO3、LiNO3Deng Li sources, the method for sintering at high temperature and obtaining active material；By transition metal nitric acid The transition metal such as salt, transition metal sulfate, transition metal hydroxide, transition metal oxide raw material and as needed The raw material dissolving of the other elements used or grinding dispersion are dried in water equal solvent, then by spray dryer etc. Shaping, is made spherical or oval spherical precursor, and LiOH, Li are then added wherein2CO3、LiNO3Deng Li sources, burn at high temperature The method tied and obtain active material；And by transition metal nitrate, transition metal sulfate, transition metal hydroxide, The transition metal such as transition metal oxide raw material and LiOH, Li2CO3、LiNO3Deng Li sources and use as needed its The raw material dissolving of his element or grinding dispersion are dried shaping in water equal solvent, then by spray dryer etc., make Glomeration or oval spherical precursor, are then sintered and are obtained method of active material etc. at high temperature.
[structure of positive pole]
Below, the structure of the positive pole to being used in the present invention is described.
[[electrode structure and facture]]
The positive pole used in the lithium secondary battery of the present invention is to be formed to contain positive active material and bonding on the current collector The positive electrode active material layer of agent and make.Manufacture using the positive pole of positive active material can enter according to usual way OK.That is, by the dry type mixing such as positive active material and adhesive and the conductive material and thickener that use as needed, system Slabbing, then obtained tablet pressure viscosity is dissolved or dispersed in liquid medium on positive electrode collector, or by these materials In, slurry is made, then the slurry is coated on positive electrode collector and is dried, it is possible thereby to form positive pole on the current collector Active material layer, so as to obtain positive pole.
In the present invention, the content of the positive active material in positive electrode active material layer is usually more than 10 mass %, excellent Elect as more than 30 mass %, particularly preferably more than 50 mass %.In addition, its upper limit is usually below 99.9 mass %, preferably For below 99 mass %.If the content of the positive electrode active material powder in positive electrode active material layer is very low, electric capacity has time-varying Obtain insufficient.If opposite too high levels, the intensity of positive pole is sometimes not enough.In addition, positive active material can be used alone One kind, can also be applied in combination with ratio and constitute different or different powder property positive poles of more than two kinds work in any combination Property material.
[[compacting]]
In order to improve the packed density of positive active material, positive electrode active material layer obtained from by being coated with, drying is excellent Choosing is compacted using hand press, roll squeezer etc..The lower limit of the density of positive electrode active material layer is preferably 1g/cm3More than, More preferably 1.5g/cm3More than, more preferably 2g/cm3More than, its upper limit is preferably 4g/cm3Hereinafter, more preferably 3.5g/cm3Hereinafter, more preferably 3g/cm3Following scope.If it exceeds the scope, then nonaqueous electrolytic solution to collector/ Permeability reduction near reactive species interface, charge-discharge characteristic particularly at higher current densities is reduced sometimes.In addition, such as Fruit is less than the scope, then the electric conductivity reduction between active material, and battery impedance increases sometimes.
[[conductive material]]
, can be arbitrarily using known conductive material as conductive material.As specific example, copper, nickel etc. can be enumerated Metal material；The graphite such as native graphite, Delanium；The carbon blacks such as acetylene black；Carbon materials such as the amorphous carbon such as needle coke etc..These Material can be used alone one kind, two or more can also be applied in combination with ratio in any combination.
Use ratio of the conductive material in positive electrode active material layer is usually more than 0.01 weight % preferably 0.1 weight More than % is measured, more preferably more than 1 weight %, its upper limit is usually preferably below 30 weight % below 50 weight %, more excellent Elect as below 15 weight %.If content is less than the scope, electric conductivity is sometimes insufficient., whereas if content is higher than the model Enclose, then battery capacity is reduced sometimes.
[[adhesive]]
As the adhesive used when manufacturing positive electrode active material layer, it is not particularly limited, during using rubbing method, as long as It is the material being dissolved or dispersed in the liquid medium used during electrode manufacture, as specific example, poly- second can be enumerated Alkene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose The resin family macromolecule such as element；SBR (SBR styrene butadiene rubberses), NBR (acrylonitrile-butadiene rubber), fluorubber, isoamyl two The rubber-like macromolecule such as alkene rubber, butadiene rubber, ethylene-propylene rubber；SBS Or it is hydrogenated with thing, EPDM (ethylene/propylene/diene terpolymer), styrene ethylene butadiene-ethylene copolymer, benzene The thermoplastic elastomer (TPE) shape macromolecule such as ethene-isoprene-styrene block copolymer or its hydrogenation thing；Syndiotactic 1,2- gathers The soft resinous high score such as butadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers Son；The fluorine class high scores such as Kynoar (PVdF), polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer Son；Polymeric composition of ionic conductivity with alkali metal ion (particularly lithium ion) etc..In addition, these materials can be with One kind is used alone, two or more can also be applied in combination with ratio in any combination.
Ratio of the adhesive in positive electrode active material layer is usually more than 0.1 mass % preferably more than 1 mass %, More preferably more than 3 mass %, its upper limit is usually below 80 mass %, preferably below 60 mass %, more preferably 40 matter Measure below %, most preferably below 10 mass %.If the ratio of adhesive is too low, positive active material can not be fully kept, The mechanical strength of positive pole is not enough, and the battery performance such as cycle characteristics deteriorates.On the other hand, if the ratio of adhesive is too high, have When battery capacity or electric conductivity can be caused to reduce.
[[liquid medium]]
As the liquid medium for forming slurry, as long as it can dissolve or disperse positive active material, conductive agent, viscous The solvent of mixture and the thickener used as needed, its species is just not particularly limited, and can use water solvent and have Any of machine solvent.
As water-medium, such as the mixed solvent that can enumerate water, alcohol and water.As organic solvent, for example, it can enumerate The aliphatic hydrocarbons such as hexane；Benzene,toluene,xylene, methyl naphthalene etc. are aromatic hydrocarbon；The heterocyclic compounds such as quinoline, pyridine；Third The ketones such as ketone, MEK, cyclohexanone；The esters such as methyl acetate, methyl acrylate；Diethylenetriamines, N, N- dimethylaminos The amines such as propylamine；The ethers such as ether, expoxy propane, tetrahydrofuran (THF)；1-METHYLPYRROLIDONE (NMP), dimethyl formyl The amide-types such as amine, dimethyl acetamide；Aprotic polar solvents such as hexylmethylphosphoramide, dimethyl sulfoxide etc..
Particularly when using water solvent, the latex of thickener and SBR styrene butadiene rubberses (SBR) etc. is preferably used It is slurried to carry out.Thickener is typically to be used to adjust the viscosity of slurry and use.As thickener, it is not particularly limited, Specifically, carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidation shallow lake can be enumerated Powder, phosphorylated starch, casein and their salt etc..They can be used alone one kind, can also in any combination and Two or more is applied in combination in ratio.In addition, during addition thickener, thickener is usually 0.1 matter relative to the ratio of active material More than %, more preferably preferably more than 0.5 mass %, more than 0.6 mass % are measured, its upper limit is usually below 5 mass %, excellent Elect as below 3 mass %, more preferably below 2 mass % scope.If less than the scope, coating significantly drops sometimes It is low.And if it exceeds the scope, then active material ratio reduction shared in positive electrode active material layer, produce battery sometimes Impedance of capacity the problem of reduce or between positive active material the problem of increase.
[[collector]]
As the material of positive electrode collector, it is not particularly limited, can be arbitrarily using known material.It is used as concrete example Son, can enumerate the metal materials such as aluminium, stainless steel, nickel plating, titanium, tantalum；The carbon materials such as carbon cloth, carbon paper.Wherein, preferred metal materials, Particularly preferred aluminium.
As the shape of collector, in the case of metal material, metal foil, metal cylinder, wire coil, gold can be enumerated Belong to plate, metallic film, expansion alloy (エ キ ス パ Application De メ タ Le), perforated metal, foaming metal etc.；The situation of carbon material Under, carbon plate, C film, carbon cylinder etc. can be enumerated.Among these, preferred metallic film.In addition, film can also be properly formed It is netted.The thickness of film is arbitrary, but usually more than 1 μm, preferably more than 3 μm, more preferably more than 5 μm, and lead to It is often below 1mm, more preferably preferably less than 100 μm, less than 50 μm.If film is thinner than the scope, sometimes as collection The necessary intensity of electric body is not enough.If on the contrary, film is thicker than the scope, operability is damaged sometimes.
The ratio between thickness of collector and positive electrode active material layer is not particularly limited, and (one before injection nonaqueous electrolytic solution The active material layer thickness of side)/(thickness of collector) be preferably less than 150, more preferably less than 20, most preferably 10 with Under, its lower limit is preferably more than 0.1, more preferably more than 0.4, most preferably more than 1 scope.If it exceeds the scope, then In high current density discharge and recharge, collector produces heating because of Joule heat sometimes.If less than the scope, collected sometimes Electric body phase is for the volume ratio increase of positive active material, the capacity reduction of battery.
[[electrode area]]
Using the present invention nonaqueous electrolytic solution when, from height output and improve high temperature when stability from the viewpoint of, it is excellent Select the area of positive electrode active material layer bigger than the external surface area of battery case.Specifically, the electrode area summation phase of above-mentioned positive pole For secondary cell shell surface area in terms of area ratio, preferably more than 15 times, more preferably more than 40 times.So-called shell External surface area, in the case where there is bottom square configuration, refer to except terminal jut be filled with power generation element in addition to The gross area that shell parts are obtained by the Size calculation of length and width and thickness.It is by except end in the case where there is bottom cylindrical shape The casing part filled with power generation element of the jut of son is approximately geometrical surface obtained from cylinder.So-called positive pole The summation of electrode area, is the positive pole plied timber layer opposed with the plied timber layer (closing material Layer) comprising negative electrode active material Geometrical surface, is clipping current collector foil in the structure that two sides forms positive pole plied timber layer, is referring to calculate each face respectively Area summation.
[[discharge capacity]]
During using non-aqueous electrolyte for secondary battery of the invention, the battery in the battery case of 1 secondary cell The electric capacity (electric capacity when battery is discharged into discharge condition by fully charged state) that key element has is if 3 ampere-hours (Ah) More than, then the raising effect of cryogenic discharging characteristic becomes big, therefore it is preferred that.
Therefore, positive plate be preferably designed in full charge discharge capacity be 3 ampere-hours (Ah) less than 20Ah, More preferably 4Ah is less than 10Ah.During less than 3Ah, when taking out high current, the voltage as caused by electrode reaction impedance is reduced Become big, power efficiency is deteriorated sometimes.During more than 20Ah, although electrode reaction impedance diminishes, and power efficiency improves, but pulse charge and discharge Caused Temperature Distribution is generated heat greatly by inside battery when electric, the poor durability of repeated charge, in addition, in overcharge or internal short Violent adstante febre when road etc. is abnormal, its exothermal efficiency is also deteriorated, and produces phenomenon (the valve work that internal pressure rises and makes vent valve work Make), cell contents are tempestuously ejected into the probability of phenomenon (rupture) of outside and raise sometimes.
[[thickness of positive plate]]
The thickness of positive plate is not particularly limited, but from the viewpoint of high power capacity and height output, subtracts the gold of core The lower limit of thickness of the plied timber layer in the one side of collector after category paper tinsel thickness is preferably more than 10 μm, more preferably 20 μm, its upper limit is preferably less than 200 μm, more preferably less than 100 μm.
＜ positive poles [1] ＞
Below, " positive active material containing manganese is being included just to the positive pole [1] used in the lithium secondary battery of the present invention Pole " is illustrated.
[positive active material of positive pole [1]]
Below, the positive active material used in positive pole [1] is illustrated.
[[composition]]
As positive active material, be containing can electrochemically occlusion and release lithium ion transition metal thing Matter, as at least a portion of transition metal, in the present invention, uses the positive active material containing manganese.Preferably further contain There are the composite oxides of lithium, further preferably lithium and manganese.
The above-mentioned positive active material containing manganese is not particularly limited, but the group that preferably there are following composition formulas (5) to represent Into positive active material.
LixMn(1-y)M1 yO2Composition formula (5)
[in composition formula (5), M1Represent selected from least one of Ni, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (5), M1Particularly preferred Ni, Co, Fe, in addition, the particularly preferred 0.2≤x≤1.15, y of x are particularly preferred 0.1≤y≤0.7.As the specific example of the material of the composition represented with composition formula (5), for example, it can enumerate LiMn0.5Ni0.5O2。
In addition, particularly preferably M1It is Ni, and the positive active material of the composition represented with following composition formulas (6).
LixMn(1-y-z)Ni1 yM2 zO2Composition formula (6)
[in composition formula (6), M2Represent selected from least one of Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb member Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8, and z represents satisfaction 0.01≤z≤0.5 Number].
In composition formula (6), M2Particularly preferred Co, Al, Fe, Mg, the particularly preferred 0.2≤x≤1.15, y of x are particularly preferred Particularly preferred 0.2≤y+z≤0.7 of the particularly preferred 0.1≤z≤0.7, y+z of 0.1≤y≤0.7, z.As with composition formula (6) table The specific example of the material of the composition shown, for example, can enumerate LiMn0.33Ni0.33Co0.33O2Deng.
As the positive active material containing manganese, the positive electrode active material of the composition preferably represented with following composition formulas (7) Matter.
LixMn(2-y)M3 yO4Composition formula (7)
[in composition formula (7), M3Represent selected from least one of Ni, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (7), M3Particularly preferred Ni, Co, Al, Mg, in addition, the particularly preferred 0.05≤x≤1.15, y of x are special It is preferred that 0.1≤y≤0.7.As the specific example of the material of the composition represented with composition formula (7), for example, it can enumerate LiMn1.8Al0.2O4、LiMn1.5Ni0.5O4Deng.
[[Surface coating]]
Additionally, it is preferred that being had and the above-mentioned positive active material group containing manganese using the surface attachment in the positive active material Into the positive active material of different materials.Species, adherence method, the adhesion amount of surface attachment material etc. are same as described above.
[[shape]]
The shape of particle of the positive active material is same as described above.
[[tap density]]
The tap density of the positive active material is same as described above.
[[median particle diameter d50]]
The median particle diameter d of the particle of the positive active material50(it is secondary when primary particle condenses and forms offspring Particle diameter) it is same as described above.
[[average primary particle diameter]]
When primary particle condenses and forms offspring, the average primary particle diameter of positive active material is same as described above.
[[BET specific surface area]]
The BET specific surface area of positive active material is same as described above.
[[autofrettage]]
As the autofrettage of the positive active material, the usual way of the autofrettage as inorganic compound is used.It is special It is not when making spherical or oval spherical active material, it is contemplated that various methods, for example, can be listed below method：By nitric acid The manganese such as manganese, manganese sulfate raw material and the dissolving of the raw material of the other elements used as needed or grinding dispersion are molten in water etc. In agent, pH is adjusted while stirring, makes and obtains spherical precursor, after being dried as needed, adds LiOH, Li2CO3、 LiNO3Deng Li sources, the method for sintering at high temperature and obtaining active material；By manganese nitrate, manganese sulfate, manganese oxide, alkali formula hydrogen-oxygen Change the manganese raw materials such as manganese and the raw material dissolving of the other elements used as needed or grinding dispersion in water equal solvent, Shaping is dried by spray dryer etc. again, spherical or oval spherical precursor is made, then wherein add LiOH, Li2CO3、LiNO3Deng Li sources, the method for sintering at high temperature and obtaining active material；And by manganese nitrate, manganese sulfate, oxidation The manganese such as manganese, manganese oxyhydroxide raw material and LiOH, Li2CO3、LiNO3Deng Li sources and the other elements used as needed Raw material dissolving or grinding dispersion be dried shaping in water equal solvent, then by spray dryer etc., be made spherical Or oval spherical precursor, the method for then being sintered at high temperature and obtaining active material.
Positive active material in the present invention can be used alone the positive active material that this contains manganese, can also be with any Combination and ratio be applied in combination positive active material that this contains manganese and it is one or more with should positive electrode active material containing manganese Matter composition difference or the different positive active material of powder property.As preferred combination now, it can enumerate containing manganese just Pole active material and LiNiO2Or part thereof Ni by other transition metal substitute obtained from material combination；Or contain manganese Positive active material and LiCoO2Or part thereof Co by other transition metal substitute obtained from material combination.In addition, conduct Particularly preferred combination, can also enumerate the positive active material and LiNiO of composition formula (5)~(7) expression2Or part thereof Ni by it The combination of material obtained from his transition metal is substituted；Or the positive active material and LiCoO that composition formula (5)~(7) are represented2 Or part thereof Co by other transition metal substitute obtained from material combination.Positive active material containing manganese, particularly group The positive active material that an accepted way of doing sth (5)~(7) are represented is preferably more than the 30 mass % of whole positive active materials, more preferably 50 More than quality %.Composition formula (5)~(7) will not be reduced sometimes if the use ratio of the positive active material represented tails off The cost of positive pole.
[structure of the positive pole of positive pole [1]]
Below, the structure of the positive pole to being used in positive pole [1] is illustrated.
Electrode structure and preparation method, the compacting of positive electrode active material layer, conductive material, positive-active in positive pole [1] The jointing material used during the manufacture of material layer, the liquid medium for forming slurry, collector, electrode area, discharge capacity, The thickness of positive plate etc. is same as described above.
＜ positive poles [2] ＞
Below, it is " specific containing having for composition formula (4) expression to the positive pole [2] used in the lithium secondary battery of the present invention The positive pole of the positive active material of composition " is illustrated.
[positive active material of positive pole [2]]
Below, the positive active material used in positive pole [2] is illustrated.
[[composition]]
As positive active material, using the composition represented with following composition formulas (4), containing can be with electrochemistry side The material (below, referred to as " positive active material ") of the transition metal of formula occlusion and releasing lithium ion.
LixNi(1-y-z)CoyMzO2Composition formula (4)
[in composition formula (4), M is represented selected from least one of Mn, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb element, X represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.5, and z represents the number of satisfaction 0.01≤z≤0.5].
In composition formula (4), M is preferably Mn, Al or Mg, in addition, x preferably 0.2≤x≤1.15.In addition, y preferably 0.08 ≤ y≤0.4, particularly preferred 0.1≤y≤0.3.In addition, z preferably 0.02≤z≤0.4, particularly preferred 0.03≤z≤0.3.
[[Surface coating]]
Additionally, it is preferred that constituting different things by from the positive active material using the surface attachment in the positive active material The positive active material of matter.Species, adherence method, the adhesion amount of surface attachment material etc. are same as described above.
[[shape]]
The shape of particle of the positive active material is same as described above.
[[tap density]]
The tap density of the positive active material is same as described above.
[[median particle diameter d50]]
The median particle diameter d of the particle of the positive active material50(it is secondary when primary particle condenses and forms offspring Particle diameter) it is same as described above.
[[average primary particle diameter]]
When primary particle condenses and forms offspring, the average primary particle diameter of positive active material is same as described above.
[[BET specific surface area]]
The BET specific surface area of positive active material is same as described above.
[[autofrettage]]
As the autofrettage of the positive active material, the usual way of the autofrettage as inorganic compound can be used. Particularly when making spherical or oval spherical active material, it is contemplated that various methods, for example, it can be listed below method：By nitre The raw material thing of the cobalt raw material such as the nickel such as sour nickel, nickel sulfate raw material and cobalt nitrate, cobaltous sulfate material and the M in composition formula (4) Matter is dissolved or grinding dispersion is in water equal solvent, and pH is adjusted while stirring, makes and obtains spherical precursor, as needed by it After drying, LiOH, Li are added2CO3、LiNO3Deng Li sources, the method for sintering at high temperature and obtaining active material；By nickel nitrate, The nickel such as nickel sulfate, nickel oxide, nickel hydroxide, nickel oxyhydroxide raw material and cobalt nitrate, cobaltous sulfate, cobalt oxide, hydroxide The cobalt raw material materials such as cobalt, alkali formula cobalt hydroxide and the M in composition formula (4) raw material dissolving or grinding dispersion are molten in water etc. In agent, then shaping is dried by spray dryer etc., spherical or oval spherical precursor is made, then adds wherein LiOH、Li2CO3、LiNO3Deng Li sources, the method for sintering at high temperature and obtaining active material；And by nickel nitrate, nickel sulfate, The nickel such as nickel oxide, nickel hydroxide, nickel oxyhydroxide raw material and cobalt nitrate, cobaltous sulfate, cobalt oxide, cobalt hydroxide, alkali formula The cobalt raw material such as cobalt hydroxide material and the M in composition formula (4) raw material and LiOH, Li2CO3、LiNO3Deng the dissolving of Li sources Or grinding dispersion is dried shaping in water equal solvent, then by spray dryer etc., be made it is spherical or it is oval it is spherical before Body, the method for then being sintered at high temperature and obtaining active material.
In order to manufacture the positive pole in the present invention, the positive active material (positive pole that composition formula (4) is represented can be used alone Active material and/or by above-mentioned surface attachment material coat composition formula (4) represent positive active material), can also with appoint The positive active material material different from positive active material composition with more than one is applied in combination in the combination of meaning and ratio. As preferred combination now, the positive active material and LiMn can be enumerated2O4Or part thereof Mn substituted by other transition metal Obtained from material combination；Or the positive active material and LiCoO2Or part thereof Co substituted and obtained by other transition metal The combination of the material arrived.
Here, it is preferred that the positive active material is more than the 30 mass % of whole positive active materials, more preferably 50 matter Measure more than %.If the use ratio of the positive active material tails off, battery capacity diminishes sometimes.In addition, will " positive pole work Property material " and " positive active material beyond the positive active material " are collectively referred to as " positive active material ".
[structure of the positive pole of positive pole [2]]
Below, the structure of the positive pole to being used in positive pole [2] is described.
Electrode structure and preparation method, the compacting of positive electrode active material layer, conductive material, positive-active in positive pole [2] The jointing material used during the manufacture of material layer, the liquid medium for forming slurry, collector, electrode area, discharge capacity, The thickness of positive plate etc. is same as described above.
＜ positive poles [3] ＞
Below, " any being selected from following (a)~(d) is included to the positive pole [3] used in the lithium secondary battery of the present invention Plant the positive pole of positive active material " illustrate.
(a) BET specific surface area is 0.4m2/ g~2m2/ g positive active material
(b) average primary particle diameter is 0.1 μm~2 μm of positive active material
(c) median particle diameter d50For 1 μm~20 μm of positive active material
(d) tap density is 1.3g/cm3~2.7g/cm3Positive active material.
[positive active material of positive pole [3]]
Below, the positive active material used in positive pole [3] is described.
[[composition]]
As positive active material, as long as can electrochemically occlusion and release lithium ion material, do not have There is special limitation.The material of lithium and at least one transition metal is preferably comprised, for example, can enumerate lithium-transition metal combined oxidation Thing, the transition metal phosphate compound containing lithium.Specifically, it can be used with the material constituted as described above.
[[Surface coating]]
It is preferred that the surface attachment of the positive active material is made up of the positive pole of different materials the positive active material from core Active material.Species, adherence method, the adhesion amount of surface attachment material etc. are same as described above.
[[shape]]
The shape of particle of the positive active material is same as described above.
[[BET specific surface area]]
The BET specific surface area of the positive active material is preferably 0.4m2/ more than g, more preferably 0.5m2/ more than g, enters one Step is preferably 0.6m2/ more than g, its upper limit is preferably 2m2/ below g, more preferably 1.8m2/ below g, more preferably 1.5m2/ below g.If BET specific surface area is smaller than the scope, battery performance is easily reduced, and if BET specific surface area ratio The scope is big, then tap density is difficult to improve, and generation problem is sometimes prone on the coating when forming positive active material.
The value that BET specific surface area is defined as：Using surface area meter (for example, the full-automatic surface that big storehouse reason development is made Product determines device), at 150 DEG C sample is carried out under nitrogen circulation 30 minutes it is predrying, then to be adjusted to nitrogen relative using correct The nitrogen helium mixture for being 0.3 in the relative pressure of atmospheric pressure, 1 point of the N2 adsorption BET carried out by using gas flow method Method and the value determined.
[[average primary particle diameter]]
When primary particle condenses and forms offspring, the average primary particle diameter of the positive active material is preferably 0.1 μm More than, more preferably more than 0.2 μm, more preferably more than 0.3 μm, most preferably more than 0.4 μm, its upper limit is preferably 2 μ Below m, more preferably less than 1.6 μm, most preferably more preferably less than 1.3 μm, less than 1 μm.If average once grain Footpath exceedes the above-mentioned upper limit, then is difficult to the glomerate offspring of shape, harmful effect, or specific surface area are brought to powder fillibility It is greatly reduced, therefore, the possibility of the battery performance such as output characteristics reduction is uprised sometimes.If on the contrary, average primary particle diameter is low In above-mentioned lower limit, be then typically due to that crystallization is incomplete, thus produce sometimes discharge and recharge it is poorly reversible the problems such as.
Primary particle size can be determined by using the observation of SEM (SEM).Specifically, by the following method Obtain：In the photo of 10000 times of multiplying power, arbitrary 50 primary particles are obtained on the straight line of horizontal direction by once grain The greatest length for the section that the left bounding lines of son are produced, and take its average value.
[[median particle diameter d50]]
The median particle diameter d of the particle of the positive active material50(it is secondary when primary particle condenses and forms offspring Particle diameter) be preferably more than 1 μm, more preferably more than 1.2 μm, more preferably more than 1.5 μm, most preferably 2 μm with On, its upper limit is preferably less than 20 μm, more preferably less than 18 μm, more preferably less than 16 μm, most preferably 15 μm with Under.If median particle diameter d50Less than above-mentioned lower limit, then the product of high-tap density can not be obtained sometimes, and if it exceeds the upper limit, Then because the diffusion of the lithium in particle needs the time, therefore battery performance reduction is produced sometimes, or battery is being made just Pole, namely by active material and conductive agent or adhesive etc. in a solvent it is slurried be coated into film-form when, produce striped The problems such as.The positive active material of the present invention is to be mixed with two or more to have different median particle diameter d50Positive active material Obtained from positive active material when, can further improve make positive pole when fillibility, be preferred.
In addition, the median particle diameter d in the present invention50Known laser diffraction/scattering formula particle size distribution dress can be utilized Put to determine.The LA-920 manufactured using HORIBA companies is as size distribution timing, as the decentralized medium used when determining, Using 0.1 mass % sodium hexametaphosphate solutions, after 5 minutes ultrasonic waves of progress are scattered, setting determines refractive index 1.24 to carry out Determine.
[[tap density]]
The tap density of the positive active material is preferably 1.3g/cm3More than, more preferably 1.5g/cm3More than, further Preferably 1.6g/cm3More than, most preferably 1.7g/cm3More than.If the tap density of positive active material is less than under above-mentioned Limit, then formed positive electrode active material layer when, it is necessary to decentralized medium amount increase, while the necessary amount of conductive material or adhesive Increase, filling rate of the positive active material in positive electrode active material layer is restricted, and battery capacity is restricted sometimes.Pass through Using the high composite oxide power of tap density, highdensity positive electrode active material layer can be formed.In general, vibration density Degree it is more big more preferred, without the special upper limit, but if tap density is too big, then in positive electrode active material layer using electrolyte as The diffusion of the lithium ion of medium turns into the factor for determining speed, and part throttle characteristics is sometimes prone to reduction, therefore, the upper limit of tap density Preferably 2.7g/cm3Hereinafter, more preferably 2.5g/cm3Below.
In the present invention, tap density is defined as below：Sample is set to fall on 20cm by the sieve in 300 μm of aperture3Jolt ramming In container, after vessel volume, using powder density determination device (for example, the Tap that society of seishin enterprises manufactures Densor), 1000 length of stroke 10mm vibration is carried out, volume density now is regard as tap density.
In terms of long-life, height output, the positive active material in lithium secondary battery of the invention is particularly preferably same When meet above-mentioned BET specific surface area, average primary particle diameter, median particle diameter d50With two or more physical property in tap density.
[[autofrettage]]
The autofrettage of the positive active material is same as described above.
Positive active material in the lithium secondary battery of the present invention can be used alone one kind, can also be in any combination The positive active materials different or different powder property with ratio combine two or more composition are used.In addition, from improve the life-span this point From the point of view of, positive pole of the invention preferably comprise positive active material (positive active material) with any one above-mentioned physical property and The positive pole of the positive active material different from positive active material composition.
[structure of the positive pole of positive pole [3]]
Below, the structure of the positive pole to being used in positive pole [3] is described.
Electrode structure and preparation method, the compacting of positive electrode active material layer, conductive material, positive-active in positive pole [3] The jointing material used during the manufacture of material layer, the liquid medium for forming slurry, collector, electrode area, discharge capacity, The thickness of positive plate etc. is same as described above.
＜ positive poles [4] ＞
Below, " any being selected from following (e)~(f) is met to the positive pole [4] used in the lithium secondary battery of the present invention The positive pole of condition " is illustrated.
(e) form the positive electrode active material layer containing positive active material, conductive material and adhesive on the current collector and The positive pole of making, wherein, the content of the conductive material in positive electrode active material layer for the mass % of 6 mass %~20 scope (side Formula 1)
(f) positive electrode active material layer containing positive active material and adhesive is formed on the current collector and is made just Pole, wherein, the density of positive electrode active material layer is 1.7g/cm3~3.5g/cm3Scope (mode 2)
(g) positive electrode active material layer containing positive active material and adhesive is formed on the current collector and is made just Pole, wherein, the ratio between thickness of positive electrode active material layer and collector (side active material layer before injection nonaqueous electrolytic solution Thickness)/the value of (thickness of collector) is 1.6~20 (modes 3).
[positive active material of positive pole [4]]
Below, the positive active material used in positive pole [4] is described.
As positive active material, as long as can electrochemically occlusion and release lithium ion material, do not have There is special limitation.The material of lithium and at least one transition metal is preferably comprised, for example, can enumerate lithium-transition metal combined oxidation Thing, the transition metal phosphate compound containing lithium.Specifically, it can be used with the material constituted as described above.
Surface coating, shape, tap density, the median particle diameter d of the positive active material50, average primary particle diameter, BET ratios Surface area, autofrettage etc. are same as described above.
[structure of the positive pole of positive pole [4]]
Below, the structure of the positive pole to being used in positive pole [4] is described.
[[electrode structure and facture]]
Positive pole [4] in the lithium secondary battery of the present invention is to be formed to contain positive active material and adhesive on the current collector Positive electrode active material layer and make.It can be carried out using the manufacture of the positive pole of positive active material according to usual way.That is, At least by positive active material, adhesive, the conductive material used as needed (being that must contain composition in mode 1) and root Dry type mixing is carried out according to thickener needed to use etc. and sheet is made, then by the flaky material pressure viscosity on positive electrode collector, Or these materials are dissolved or dispersed in liquid medium, slurry is made, then the slurry is coated on positive electrode collector simultaneously It is dried, it is possible thereby to positive electrode active material layer be formed on the current collector, so as to obtain positive pole.
The content of positive active material in positive electrode active material layer is preferably more than 80 mass % more preferably 82 matter Measure more than %, particularly preferably more than 84 mass %.Its upper limit is preferably below 95 mass %, more preferably 93 mass % with Under.If the content of the positive active material in positive electrode active material layer is low, electric capacity becomes insufficient sometimes.If on the contrary, The content of positive active material is too high, then the intensity of positive pole is sometimes insufficient.
[[conductive material]]
, can be arbitrarily using known conductive material as conductive material.As specific example, it can enumerate and above-mentioned phase Same conductive material.
Content of the conductive material used in the positive pole of the lithium secondary battery of the present invention in positive electrode active material layer is as follows： It is necessary in mode 1 more than 6 mass %, preferably more than 7 mass %, more preferably more than 8 mass %, more preferably More than 9 mass %；In addition, be not particularly limited in mode 2 and mode 3, but preferably more than 6 mass %, more preferably 7 matter Measure more than %, more preferably more than 8 mass %.If the content of the conductive material in positive electrode active material layer is very little Words, electric conductivity is insufficient, cannot get height output sometimes.
In addition, the upper limit of the content of conductive material in positive electrode active material layer is as follows：20 matter are necessary in mode 1 Measure below %, particularly preferably preferably below 18 mass %, below 15 mass %；In addition, not having in mode 2 and mode 3 It is particularly limited to, but preferably below 20 mass %, more preferably below 18 mass %, more preferably below 15 mass %. If its content is too many, battery capacity reduction cannot get height output sometimes.
[[adhesive]]
As the adhesive used in the manufacture of positive electrode active material layer, it is not particularly limited, during using rubbing method, only If material when being dissolved or dispersed in electrode manufacture in the liquid medium that uses, as specific example, can enumerate with Above-mentioned identical material.
Ratio of the adhesive in positive electrode active material layer is usually more than 0.1 mass % preferably more than 1 mass %, More preferably more than 3 mass %, its upper limit is usually below 80 mass %, preferably below 60 mass %, more preferably 40 matter Measure below %, more preferably below 10 mass %.If the ratio of adhesive is too low, positive pole can not be fully kept sometimes Active material, the mechanical strength of positive pole is not enough, and the battery performance such as cycle characteristics deteriorates.On the other hand, if the ratio of adhesive It is too high, then sometimes result in battery capacity or electric conductivity reduction.
[[being used for the liquid medium for forming slurry]]
As the liquid medium for forming slurry, as long as it can dissolve or disperse positive active material, conductive agent, viscous The solvent of mixture and the thickener used as needed, its species is just not particularly limited, and can use water solvent and have Any of machine solvent.As specific example, material similar to the above can be enumerated.The species and addition of Tackifier materials It is same as described above.
[[compacting]]
In order to improve the packed density of positive active material, positive electrode active material layer obtained from by being coated with, drying is excellent Choosing is compacted using hand press, roll squeezer etc..The lower limit of the density of positive electrode active material layer is necessary in mode 2 1.7g/cm3More than, preferably 2.0g/cm3More than, particularly preferably 2.2g/cm3More than；In addition, not having in mode 1 and mode 3 It is particularly limited to, but preferably 1.7g/cm3More than, more preferably 2.0g/cm3More than, more preferably 2.2g/cm3More than. If density is less than the electric conductivity reduction between the scope, active material, battery impedance increase can not obtain height output sometimes.
The upper limit of the density of positive electrode active material layer is necessary for 3.5g/cm in mode 23Hereinafter, preferably 3.0g/cm3With Under, particularly preferably 2.8g/cm3Below；In addition, be not particularly limited in mode 1 and mode 3, but preferably 3.5g/cm3With Under, more preferably 3.0g/cm3Hereinafter, more preferably 2.8g/cm3Below.If density is higher than the scope, non-aqueous solution electrolysis Liquid is reduced to the permeability reduction near collector/reactive species interface, charge-discharge characteristic particularly at higher current densities, Sometimes height output can not be obtained.
[[collector]]
As the material of positive electrode collector, it is not particularly limited, it is same as described above.In addition, the shape and film of collector Thickness it is also same as described above.
The ratio between thickness for positive electrode active material layer and the collector, (activity of the side before injection nonaqueous electrolytic solution Material layer thickness)/the value of (thickness of collector) is necessary for less than 20, preferably less than 15, particularly preferably 10 in mode 3 Below；In addition, be not particularly limited in mode 1 and mode 2, but preferably less than 20, more preferably less than 15, particularly preferably For less than 10.If it exceeds the scope, then in high current density discharge and recharge, collector can produce hair because of Joule heat sometimes Heat, positive pole sustains damage.
For under the value of (the active material layer thickness of the side before injection nonaqueous electrolytic solution)/(thickness of collector) Limit, is necessary for more than 1.6, preferably more than 1.8, particularly preferably more than 2 in mode 1；In addition, in mode 1 and mode 2 It is not particularly limited, but preferably more than 1.6, more preferably more than 1.8, more preferably more than 2.If less than the model Enclose, then the volume ratio increase due to collector relative to positive active material, the capacity of battery is reduced, and can not obtain high defeated sometimes Go out.
Above-mentioned " content of the conductive material in positive electrode active material layer ", " density of positive electrode active material layer ", " positive pole work Property material layer and collector the ratio between thickness, i.e. (the active material layer thickness of the side before injection nonaqueous electrolytic solution)/(current collection The thickness of body) value " if the respective preferred scope of combination, can form the lithium secondary battery of preferred height output.
[[electrode area]]
Using the present invention nonaqueous electrolytic solution when, from height output and improve high temperature when stability from the viewpoint of, it is excellent Select the area of positive electrode active material layer bigger than the external surface area of battery case, this with it is above-mentioned be identical.
[[discharge capacity]]
During using non-aqueous electrolyte for secondary battery of the invention, the battery in the battery case of 1 secondary cell The electric capacity (electric capacity when battery is discharged into discharge condition by fully charged state) that key element has is if 3 ampere-hours (Ah) More than, then the raising effect of output characteristics becomes big, therefore it is preferred that.
Therefore, design of positive plate etc. etc. is also same as described above.
[[thickness of positive plate]]
The thickness of positive plate is not particularly limited, same as described above.
＜ positive poles [5] ＞
Below, the positive pole [5] used in the lithium secondary battery of the present invention is illustrated.
[positive active material of positive pole [5]]
Below, the positive active material used in positive pole [5] is illustrated.
[[composition]]
As positive active material, as long as can electrochemically occlusion and release lithium ion material, do not have There is special limitation.The material of lithium and at least one transition metal is preferably comprised, for example, can enumerate lithium-transition metal combined oxidation Thing, the transition metal phosphate compound containing lithium.
As the transition metal of lithium-compound transition metal oxide, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc., as Specific example, can enumerate LiCoO2Deng lithium-cobalt composite oxide；LiNiO2Deng lithium-ni compound oxide；LiMnO2、LiMn2O4、 Li2MnO3Deng lithium-manganese composite oxide；With other gold such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si Belong to material obtained from the part to substitute the transition metal atoms to form these lithiums-compound transition metal oxide main body Deng.
Above-mentioned lithium-cobalt composite oxide is not particularly limited, but preferably has the thing of the composition of following composition formulas (8) expression Matter.
LixCo(1-y)M1 yO2Composition formula (8)
[in composition formula (8), M1Represent selected from least one of Ni, Mn, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (8), M1Particularly preferred Ni, Mn, Al, Fe, in addition, the particularly preferred 0.2≤x≤1.15, y of x are special It is preferred that 0.1≤y≤0.5.
Above-mentioned lithium-ni compound oxide is not particularly limited, but preferably has the thing of the composition of following composition formulas (9) expression Matter.
LixNi(1-y)M2 yO2Composition formula (9)
[in composition formula (9), M2Represent selected from least one of Co, Mn, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (9), M2Particularly preferred Co, Mn, Al, Fe, in addition, the particularly preferred 0.2≤x≤1.15, y of x are special It is preferred that 0.1≤y≤0.5.
Above-mentioned lithium-manganese composite oxide is not particularly limited, but preferably there is the composition of following composition formulas (10) expression Material.
LixMn(1-y)M3 yO2Composition formula (10)
[in composition formula (10), M3Represent selected from least one of Ni, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (10), M3Particularly preferred Ni, Co, Fe, in addition, the particularly preferred 0.2≤x≤1.15, y of x are especially excellent Select 0.1≤y≤0.7.
As above-mentioned lithium-manganese composite oxide, the material of the composition preferably represented with following composition formulas (11).
LixMn(2-y)M4 yO4Composition formula (11)
[in composition formula (11), M4Represent selected from least one of Ni, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (11), M4Particularly preferred Ni, Co, Al, Mg, in addition, the particularly preferred 0.05≤x≤1.15, y of x are special Not other preferred 0.1≤y≤0.7.
As above-mentioned lithium-manganese composite oxide, the material of the composition preferably represented with following composition formulas (12).
LixMn(1-y)M5 yO3Composition formula (12)
[in composition formula (12), M5Represent selected from least one of Ni, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤2.4 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (12), M5Particularly preferred Ni, Co, Al, Mg, in addition, the particularly preferred 0.1≤x≤2.3, y of x are special It is preferred that 0.1≤y≤0.5.
It is used as the transition metal of the transition metal phosphate compound containing lithium, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu Deng as specific example, such as LiFePO can be enumerated4、Li3Fe2(PO4)3、LiFeP2O7Deng ferric phosphate class；LiCoPO4Deng phosphoric acid Cobalt class；With other metals such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si these are formed to substitute Material etc. obtained from a part for the transition metal atoms of the main body of transition metal phosphate compound containing lithium.
Above-mentioned ferric phosphate class is not particularly limited, but preferably has the material of the composition of following composition formulas (13) expression.
LixFe(1-y)M6 yPO4Composition formula (13)
[in composition formula (13), M6Represent selected from least one of Ni, Co, Mn, Al, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element, x represents the number of 0 ＜ x≤1.2 of satisfaction, and y represents the number of satisfaction 0.05≤y≤0.8].
In composition formula (13), M6Particularly preferred Ni, Co, Mn, Al, in addition, the particularly preferred 0.2≤x≤1.15, y of x are special It is preferred that 0.1≤y≤0.5.
Above-mentioned positive active material is preferably applied in combination in positive active material in the present invention with ratio in any combination In different two or more material of composition.By the performance that various positive active materials are each good at is different, therefore positive pole is lived Property material preferably combines the performance of needs according to the purposes of target battery.In general, it is believed that performance phase can be made by combination Plus it is average, but for the life-span, the effect of the positive active material of long lifespan unexpectedly can be further obtained sometimes, passes through group Close life-span better positive active material and the life-span be poor but other positive active materials of good performance, it is possible to achieve The height output of the present invention, Large Copacity, long-life lithium secondary battery.
As the example of preferred combination, combination can be listed below：
The positive active material for positive active material and composition formula (10) expression that composition formula (8) is represented,
The positive active material for positive active material and composition formula (11) expression that composition formula (8) is represented,
The positive active material for positive active material and composition formula (12) expression that composition formula (8) is represented,
The positive active material for positive active material and composition formula (13) expression that composition formula (8) is represented,
The positive active material for positive active material and composition formula (10) expression that composition formula (9) is represented,
The positive active material for positive active material and composition formula (11) expression that composition formula (9) is represented,
The positive active material for positive active material and composition formula (12) expression that composition formula (9) is represented,
The positive active material for positive active material and composition formula (13) expression that composition formula (9) is represented,
The positive active material for positive active material and composition formula (11) expression that composition formula (10) is represented,
The positive active material for positive active material and composition formula (12) expression that composition formula (10) is represented,
The positive active material that the positive active material and composition formula (13) that composition formula (10) is represented are represented.
It is particularly preferred that
The positive active material for positive active material and composition formula (11) expression that composition formula (9) is represented,
The positive active material that the positive active material and composition formula (11) that composition formula (10) is represented are represented.
Portfolio ratio is not particularly limited, but preferably 10:90~90:10, more preferably 20:80~80:20.
In the positive pole used in the lithium secondary battery of the present invention, containing the different positive active materials of more than two kinds of composition, The BET specific surface area of at least one positive active material preferably wherein, average primary particle diameter, median particle diameter d50And/or jolt ramming Density (following, to be abbreviated as " following physical property ") is in following specific scopes.The different positive active material of more than two kinds of composition In, also comprising the positive active material certain physical property not in following ranges, but the preferably institute of positive active material of more than two kinds There is certain physical property of material in following ranges." all positive-actives of following any physical property in following particular ranges Material " depends on its physical property relative to the content ratio of " all positive active materials contained in positive pole ", is not particularly limited, But preferably more than 30 mass %, more preferably more than 50 mass %, particularly preferably its whole.It is preferred that 2 contained by positive pole Each in the positive active material of the above is planted, physical property more than any one in its following physical property is in following specific In the range of, two or more more preferably arbitrary physical property is in following specific scopes, particularly preferred arbitrary more than 3 kinds physical property In following specific scopes, most preferably following all physical property are in following specific scopes.
[[BET specific surface area]]
The BET specific surface area of at least one of positive active material positive active material is preferably 0.4m2/ more than g, More preferably 0.5m2/ more than g, more preferably 0.6m2/ more than g, is limited to 2m thereon2/ below g, preferably 1.8m2/ g with Under, more preferably 1.5m2/ below g.If BET specific surface area is smaller than the scope, battery performance is easily reduced, and if BET Specific surface area is bigger than the scope, then tap density is difficult to improve, and is sometimes prone on the coating when forming positive active material Generation problem.
The value that BET specific surface area is defined as：Using surface area meter (for example, the full-automatic surface that big storehouse reason development is made Product determines device), at 150 DEG C sample is carried out under nitrogen circulation 30 minutes it is predrying, then to be adjusted to nitrogen relative using correct The nitrogen helium mixture for being 0.3 in the relative pressure of atmospheric pressure, 1 point of the N2 adsorption BET carried out by using gas flow method Method and the value determined.
[[average primary particle diameter]]
It is used as the average primary particle diameter of at least one of positive active material positive active material, preferably 0.1 μm More than, more preferably more than 0.2 μm, more preferably more than 0.3 μm, most preferably more than 0.4 μm, its upper limit is preferably 2 μ Below m, more preferably less than 1.6 μm, most preferably more preferably less than 1.3 μm, less than 1 μm.If it exceeds on above-mentioned Limit, then be difficult to the glomerate offspring of shape, bring harmful effect, or specific surface area to be greatly reduced powder fillibility, because This, the possibility of the battery performance such as output characteristics reduction is uprised sometimes.If on the contrary, less than above-mentioned lower limit, being typically due to knot It is brilliant not exclusively, therefore produce sometimes discharge and recharge it is poorly reversible the problems such as.
In addition, primary particle size can be determined by using the observation of SEM (SEM).Specifically, by such as Lower method is obtained：In the photo of 10000 times of multiplying power, arbitrary 50 primary particles are obtained on the straight line of horizontal direction by The greatest length for the section that the left bounding lines of primary particle are produced, and take its average value.Although there is primary particle cohesion and shape Into the situation of offspring, but in this case, also only primary particle is measured.
[[median particle diameter d50]]
The median particle diameter d of the particle of at least one of positive active material positive active material50(primary particle condenses And be offspring diameter when forming offspring) it is preferably more than 1 μm, more preferably more than 1.2 μm, more preferably More than 1.5 μm, most preferably more than 2 μm, its upper limit is preferably less than 20 μm, more preferably less than 18 μm, more preferably Less than 16 μm, most preferably less than 15 μm.If less than above-mentioned lower limit, the product of high-tap density can not be obtained sometimes, and If it exceeds the upper limit, then because the diffusion of the lithium in particle needs the time, therefore produce battery performance reduction, Huo Zhe sometimes The positive pole of battery is made, namely film-form is coated into by active material and conductive agent or adhesive etc. are slurried in a solvent When, the problems such as producing striped.Here, there are different median particle diameter d by mixing two or more50Positive active material, can be with Further improve fillibility when making positive pole.
Median particle diameter d in the present invention50It can be surveyed using known laser diffraction/scattering formula particle size distribution device It is fixed.The LA-920 manufactured using HORIBA companies, as the decentralized medium used when determining, is used as size distribution timing 0.1 mass % sodium hexametaphosphate solutions, after 5 minutes ultrasonic waves of progress are scattered, setting determines refractive index 1.24 and is measured.
[[[tap density]]]
The tap density of at least one of positive active material positive active material is preferably 1.3g/cm3More than, more Preferably 1.5g/cm3More than, more preferably 1.6g/cm3More than, most preferably 1.7g/cm3More than.Positive active material If tap density be less than above-mentioned lower limit, formed positive electrode active material layer when, it is necessary to decentralized medium amount increase, simultaneously The necessary amount increase of conductive material or adhesive, filling rate of the positive active material in positive electrode active material layer is restricted, Battery capacity is restricted sometimes.By using the high composite oxide power of tap density, highdensity positive pole can be formed Active material layer.In general, tap density is more big more preferred, without the special upper limit, but if tap density is too big, then just The diffusion by the lithium ion of medium of nonaqueous electrolytic solution in the active material layer of pole turns into the factor for determining speed, and part throttle characteristics has When be easily reduced, therefore, the upper limit of tap density is preferably 2.7g/cm3Hereinafter, more preferably 2.5g/cm3Below.
In the present invention, tap density is defined as below：Sample is set to fall on 20cm by the sieve in 300 μm of aperture3Jolt ramming In container, after vessel volume, using powder density determination device (for example, the Tap that society of seishin enterprises manufactures Densor), 1000 length of stroke 10mm vibration is carried out, volume density now is regard as tap density.
[[Surface coating]]
At least one of positive active material positive active material, which preferably uses its surface attachment, to be had with constituting it just The positive active material of pole active material main body or the positive active material of core constitute different materials and (below, are abbreviated as " surface Attachment material ").Species, adherence method, the adhesion amount of surface attachment material etc. are same as described above.
[[shape]]
The shape of particle of at least one of positive active material positive active material can be used as used in the past Shape same as described above.
[[autofrettage]]
As the autofrettage of positive active material, the logical of the autofrettage similar to the above as inorganic compound can be used Normal method.
[structure of the positive pole of positive pole [5]]
Below, the structure of the positive pole to being used in positive pole [5] is described.
In the present invention, electrode structure and preparation method, the compacting of positive electrode active material layer, conductive material, positive-active The jointing material used during the manufacture of material layer, the liquid medium for forming slurry, collector, electrode area, discharge capacity, The thickness of positive plate etc. is same as described above.When making positive pole, positive active material can mix two or more in advance and use, It can simultaneously add to be mixed when making positive pole.
＜ negative poles ＞
The negative pole that uses in the lithium secondary battery of the present invention, as long as formed on the current collector containing being capable of occlusion and releasing The negative pole of the active material layer of the active material of lithium ion, is not particularly limited, but the negative pole is preferably selected from following negative poles [1] any one negative pole in~negative pole [10]：
Negative pole [1]：Contain the different carbonaceous material of two or more crystallinity as the negative pole of negative electrode active material；
Negative pole [2]：Contain amorphous carbonaceous as the negative pole of negative electrode active material, the amorphous carbonaceous passes through wide-angle X The interplanar distance (d002) in (002) face that ray diffraction method is determined is more than 0.337nm, and crystallite size (Lc) is below 80nm, is adopted With argon laser Raman spectroscopy measure with 1360cm-1Peak intensity relative to 1580cm-1The ratio between peak intensity definition Raman R value is more than 0.2；
Negative pole [3]：Contain metal oxide as the negative pole of negative electrode active material, the metal oxide, which contains, to be inhaled Stay and release the titanium of lithium ion；
Negative pole [4]：Contain carbonaceous material as the negative pole of negative electrode active material, the circularity of the carbonaceous material is 0.85 More than, surface functional group amount O/C values are 0~0.01；
Negative pole [5]：Contain different orientation carbon complex as the negative pole of negative electrode active material, the different orientation carbon is combined Thing contains the different carbonaceous material of two or more orientation；
Negative pole [6]：Contain graphite carbon particle as the negative pole of negative electrode active material, the circle of the graphite carbon particle Spend for more than 0.85, the interplanar distance (d002) in (002) face determined by wide-angle x-ray diffraction is less than 0.337nm, using argon Ion laser Raman spectroscopy determine with 1360cm-1Peak intensity relative to 1580cm-1The definition of the ratio between peak intensity Raman R values are 0.12~0.8；
Negative pole [7]：Containing negative pole of following negative electrode active materials (C) comprising multielement as negative electrode active material, The negative electrode active material (C) comprising multielement contain selected from Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, At least one of Pt, Pd and Sb lithium occlusion metal (A) and/or lithium occlusion alloy (B), and contain C and/or N as member Plain Z；
Negative pole [8]：Contain the different negative electrode active material of more than two kinds of property as the negative pole of negative electrode active material；
Negative pole [9]：It is 0.1g/cm containing tap density3More than, and using mercury, Hg porosimeter measure equivalent to straight The micropore volume of the particle of the μ m of footpath 0.01 μm~1 is the negative pole of more than 0.01mL/g negative electrode active material；
Negative pole [10]：Be charged to the negative pole nominal capacity 60% when, by negative pole opposed battery produce reaction electricity Hinder for 500 below Ω negative pole.
Below, negative pole usually used in the lithium secondary battery of the present invention is illustrated first.
[negative electrode active material]
Below, negative electrode active material usually used in negative pole is described.
[[composition]]
As negative electrode active material, as long as electrochemically occlusion and lithium ion can be released, without special Limitation, can enumerate the metal oxides such as carbonaceous material, tin oxide or silica, composite oxide of metal, lithium simple substance or lithium aluminium and close The lithium alloys such as gold, Sn or Si etc. can form metal of alloy etc. with lithium.They can be used alone, can also be with arbitrary group Close and two or more is applied in combination in ratio.Wherein, from a security perspective, carbonaceous material or lithium composite xoide are preferably used.
As composite oxide of metal, as long as with occlusion and lithium can be released, have no particular limits, but in high current From the point of view of in density charge-discharge characteristic this point, titanium and/or lithium are preferably comprised as constituent.
As carbonaceous material, from initial stage irreversible capacity, from the point of view of the balance of high current density charge-discharge characteristic, it is preferably following Carbonaceous material：
(1) native graphite；
(2) artificial carbonaceous material and Delanium material；By carbonaceous material [for example, native graphite, coal class coke, stone Petroleum coke, coal class pitch, petroleum-type pitch or by these bitumen blowings processing obtained from material, needle coke, pitch coke Charcoal and by carbon material obtained from their part graphitizations；The heat of the organic matters such as furnace black, acetylene black, pitch-based carbon fiber point Solution product, the organic matter that can be carbonized are (for example, the coal class weight such as coal tar asphalt or destructive distillation liquefaction oil from maltha to pitch The straight run class heavy oil such as oil, atmospheric resids, decompression residual oil；Ethylene bottom oil of by-product etc. decomposes class when crude oil, naphtha etc. are thermally decomposed Black petroleum products；And the aromatic hydrocarbon such as acenaphthylene, decacyclene, anthracene, phenanthrene；The azo-cycle compound such as azophenlyene or acridine；Thiophene, di- thiophene Deng sulphur cycle compound；The polyphenyl such as biphenyl, terphenyl；Polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, they insoluble The organic polymers such as processed material, nitrogenous polyacrylonitrile, polypyrrole；The organic polymers such as polythiophene, the polystyrene of sulfur-bearing；With Cellulose, lignin, mannosan, polygalacturonic acid, chitosan, sucrose are the natural polymers such as the polysaccharide of representative；It is poly- The thermoplastic resins such as diphenyl sulfide, polyphenylene oxide；The thermosetting resins such as furfuryl alcohol resin, phenolic resin, imide resin) and they Carbide；Or the organic matter that can be carbonized is dissolved in the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane Formed by solution and their carbide] carried out in the range of 400~3200 DEG C formed by heat treatment more than once Carbon material；
(3) negative electrode active material layer has that different crystalline carbonaceous are constituted, and/or its difference is tied more than at least two kinds of The carbonaceous of crystalline substance has the carbon material at the interface being in contact；
(4) carbonaceous that negative electrode active material layer has different orientation more than at least two kinds of is constituted, and/or its difference takes The carbonaceous of tropism has the carbon material at the interface being in contact.
[structure, physical property and the preparation method of negative pole]
Property on carbon material, the negative electrode comprising carbon material, electric polarization method, collector and lithium secondary battery, It is preferred that meeting wantonly 1 or multinomial in (1)~(9) item as shown below simultaneously.
(1) X-ray parameter
Carbon material is preferably by using the d values (interfloor distance) for learning the lattice plane (002) that the X-ray diffraction of method tries to achieve of shaking More than 0.335nm, its upper limit is usually below 0.36nm, preferably below 0.35nm, more preferably below 0.345nm.In addition, The crystallite dimension (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is preferably more than 1nm, more preferably 1.5nm more than.
(2) ash content
Contained ash content is preferably below 1 mass %, more preferably relative to the gross mass of carbonaceous material in carbonaceous material Below 0.5 mass %, particularly preferably below 0.1 mass %, are used as lower limit, preferably more than 1ppm.If it exceeds above-mentioned model Enclose, then the deterioration of battery performance can not be ignored caused by the reaction with nonaqueous electrolytic solution during discharge and recharge.Should if be less than Scope, then need long period and energy and the equipment for preventing pollution in manufacture, and cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of carbonaceous material is the average grain for the volume reference tried to achieve by laser diffraction/scattering method Footpath (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, more than 7 μm. In addition, its upper limit is usually less than 100 μm, preferably less than 50 μm, more preferably less than 40 μm, more preferably 30 μm with Under, particularly preferably less than 25 μm.If less than above range, irreversible capacity increase occasionally results in initial cell capacity Loss.In addition, if more than above range, then when making electrode by being coated with, easily forming uneven coated face, sometimes It is undesirable in battery production process.
In the present invention, volume reference average grain diameter is defined with median particle diameter, and the median particle diameter is by the following method Determine：Carbon dust is set to be dispersed in 0.2 matter of polyoxyethylene (20) Span-20 as surfactant Measure in the % aqueous solution (about 10mL), using laser diffraction/scattering formula particle size distribution meter (for example, what Ku Chang manufacturing companies manufactured LA-700) determine.
(4) Raman R value, Raman half breadth
Using argon laser Raman light method determine carbonaceous material R values usually more than 0.01, preferably 0.03 with On, more preferably more than 0.1, less than 1.5, preferably less than 1.2, more preferably less than 1.0 are limited to thereon, more preferably Less than 0.5 scope.If R values are less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters interlayer (サ イ ト) tails off sometimes in site.That is, charging acceptance is reduced sometimes.In addition, after coating on the current collector, being made by compacting During negative pole densification, crystallization is easily oriented to the direction parallel with battery lead plate, occasionally results in part throttle characteristics reduction.The opposing party Face, if it exceeds the crystallinity reduction of the scope, then particle surface, increases with the reactivity of nonaqueous electrolytic solution, occasionally result in effect The gas increase that rate is reduced or produced.
In addition, carbonaceous material is in 1580cm-1Neighbouring Raman half breadth has no particular limits, usually 10cm-1With On, preferably 15cm-1More than, its upper limit is usually 100cm-1Hereinafter, preferably 80cm-1Hereinafter, more preferably 60cm-1Hereinafter, More preferably 40cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity mistake of particle surface Height, as the discharge and recharge Li sites (サ イ ト) for entering interlayer tail off sometimes.That is, charging acceptance is reduced sometimes.In addition, coating After on the current collector, when making negative pole densification by compacting, crystallization is easily oriented to the direction parallel with battery lead plate, sometimes Part throttle characteristics is caused to reduce.On the other hand, if above the scope, then the crystallinity reduction of particle surface, with nonaqueous electrolytic solution Reactivity increase, occasionally result in efficiency reduction or produce gas increase.
Raman spectrum is determined as follows progress：Use raman spectroscopy device (such as raman spectroscopy that Japanese light splitting company manufactures Device), sample is fallen and is filled in cell (cell) naturally, argon laser is irradiated to the specimen surface in pond, simultaneously Pond is set to be rotated in the face with laser vertical.For obtained Raman spectrum, 1580cm is determined-1Neighbouring peak PAIntensity IAWith 1360cm-1Neighbouring peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as the Raman R value of carbonaceous material. In addition, determining obtained Raman spectrum in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the Raman of carbonaceous material Half breadth.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
R values, half breadth analysis：Background (background) processing
Smooth (smoothing) processing：Simple average, 5 points of convolution (the Port イ Application ト of U Application ボ リ ュ シ ョ Application 5)
(5) BET specific surface area
The specific surface area of the carbonaceous material of the invention determined using BET method usually 0.1m2/ more than g, be preferably 0.7m2/ more than g, more preferably 1.0m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ g with Under, preferably 25m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area Less than above range, then as negative pole in the case of, in charging, the acceptance of lithium is deteriorated, and lithium is easily separated out in electrode surface. On the other hand, if above above range, then when as negative material, increase with the reactivity of nonaqueous electrolytic solution, the gas of generation Body easily becomes many, is difficult to obtain preferred battery sometimes.
The specific surface area determined using BET method uses the value determined as follows：Using surface area meter (for example, big storehouse reason is developed The full-automatic surface area determination unit made), nitrogen circulation under, at 350 DEG C to sample carry out 15 minutes it is predrying, then, 0.3 nitrogen helium mixture is accurately adjusted to relative to the relative pressure of atmospheric pressure using nitrogen, is flowed by using gas 1 method of N2 adsorption BET of method is determined.
(6) micropore diameter is distributed
The micropore diameter distribution of the carbonaceous material used in the present invention is tried to achieve by mercury, Hg porosimeter (mercury penetration method) Equivalent to micro-pore diameter for the space in 0.01 μm~1 μm of particle, due to particle surface be uneven cause it is concavo-convex, The amount of interparticle contact surface etc. be more than 0.01mL/g, more preferably preferably more than 0.05mL/g, more than 0.1mL/g, its The upper limit is below 0.6mL/g, preferably below 0.4mL/g, more preferably below 0.3mL/g scope.If it exceeds the scope, Then need substantial amounts of adhesive when manufacturing pole plate sometimes.If less than the scope, high current density charge-discharge characteristic is reduced, Also, the alleviation effects that electrode expansion when can not obtain discharge and recharge sometimes shrinks.
In addition, total micropore volume equivalent to the micropore diameter of 0.01 μm~100 μ ms is preferably more than 0.1mL/g, more Preferably more than 0.25mL/g, more preferably more than 0.4mL/g, are limited to below 10mL/g thereon, preferably 5mL/g with Under, more preferably below 2mL/g scope.If above the scope, then substantial amounts of adhesive is needed when manufacturing pole plate sometimes. If less than the scope, the dispersion effect of thickener or binding agent can not be obtained sometimes when manufacturing pole plate.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope are limited to thereon.If it exceeds the scope, then have When need substantial amounts of adhesive.If less than the scope, sometimes high current density charge-discharge characteristic reduction.
As the device as mercury, Hg porosimeter, mercury void determination instrument (autopore (オ ー ト Port ア) can be used 9520；Micrometritics (マ イ Network ロ メ リ テ ッ Network ス) company manufactures).About 0.2g samples are encapsulated into powder container In, (50 μm of below Hg) deaerate within 10 minutes in vacuum at room temperature, carries out pre-treatment.Then, it is decompressed to 4psia (about 28kPa), mercury is imported, is boosted to from 4psia (about 28kPa) stage shape after 40000psia (about 280MPa), then be depressurized to 25psia (about 170kPa).Number of stages during boosting more than the stage, in each stage, after the equilibration time of 10 seconds, is surveyed for 80 Determine mercury intrusion.Micropore diameter is calculated using Washburn formulas from the mercury press-in curve so obtained to be distributed.In addition, mercury Surface tension (γ) be 485dyne/cm, contact angle (φ) be 140 °.Mean pore footpath is reached using accumulation micro pore volume Micropore diameter when 50%.
(7) circularity
Spherical degree using circularity as carbonaceous material, its particle diameter is the circularity of the particle of 3~40 μ ms Preferably more than 0.1, particularly preferably more than 0.5, more preferably more than 0.8, more preferably more than 0.85, be most preferably More than 0.9.When circularity is big, high current density charge-discharge characteristic is improved, therefore preferably.
Circularity is defined with following formula, is theoretical proper sphere when circularity is 1.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using such as flow-type particle image analysis device (for example, The FPIA of Sysmex Industrial (シ ス メ ッ Network ス イ Application ダ ス ト リ ア Le) company manufacture), about 0.2g samples are disperseed In the 0.2 mass % aqueous solution (about 50mL) of polyoxyethylene (20) Span-20 as surfactant In, after the ultrasonic wave that 1 minute 28kHz is irradiated with 60W power output, it is detection range to specify 0.6~400 μm, to particle diameter 3~ The particle of 40 μ ms is measured.
The method for improving circularity has no particular limits, but is allowed into by implementing spheroidization processing (mechanical energy processing) For it is spherical can make to be made electrode body when inter-particle voids shape it is neat uniform, therefore it is preferred that.The example handled as spheroidization, It can enumerate, by applying shearing force, compression stress come the method for mechanically subglobular, have by adhesive or particle itself Adhesive force machinery/physical treatment method for granulating multiple particulates etc..
(8) real density
The real density of carbonaceous material is usually 1.4g/cm3More than, preferably 1.6g/cm3More than, more preferably 1.8g/cm3 More than, more preferably 2.0g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theoretical value of graphite.If low In the scope, then the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.In the present invention, real density is defined as leading to Cross the value determined using the Liquid displacement methods (hydrometer method) of butanol.
(9) tap density
The tap density of carbonaceous material is usually 0.1g/cm3More than, preferably 0.5g/cm3More than, more preferably 0.7g/ cm3More than, particularly preferably 1.0g/cm3More than.In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3With Under, particularly preferably 1.6g/cm3Below.If tap density be less than the scope, as negative pole in use, packed density very Hardly possible is improved, and the battery of high power capacity can not be obtained sometimes.On the other hand, if it exceeds the scope, then the interparticle sky in electrode Gap is very few, it is difficult to ensure interparticle electric conductivity, is difficult to obtain preferred battery behavior sometimes.Tap density by with positive pole The same method of the method for elaboration is defined to determine by this method.
(10) orientation ratio
The orientation ratio of carbonaceous material is usually more than 0.005, and preferably more than 0.01, more preferably more than 0.015, thereon It is limited to scope of the theoretical value below 0.67.If being less than the scope, high density charge-discharge characteristic can be reduced sometimes.
Orientation ratio is to be measured after sample is press-formed by X-ray diffraction.0.47g samples are filled into directly In footpath 17mm forming machine, with 600kgf/cm2Compression obtains formed body, fixes above-mentioned formed body using clay, makes itself and measure Face with sample retainer is the same face, then determines X-ray diffraction.From (110) diffraction and (004) diffraction of obtained carbon Peak intensity calculates the ratio represented with (110) diffraction integral intensity/(004) diffraction integral intensity, and the ratio is defined as to live The orientation ratio of property material.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：
Divergent slit=0.5 degree, by optical slits=0.15mm, scatter slit=0.5 degree
Measurement range and stepping angle/minute
(110) face：75 degree≤2 1 degree of θ≤80 degree/60 seconds
(004) face：52 degree≤2 1 degree of θ≤57 degree/60 seconds
(11) draw ratio (powder)
Draw ratio is theoretically more than 1, and the upper limit is less than 10, preferably less than 8, more preferably less than 5.If it exceeds on Limit, then produce striped, can not obtain uniform coated face sometimes when manufacturing pole plate, the reduction of high current density charge-discharge characteristic.
In addition, during draw ratio three dimensional viewing the most major diameter A of carbonaceous material particle and perpendicular most minor axis B ratio A/B is represented.The observation of carbon particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection is fixed on thickness Any 50 graphite particles on the end face of less than 50 microns of metallic plate, rotation, inclination are fixed with the objective table of sample, respectively A, B of these particles are determined, A/B average value is obtained.
(12) auxiliary material is mixed
So-called " auxiliary material mixing " refers to contain two or more property difference in negative electrode and/or in negative electrode active material Carbonaceous material.Property mentioned here, refers to X-ray diffraction parameter, median particle diameter, draw ratio, BET specific surface area, orientation Than the more than one characteristic in, Raman R value, tap density, real density, micropore distribution, circularity, ash amount.
As particularly preferred embodiment, it can enumerate, volume reference size distribution is when centered on median particle diameter It is left-right asymmetry, not equal containing the different carbonaceous material of two or more Raman R value or X-ray parameter.
As an example of its effect, it can enumerate, by containing the graphite such as native graphite, Delanium；Acetylene black Deng carbon black；The carbonaceous materials such as the amorphous carbon such as needle coke can reduce resistance as conductive agent.They can be used alone, Two or more can be applied in combination with arbitrary proportion in any combination.It is more than 0.1 mass %, preferably when being added as conductive agent For more than 0.5 mass %, more preferably more than 0.6 mass %, it is limited to thereon below 45 mass %, preferably 40 mass % model Enclose.If less than the scope, the effect for obtaining electric conductivity raising is difficult to sometimes.If above above range, then lead sometimes The increase of cause irreversible capacity at initial stage.
(13) electrode fabrication
Usual way can be used by making electrode.For example, adding adhesive, solvent, basis in negative electrode active material Thickener, conductive material, packing material of addition etc. are needed, slurry is made, is coated with the current collector, passes through pressure after drying Make and form electrode.Stage before nonaqueous electrolytic solution injection process, the thickness of the negative electrode active material in every face of battery leads to Be often more than 15 μm, preferably more than 20 μm, more preferably more than 30 μm, be limited to less than 150 μm thereon, preferably 120 μm with Under, more preferably less than 100 μm.If it exceeds the scope, then nonaqueous electrolytic solution is difficult to be impregnated into collector near interface, because This, the reduction of high current density charge-discharge characteristic.In addition, if less than the scope, then collector is relative to negative electrode active material Volume ratio increase, battery capacity is reduced sometimes.Furthermore it is possible to negative electrode active material is carried out into roller shaping is made pellet electrode, Or mosaic electrode is made by compression forming.
(14) collector
, can be arbitrarily using known collector as collector.As the collector of negative pole, it can enumerate, copper, The metal materials such as nickel, stainless steel, nickel-plated steel, wherein, from the viewpoint of handling ease and cost, preferred copper.The shape of collector Shape can enumerate metal foil, metal cylinder, wire coil, metallic plate, metallic film, expansion conjunction when collector is metal material Gold, perforated metal, foaming metal etc..Wherein, preferably metallic film, more preferably copper foil, are further preferably made using rolling process Rolled copper foil and using electrolytic copper foil made from electrolysis, any one can be used as collector.The thickness of copper foil When thinner than 25 μm, the copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu-Cr-Zr alloy etc.) higher than fine copper intensity can be used. In addition, aluminium foil is due to its light specific gravity, therefore when being used in collector, it is possible to reduce the weight of battery, therefore preferably use.
In the collector made by the copper foil made using rolling process, because copper crystallization is in rolling direction arrangement, even if will Negative pole closely bending or negative pole is bent it is at an acute angle, it is all not easy to break, it is adaptable to small cylinder shape battery.Electrolytic copper foil is made as follows ：For example, the drum that impregnating metal is manufactured in the nonaqueous electrolytic solution for be dissolved with copper ion, the circulating current when rotating the drum, Thus copper is separated out on bulging surface, then peeled off.Copper can also be separated out by electrolysis on the surface of above-mentioned rolled copper foil. The one or both sides of copper foil can be roughened or are surface-treated (for example, thickness is the chromic acid of a few nm~1 μm or so Salt treatment, Ti etc. bottom layer treatment etc.).
For current collection structure base board, it is desirable to following physical property.
(1) average surface roughness (Ra)
The active material film formation face of current collection structure base board specified in the method recorded according to JIS B 0601-1994 Average surface roughness (Ra) has no particular limits, but usually more than 0.05 μm, preferably more than 0.1 μm, particularly preferably For more than 0.15 μm, its upper limit is usually less than 1.5 μm, preferably less than 1.3 μm, particularly preferably less than 1.0 μm.By making Scope of the average surface roughness (Ra) of current collection structure base board between above-mentioned lower and upper limit, can expect good discharge and recharge Cycle characteristics.By being set as more than above-mentioned lower limit, become big with the interfacial area of active material film, it is close with active material Conjunction property is improved.The higher limit of average surface roughness (Ra) has no particular limits, and average surface roughness (Ra) is more than 1.5 μm When, it is difficult to obtain the paper tinsel as battery suitable thickness, therefore preferably less than 1.5 μm.
(2) tensile strength
The tensile strength of current collection structure base board has no particular limits, but usually 100N/mm2More than, preferably 250N/mm2 More than, more preferably 400N/mm2More than, particularly preferably 500N/mm2More than.So-called tensile strength, refers to that test film reaches disconnected Value obtained from the sectional area of required maximum pull divided by test film when splitting.Tensile strength in the present invention, can use with The same apparatus and method of elongation are determined to determine.If the high current collection structure base board of tensile strength, then it can suppress to charge/put It is special so as to obtain good circulation due to the cracking of active material film expansion/current collection structure base board caused by contraction when electric Property.
(3) 0.2% endurance
0.2% endurance of current collection structure base board has no particular limits, but usually 30N/mm2More than, preferably 150N/mm2 More than, particularly preferably 300N/mm2More than.So-called 0.2% endurance, refers to that (permanent) deformation of the plasticity for producing 0.2% is required Payload, after the load for applying the size, 0.2 deformation can also be kept by removing load.0.2% endurance in the present invention can By being determined with determining elongation identical apparatus and method.If the high current collection structure base board of 0.2% endurance, then can press down Due to the plastic deformation of active material film expansion/current collection structure base board caused by contraction during charge/discharge processed, so as to obtain Good cycle characteristics.
The thickness of metallic film is arbitrary, usually more than 1 μm, more preferably preferably more than 3 μm, more than 5 μm.Separately Outside, its upper limit is usually below 1mm, preferably less than 100 μm, more preferably less than 30 μm.If thinner than 1 μm, intensity drop It is low, application difficulties sometimes.In addition, if than 100 μ m-thicks, then making the shape of electrode occur the deformation such as curling sometimes.In addition, golden It can also be netted to belong to film.
(15) the ratio between thickness of collector and active material layer
The ratio between thickness of collector and active material layer has no particular limits, (the side before injection nonaqueous electrolytic solution The thickness of active material layer)/(thickness of collector) be preferably less than 150, particularly preferably less than 20, more preferably 10 with Under, its lower limit is preferably more than 0.1, more preferably less than 0.4, more preferably more than 1 scope.If it exceeds the model Enclose, then during high current density discharge and recharge, collector produces heating because of Joule heat sometimes.If less than the scope, had When collector relative to the volume ratio increase of negative electrode active material, the capacity of battery reduces.
(16) electrode density
Electrode structure when negative electrode active material to be made to electrode has no particular limits, and is present in the activity on collector The density of material is preferably 1.0g/cm3More than, more preferably 1.2g/cm3More than, more preferably 1.3g/cm3More than, its The upper limit is usually 2.0g/cm3Hereinafter, preferably 1.9g/cm3Hereinafter, more preferably 1.8g/cm3Hereinafter, more preferably 1.7g/cm3Following scope.If it exceeds the scope, then active material is destroyed, and causes irreversible capacity increase at initial stage, non- Water electrolysis liquid is reduced to the impregnability near collector/reactive species interface, so as to cause high current density charge-discharge characteristic to be disliked Change.In addition, if less than the scope, then the electric conductivity decline between active material, cell resistance increases, sometimes the electricity of unit volume Tankage is reduced.
(17) adhesive
As the adhesive for bonding active material, as long as the solvent-stable used to nonaqueous electrolytic solution or when manufacturing electrode Material, have no particular limits.Specifically, polyethylene can be enumerated, it is polypropylene, polyethylene terephthalate, poly- The resin family macromolecule such as methyl methacrylate, aromatic polyamide, cellulose, NC Nitroncellulose；It is SBR (butadiene-styrene rubber), different The rubber-like such as pentadiene rubber, butadiene rubber, fluorubber, NBR (acrylonitrile-butadiene rubber), styrene-propene rubber are high Molecule；SBS or its hydrogenation thing；EPDM (ethylene-propylene-diene terpolymer), The heat such as SIS/SEBS, styreneisobutylene-styrene block copolymer or its hydrogenation thing Thermoplastic elastic shape macromolecule；The polybutadiene of syndiotactic 1,2, polyvinyl acetate, ethylene-vinyl acetate copolymer, propylene-α- The soft resinous macromolecule such as olefin copolymer；Kynoar, polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)- The fluorine class macromolecule such as ethylene copolymer；The polymeric composition of ionic conductivity with alkali metal ion (particularly lithium ion) Deng.They can be used alone one kind, two or more can also be applied in combination with ratio in any combination.
As the solvent for forming slurry, as long as it can dissolve or dispersed actives, adhesive and according to need The thickener and the solvent of conductive agent to be used, its species have no particular limits, and can use water solvent or organic Any of class solvent.As the example of water solvent, water, alcohol etc. can be enumerated；As the example of organic solvent, it can enumerate 1-METHYLPYRROLIDONE (NMP), dimethylformamide, dimethyl acetamide, MEK, cyclohexanone, methyl acetate, acrylic acid first Ester, diethyl triamine, N, N- dimethylamino propylamines, expoxy propane, tetrahydrofuran (THF), toluene, acetone, ether, dimethyl Acetamide, hexamethyl phosphoramide, dimethyl sulfide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc..Particularly using During water solvent, while adding above-mentioned thickener and dispersant etc., carried out using SBR etc. latex slurried.In addition, they can So that one kind is used alone, two or more can also be applied in combination with ratio in any combination.
Adhesive is preferably more than 0.1 mass % relative to the ratio of active material, particularly preferably 0.5 mass % with On, more preferably more than 0.6 mass %, its upper limit is usually preferably below 15 mass % below 20 mass %, more preferably Below 10 mass %, more preferably below 8 mass % scope.If it exceeds the scope, then will not in the amount of adhesive The adhesive ratio of help is brought to battery capacity to be increased, and occasionally results in battery capacity reduction.In addition, if less than above-mentioned model Enclose, then occasionally result in the intensity decreases of negative electrode.Particularly, the rubber-like high score using SBR as representative is contained in main component The period of the day from 11 p.m. to 1 a.m, adhesive is usually more than 0.1 mass % preferably more than 0.5 mass % relative to the ratio of active material, more preferably For more than 0.6 mass %, its upper limit is usually preferably below 3 mass %, more preferably below 2 mass % below 5 mass % Scope.In addition, when containing the fluorine class macromolecule using Kynoar as representative in main component, adhesive is relative to active matter The ratio of matter is usually more than 1 mass % preferably more than 2 mass %, more preferably more than 3 mass %, and its upper limit is usually Below 15 mass %, preferably below 10 mass %, more preferably below 8 mass %.
Thickener is used typically to the viscosity of regulation slurry.As thickener, have no particular limits, specifically Ground, can enumerate carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorus Acidified starch, casein and their salt etc..They can be used alone one kind, can also be combined in any combination with ratio Use two or more.In addition, when adding thickener, thickener relative to the ratio of active material be usually 0.1 mass % with On, preferably more than 0.5 mass %, more preferably more than 0.6 mass %, its upper limit are usually below 5 mass % preferably 3 Below quality %, more preferably below 2 mass % scope.If being less than the scope, coating is significantly reduced sometimes.If More than the ratio reduction of the scope, the then active material shared by negative electrode active material layer, asking for battery capacity reduction is produced sometimes Topic or negative electrode active material between resistance increase the problem of.
(18) pole plate orientation ratio
Pole plate orientation ratio is preferably more than 0.001, and more preferably more than 0.005, particularly preferably more than 0.01, the upper limit is Theoretical value, i.e., less than 0.67.If less than the scope, sometimes high density charge-discharge characteristic reduction.
Pole plate orientation ratio is determined as follows progress.Surveyed to being pressed into the negative electrode after target density by X-ray diffraction The active material orientation ratio of fixed electrode.Specific method is not particularly limited, and as the method for standard, uses asymmetric Pearson (ピ ア ソ Application) VII as distribution (profile) function, be fitted (110) diffraction of carbon that is obtained by X-ray diffraction with (004) peak of diffraction, carries out peak separation, and the integrated intensity at the peak of (110) diffraction and (004) diffraction is calculated respectively.By obtaining Integrated intensity, calculate the ratio represented by (110) diffraction integral intensity/(004) diffraction integral intensity.By the measure and calculation The active material orientation ratio of the electrode gone out is defined as pole plate orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K α lines) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
It is prepared by sample：Electrode is fixed on a glass with 0.1mm thick two-sided tapes
(19) impedance
Cathode impedance when the 60% of nominal capacity is charged to from discharge condition is preferably 100 below Ω, more preferably 50 Below Ω, particularly preferably 20 below Ω, and/or electric double layer capacity is preferably 1 × 10-6More than F, more preferably 1 × 10-5F, Particularly preferably 1 × 10-4F.The scope output characteristics is good, therefore it is preferred that.
Negative pole resistance and electric double layer capacity are determined by the following method.Lithium secondary battery to be determined uses following electricity Pond：After being charged with the current value that can charge to nominal capacity with 5 hours, 20 minutes shapes without discharge and recharge are maintained State, then, with that the current value that nominal capacity discharges can be discharged with 1 hour, capacity now is nominal capacity More than 80%.For the lithium secondary battery of above-mentioned discharge condition, filled by the current value that can charge to nominal capacity with 5 hours Electricity arrives the 60% of nominal capacity, is immediately transferred to lithium secondary battery in the spherical container under argon atmosphere.Do not discharging or not The lithium secondary battery is disintegrated rapidly in the state of short circuit, negative pole is taken out, if double spread electrode, then by the electricity of one side 2 negative electrodes are punched into 12.5mm φ by the electrode active material that pole active material is peeled off without damaging another side, sandwich every Plate, makes active material face not have mistake liftoff opposed.The μ of nonaqueous electrolytic solution 60 used in battery is added dropwise between dividing plate and two negative poles L, is bonded, and keeps the state not contacted with the external world, is made the collector of two negative poles conductive, is implemented AC impedence method.Determine such as It is lower to carry out, at a temperature of 25 DEG C, 10-2~105Hz frequency band determines complex impedance, by the callcallplot tried to achieve The circular arcs of negative pole resistance components be approximately semicircle, obtain sheet resistance (R) and electric double layer capacity (Cd1).
(20) area and thickness of negative plate
The area of negative plate has no particular limits, and is usually designed to more slightly larger than opposed positive plate, makes positive plate will not It is exposed to outside negative plate.From the cycle life of repeated charge or suppression due to the viewpoint deteriorated caused by High temperature storage See, if as close possible to the area equal with positive pole, then can further improve the electrode ratio evenly and effectively worked Example, so that characteristic is improved, therefore preferably.Particularly, with high current in use, the design of the electrode area is important.
The thickness of negative plate is designed according to the positive plate used, is had no particular limits, but subtracts the metal foil of core The thickness of plied timber layer after thickness is usually more than 15 μm, preferably more than 20 μm, more preferably more than 30 μm, thereon Limit is usually less than 150 μm, more preferably preferably less than 120 μm, less than 100 μm.
<Negative pole [1]>
Hereinafter, " two or more is contained as negative electrode active material to the negative pole [1] used in the lithium secondary battery of the present invention The different carbonaceous material of crystallinity negative pole " illustrate.
[negative electrode active material of negative pole [1]]
Below, the negative electrode active material that negative pole [1] is used is illustrated.
[[composition]]
The negative electrode active material used in the negative pole [1] of the lithium secondary battery of the present invention is characterised by containing two or more The different carbonaceous material of crystallinity.Here, " containing the different carbonaceous material of two or more crystallinity " represents that knot has coexisted in negative pole The different carbonaceous material of crystalline substance, in addition, it can have and be blended in one in the form of single particle one by one that form, which coexists, in it The state risen, or included in an offspring, or said two devices mixing.In addition, being used as negative electrode active material Matter, preferably comprises the composite carbonaceous material for including the different carbonaceous material of two or more crystallinity, more preferably in the composite carbonaceous thing Also make in matter containing more than one carbonaceous materials (carbonaceous material) different in terms of the physical property of carbonaceous from the composite carbonaceous material For auxiliary material.
" being included in an offspring " mentioned here represents that the different carbonaceous material of crystallinity is bonded and constrained in State together, the state of physical constraint, state of shape etc. is maintained by electrostatic confinement." physical constraint " mentioned here The state that a kind of different carbonaceous material of crystallinity is mingled with the state in another carbonaceous material, mutually tangled is represented, it is so-called " electrostatic confinement " represents that a kind of different carbonaceous material of crystallization is attached to the state in another carbonaceous material by electrostatic energy. In addition, " by the state for being bonded constraint " represents the chemical bonds such as hydrogen bond, covalent bond, ionic bond.
Wherein, at least part surface of the carbonaceous material as core has different from the crystallinity by bonding together to form cover In the state of the interface of cap rock, the mobile impedance of the lithium between the different carbonaceous material of crystallinity is small, therefore favorably.The coating can be with Formed by being bonded for the material with being externally supplied and/or their modifier, or the surface element for passing through carbonaceous material The modification of material formed.Here, so-called covering, expression has with least a portion in the interface on the surface of carbonaceous material Chemical bond, and show the local state of the state of (1) covering all surfaces, (2) covering carbon particle, (3) optionally covering part The state on point surface, (4) are present in the state in the very small region containing chemical bond.In addition, crystallinity can connect on interface Continuous change, can also discontinuously change.
Composite carbonaceous material preferably has in particle shape carbonaceous material covered with crystallinity and the particle shape carbonaceous material Interface formed by different carbonaceous materials, and/or crystallinity and the particle shape carbonaceous are bonded with particle shape carbonaceous material Interface formed by the different carbonaceous material of material, and the crystallinity at the interface is continuous and/or discontinuously changes." particle Shape carbonaceous material " and " carbonaceous materials different from the particle shape carbonaceous material crystallinity " which high this point of crystallinity do not have Have a special restriction, but particle shape carbonaceous material crystallinity it is high when, it is possible to achieve the effect above of the invention, therefore it is preferred that.
Here, the interplanar distance (d002) in (002) face that crystalline difference is determined by using X-ray wide-angle diffraction method Difference, Lc difference, La difference judges, from the point of view of the effect of the present invention this point is shown, preferably crystalline difference with (d002) more than 0.0002nm is calculated as, either La is that more than 1nm or Lc is more than 1nm.In above range, the difference of (d002) Different is preferably more than 0.0005nm, more preferably more preferably more than 0.001nm, more than 0.003nm, and its upper limit is usually Below 0.03nm, preferably below 0.02nm scope.If less than the scope, the effect as caused by crystalline difference is sometimes It can diminish.On the other hand, if it exceeds above range, then the crystallinity of the low part of crystallinity has the tendency of step-down, thus draws The irreversible capacity risen may increase.In addition, in above range, La or Lc difference are preferably more than 2nm, more preferably More than 5nm, more preferably more than 10nm scope.Generally, graphite in 100nm above is can not define, therefore can not Specify the upper limit.If less than the scope, the effect caused by crystalline difference diminishes sometimes.
Composite carbonaceous material is to cover and/or be bonded crystallinity and the particle shape Carbonaceous matter in particle shape carbonaceous material The different carbonaceous material of matter, " particle shape carbonaceous material " and " carbonaceous different from the particle shape carbonaceous material crystallinity Material " is as long as any one is graphite-like carbonaceous material, and another is low-crystalline carbonaceous material, additionally, it is preferred that " grain Sub- shape carbonaceous material " is graphite-like carbonaceous material, and " carbonaceous materials different from the particle shape carbonaceous material crystallinity " are low Crystallinity carbonaceous material.
[[[particle shape carbonaceous material]]]
As particle shape carbonaceous material, the graphite-like carbonaceous material of native graphite and/or Delanium is preferably comprised, or is contained There is the carbonaceous material selected from least one of (a), (b) and (c) more slightly lower than their crystallinity,
(a) heat of the organic matter in coal class coke, petroleum-type coke, furnace black, acetylene black and pitch-based carbon fiber Analyte；
(b) carbide of organic gas；
(c) by carbonaceous material obtained from part or all of progress graphitization of (a) or (b).
[[[[graphite-like carbonaceous material]]]]
Particle shape carbonaceous material preferably comprises the graphite-like carbonaceous material of native graphite and/or Delanium.Graphite-like carbon Metallic substance refers to that the interplanar distance (d002) in (002) face determined using X-ray wide-angle diffraction method shows the crystallization less than 0.340nm The high various carbonaceous materials of property.
As the specific example of graphite-like carbonaceous material, the powder of following product is preferably selected from：Native graphite, artificial stone The heat treated article again or the height of these graphite of black or their mechanical crushing thing, again heat treated article, expanded graphite Purity purified product.As the specific example of above-mentioned Delanium, preferably by more than one organic substance generally at 2500 DEG C Graphitization is carried out under~3200 DEG C or so of sintering temperature, then passes through thing obtained from appropriate breaking method progress powdered Matter, the organic substance is selected from：Coal tar asphalt, coal class heavy oil, atmospheric resids, petroleum-type heavy oil, aromatic hydrocarbon, nitrogenous ring-type Compound, sulphur-containing cyclic compound, polyphenyl, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral resin, natural polymer Son, polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenolic resin, imide resin etc..
(physical property of graphite-like carbonaceous material)
The property of graphite-like carbonaceous material preferably meets any one or many in (1)~(11) shown below simultaneously .
(1) X-ray parameter
Graphite-like carbonaceous material is by using the d value (interlamellar spacings for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve From) it is preferably more than 0.335nm.In addition, from the point of view of definition, lower limit is less than 0.340nm, preferably below 0.337nm.If D values are excessive, then crystallinity is reduced, and increase irreversible capacity at initial stage sometimes.On the other hand, 0.335 be graphite theoretical value.Separately Outside, the crystallite size (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is usually more than 30nm, is preferably More than 50nm, more preferably more than 100nm scope.If less than the scope, crystallinity reduction, it is possible to increase initial stage not Reversible capacity.
(2) ash content
In graphite-like carbonaceous material contained ash content relative to the gross mass of graphite-like carbonaceous material be preferably 1 mass % with Under, more preferably below 0.5 mass %, particularly preferred below 0.1 mass %, lower limit are more than 1ppm.If it exceeds above range, Then the deterioration of battery performance can not be ignored during discharge and recharge and caused by the reaction of electrolyte.If less than the scope, in system Making needs long period and energy and the equipment for preventing pollution, and cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of graphite-like carbonaceous material is the volume reference tried to achieve by laser diffraction/scattering method Average grain diameter (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, 7 μ More than m.In addition, its upper limit is usually less than 100 μm, and preferably less than 50 μm, more preferably less than 40 μm, more preferably Less than 30 μm, particularly preferably less than 25 μm.If less than above range, irreversible capacity increase occasionally results in electricity at initial stage The loss of tankage.In addition, if more than above range, then when electrode pad is made, uneven coated face is easily formed, Sometimes it is undesirable in battery production process.
In the present invention, volume reference average grain diameter is defined with median particle diameter, and the median particle diameter is by the following method Determine：Carbon dust is set to be dispersed in 0.2 matter of polyoxyethylene (20) Span-20 as surfactant Measure in the % aqueous solution (about 1mL), using laser diffraction/scattering formula particle size distribution meter (for example, what Ku Chang manufacturing companies manufactured LA-700) determine.
(4) Raman R value, Raman half breadth
The R values of the graphite-like carbonaceous material determined using argon laser Raman spectroscopy are usually more than 0.01, preferably For more than 0.03, more preferably more than 0.10, its upper limit is usually less than 0.60, preferably less than 0.40 scope.If R values Less than the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, charge Acceptance is reduced sometimes.On the other hand, if it exceeds the crystallinity reduction of the scope, then particle surface, the reaction with electrolyte Property increase, occasionally result in efficiency reduction or produce gas increase.
In addition, graphite-like carbonaceous material is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and is usually 10cm-1More than, preferably 15cm-1More than, the upper limit is usually 60cm-1Hereinafter, preferably 45cm-1Hereinafter, more preferably 40cm-1With Under scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters layer Between site tail off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if above the knot of the scope, then particle surface Crystalline substance is reduced, and is increased with the reactivity of electrolyte, the gas increase for occasionally resulting in efficiency reduction or producing.
Raman spectrum is determined as follows progress：Use raman spectroscopy device (such as raman spectroscopy that Japanese light splitting society manufactures Device), sample is fallen and is filled in cell naturally, argon laser is irradiated to the specimen surface in pond, meanwhile, pond is existed With being rotated in the face of laser vertical.For obtained Raman spectrum, 1580cm is determined-1Neighbouring peak PAIntensity IAAnd 1360cm-1Neighbouring peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as the Raman R value of carbon material.In addition, surveying Surely the Raman spectrum obtained is in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the Raman half breadth of carbon material.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
R values, half breadth analysis：Background processing
Smooth treatment：Simple average, 5 points of convolution
(5) BET specific surface area
The specific surface area of the graphite-like carbonaceous material of the invention determined using BET method usually 0.1m2/ more than g, preferably For 0.7m2/ more than g, more preferably 1m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ g with Under, preferably 25m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area Less than above range, then in the case of being used as negative pole, in charging, the acceptance of lithium is deteriorated, and lithium is easily in electrode surface Separate out.On the other hand, if it exceeds above range, then as negative material in use, increasing with the reactivity of electrolyte, production Raw gas becomes many, is difficult to obtain preferred battery sometimes.
BET specific surface area is defined as the value determined：Using surface area meter (for example, big storehouse reason develops make full-automatic Surface area determination unit), nitrogen circulation, sample is carried out at 350 DEG C 15 minutes it is predrying, then, using nitrogen relative to The relative pressure of atmospheric pressure is accurately adjusted to 0.3 nitrogen helium mixture, by using the N2 adsorption BET1 of gas flow method Point method is determined.
(6) micropore is distributed
As graphite-like carbonaceous material, by mercury, Hg porosimeter (mercury penetration method) try to achieve equivalent to a diameter of 0.01 μm~1 μm of particle in space, due to the concavo-convex amount that causes of being uneven of particle surface be usually more than 0.01mL/g, Preferably more than 0.05mL/g, more preferably more than 0.1mL/g, the upper limit are usually below 0.6mL/g, preferably 0.4mL/g with Under, more preferably below 0.3mL/g scope.If it exceeds the scope, then need substantial amounts of adhesive when being manufactured into pole plate.Separately On the one hand, if less than the scope, high current density charge-discharge characteristic reduction, also, when can not obtain discharge and recharge sometimes The alleviation effects that electrode expansion shrinks.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.On the other hand, if being less than the scope, high current density charge-discharge characteristic drops sometimes It is low.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).About 0.2g samples (negative material) are weighed, are encapsulated into powder container, in room temperature, very (50 μm of below Hg) deaerate within 10 minutes under sky, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, mercury is imported, 40000psia (about 280MPa) is boosted to from 4psia (about 28kPa) stage shape, 25psia (about 170kPa) is then depressurized to.Rise Number of stages during pressure more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury intrusion for 80.Use Washburn formulas calculate micropore distribution from the mercury press-in curve so obtained.In addition, the surface tension (γ) of mercury is 485dyne/cm, contact angle (φ) is 140 °.Micropore diameter when mean pore footpath reaches 50% using accumulation micro pore volume.
(7) circularity
Using circularity as the spherical degree of graphite-like carbonaceous material, the particle diameter of graphite-like carbonaceous material is 3~40 μ The circularity of the particle of m scopes is preferably more than 0.1, and particularly preferably more than 0.5, more preferably more than 0.8, further preferably For more than 0.85, most preferably more than 0.9.When circularity is big, high current density charge-discharge characteristic is improved, therefore preferably.It is circular Degree is defined by following formula, when circularity is 1, as theoretical proper sphere.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using such as flow-type particle image analysis device (for example, The FPIA of Sysmex Industrial companies manufacture), about 0.2g samples are scattered in the polyoxyethylene as surfactant (20) in the 0.2 mass % aqueous solution (about 50mL) of Span-20, irradiated 1 minute with 60W power output After 28kHz ultrasonic wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured.
The method for improving circularity is not particularly limited, but makes spherical by implementing spheroidization processing and can make system Shape into inter-particle voids during electrode body is neat uniform, therefore it is preferred that.The example handled as spheroidization, can enumerate, pass through Apply the method that shearing force, compression stress carry out mechanically subglobular；The adhesive force having by adhesive or particle itself will be many Machinery/physical treatment method of individual particulate granulation etc..
(8) real density
The real density of graphite-like carbonaceous material is usually 2g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.In the present invention, real density It is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol.
(9) tap density
The tap density of graphite-like carbonaceous material is usually 0.1g/cm3More than, preferably 0.5g/cm3More than, more preferably 0.7g/cm3More than, particularly preferably 0.9g/cm3More than.In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/ cm3Hereinafter, particularly preferably 1.6g/cm3Below.If tap density be less than the scope, as negative pole in use, filling Density is difficult to improve, and the battery of high power capacity can not be obtained sometimes.On the other hand, if above the scope, then the particle in electrode Between space it is very few, it is difficult to ensure interparticle electric conductivity, be difficult to obtain preferred battery behavior sometimes.
In the present invention, tap density is defined as below：Sample is set to fall by the sieve in 300 μm of aperture in 20cm3Jolt ramming In container, until behind upper surface of the sample full of container, using powder density determination device (for example, seishin enterprise-like corporations manufacture Tap densor), carry out 1000 length of stroke 10mm vibration, volume density now is defined as tap density.
(10) orientation ratio (powder)
The orientation ratio of graphite-like carbonaceous material is usually more than 0.005, preferably more than 0.01, more preferably 0.015 with On, the upper limit is less than 0.67 scope in theory.If less than the scope, sometimes high density charge-discharge characteristic reduction.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：
Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
(11) draw ratio (powder)
The draw ratio of graphite-like carbonaceous material is theoretically more than 1, and the upper limit is usually less than 10, and preferably less than 8, it is more excellent Elect less than 5 as.If it exceeds its upper limit, can produce striped, can not obtain uniform coated face, high current density when pole plate is made Charge-discharge characteristic is reduced sometimes.
In addition, during draw ratio three dimensional viewing the most major diameter A of carbon material particle and perpendicular most minor axis B ratio A/ B is represented.The observation of carbon particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection is fixed on thickness 50 Any 50 graphite particles on the end face of metal below μm, rotation, inclination are fixed with the objective table of sample, and this is determined respectively A, B of a little particles, obtain A/B average value.
[[[[low-crystalline carbonaceous material]]]]
Low-crystalline carbonaceous material refers to that the interplanar distance (d002) in (002) face determined by X-ray wide-angle diffraction method is The low carbonaceous material of more than 0.340nm crystallinity.
(composition of low-crystalline carbonaceous material)
The crystallinity of " carbonaceous materials different from the crystallization of particle shape carbonaceous material " preferably than particle shape carbonaceous material is low Low-crystalline carbonaceous material.In addition, the carbide of (d) or (e) below particularly preferably.
(d) closed selected from coal class heavy oil, straight run class heavy oil, decomposition class black petroleum products, aromatic hydrocarbon, N cycle compounds, S cyclisation The organic matter being carbonized in thing, polyphenyl, organic synthesis macromolecule, natural polymer, thermoplastic resin and heat reactive resin；
(e) solution obtained from these organic matters that can be carbonized are dissolved in small molecular organic solvent.
It is used as coal class heavy oil, coal tar asphalt or destructive distillation liquefaction oil preferably from maltha to pitch etc.；As straight Evaporate class heavy oil, preferably atmospheric resids, decompression residual oil etc.；During as decomposing class black petroleum products, the preferably thermal decomposition such as crude oil, naphtha Ethylene bottom oil of by-product etc.；It is used as aromatic hydrocarbon, preferably acenaphthylene, decacyclene, anthracene, phenanthrene etc.；As N cycle compounds, preferably azophenlyene, Acridine etc.；It is used as S cycle compounds, preferably thiophene, di- thiophene etc.；It is used as polyphenyl, preferably biphenyl, terphenyl etc.；As organic Macromolecule, preferably polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, their insoluble processed material, polyacrylonitrile, poly- pyrrole Cough up, polythiophene, polystyrene etc.；As natural polymer, preferred cellulose, lignin, mannosan, polygalacturonic acid, Polysaccharides such as chitosan, sucrose etc.；It is used as thermoplastic resin, preferably polyphenylene sulfide, polyphenylene oxide etc.；It is excellent as thermosetting resin Select furfuryl alcohol resin, phenolic resin, imide resin etc..
The carbonization of " carbonaceous materials different from particle shape carbonaceous material crystallinity " preferably above-mentioned " organic matter that can be carbonized " Thing, it is also preferable to which these " organic matters that can be carbonized " are dissolved in into the low molecules such as benzene,toluene,xylene, quinoline, n-hexane The carbide of solution etc. is obtained in organic solvent.In addition, " carbonaceous materials different from particle shape carbonaceous material crystallinity " are excellent Coal separation class coke, the carbide of petroleum-type coke.
As above-mentioned (d) or (e), particularly preferred liquid.That is, from the viewpoint that interface is generated with graphite-like carbonaceous material part From the point of view of, preferably it is carbonized in the liquid phase.
(physical property of low-crystalline carbonaceous material)
Preferably any one or more in (1) shown below~(5) is met as the physical property of low-crystalline carbonaceous material simultaneously.Separately Outside, a kind of low-crystalline carbonaceous material for showing these physical property is can be used alone, can also be combined in any combination with ratio Use two or more.
(1) X-ray parameter
For low-crystalline carbonaceous material part, by using learning the lattice plane that the X-ray diffraction of method progress that shakes is tried to achieve The d values (interfloor distance) in (002 face) are more than 0.340nm, preferably more than 0.340nm for definition above, are particularly preferably More than 0.341nm.In addition, below 0.380nm is limited to thereon, particularly preferably below 0.355nm, more preferably 0.350 Below.If d values are excessive, the obvious low surface of crystallinity is formed, increases irreversible capacity sometimes, and if d values are too small, The effect that charging acceptance obtained from then setting low-crystalline carbonaceous material on surface is improved diminishes, so that the effect of the present invention Diminish.In addition, the crystallite size (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is usually more than 1nm, it is excellent Elect more than 1.5nm scope as.If less than the scope, crystallinity reduction increases the increasing of irreversible capacity at initial stage sometimes Greatly.
(2) ash content
Ash content contained by low-crystalline carbonaceous material part is preferably 1 mass % relative to the gross mass of composite carbonaceous material Hereinafter, more preferably below 0.5 mass %, particularly preferably below 0.1 mass %, are used as lower limit, preferably more than 1ppm.Such as Fruit exceedes above range, then the deterioration of battery performance can not be ignored during discharge and recharge and caused by the reaction of electrolyte.And if Less than the scope, then long period and energy and the equipment for preventing pollution are needed in manufacture, cost can rise sometimes.
(3) Raman R value, Raman half breadth
The R values of the low-crystalline carbonaceous material part determined using argon laser Raman spectroscopy are usually more than 0.5, Preferably more than 0.7, more preferably more than 0.9, its upper limit is usually less than 1.5, preferably less than 1.2 scope.If R values Less than the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, charge Acceptance is reduced sometimes.In addition, after coating on the current collector, when making negative pole densification by compacting, crystallization is easily orientated For the direction parallel with battery lead plate, part throttle characteristics reduction is occasionally resulted in.On the other hand, if it exceeds the scope, then particle surface Crystallinity reduction, with electrolyte reactivity increase, occasionally result in efficiency reduction or produce gas increase.
In addition, low-crystalline carbonaceous material part is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and leads to It is often 40cm-1More than, preferably 50cm-1More than, its upper limit is usually 100cm-1Hereinafter, preferably 90cm-1Hereinafter, more preferably For 80cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, with charge and discharge The site that electric Li enters interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.In addition, after coating on the current collector, passing through When compacting makes negative pole densification, crystallization is easily oriented to the direction parallel with battery lead plate, occasionally results in part throttle characteristics reduction.Separately On the one hand, if it exceeds the crystallinity reduction of the scope, then particle surface, increases with the reactivity of electrolyte, occasionally result in effect The gas increase that rate is reduced or produced.
(4) real density
The real density of low-crystalline carbonaceous material part is usually 1.4g/cm3More than, preferably 1.5g/cm3More than, it is more excellent Elect 1.6g/cm as3More than, more preferably 1.7g/cm3More than, its upper limit is usually 2.1g/cm3Hereinafter, preferably 2g/ cm3Below.If it exceeds the scope, the then acceptance that charges may be damaged.If less than the scope, the crystallinity of carbon is too low, Initial stage, irreversible capacity increased sometimes.
(5) orientation ratio (powder)
The orientation ratio of low-crystalline carbonaceous material part is usually more than 0.005, and preferably more than 0.01, more preferably More than 0.015, theoretical value is limited to thereon below 0.67.If less than the scope, high density charge-discharge characteristic is reduced sometimes, no It is preferred that.Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting carbon passes through X-ray (110) diffraction and the peak of (004) diffraction that diffraction is obtained, carry out peak separation, (110) diffraction and (004) diffraction are calculated respectively Peak integrated intensity.Calculated by obtained integrated intensity by (110) diffraction integral intensity/(004) diffraction integral intensity table The ratio shown, active material orientation ratio is defined as by the ratio.
[[[composite carbonaceous material]]]
The composite carbonaceous material used in negative pole [1] in the lithium secondary battery of the present invention preferably comprises " particle shape carbonaceous Material " and " carbonaceous materials different from the particle shape carbonaceous material crystallinity ", now, as long as any of which one is graphite-like Carbonaceous material, and another is low-crystalline carbonaceous material.Additionally, it is preferred that " particle shape carbonaceous material " is graphite-like carbonaceous Material, " carbonaceous materials different from the particle shape carbonaceous material crystallinity " are low-crystalline carbonaceous material.
In composite carbonaceous material, the mass ratio of graphite-like carbonaceous material and low-crystalline carbonaceous material is preferably 50/50 More than, more preferably more than 80/20, particularly preferably more than 90/10, and preferably below 99.9/0.1, more preferably 99/1 Hereinafter, particularly preferably less than 98/2 scope.If it exceeds above range, then can not obtain crystalline with 2 kinds sometimes The effect of carbonaceous material, if less than above range, initial stage, irreversible capacity showed increased tendency, sometimes in battery design On there is problem.Graphite-like carbonaceous material is more than 50 mass % relative to all composite carbonaceous materials.
(physical property of composite carbonaceous material)
As composite carbonaceous material, preferably any one or more in (1)~(11) shown below is met simultaneously.Separately Outside, a kind of composite carbonaceous material for showing these physical property is can be used alone, 2 can also be applied in combination with ratio in any combination More than kind.
(1) X-ray parameter
Composite carbonaceous material is by using the d values (interfloor distance) for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve Preferably more than 0.335nm, and usually below 0.350nm, preferably below 0.345nm, more preferably 0.340nm with Under.In addition, the crystallite dimension (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is usually more than 1.5nm, it is excellent Elect more than 3.0nm scope as.If less than the scope, crystallinity reduction, it is possible to increase the increasing of irreversible capacity at initial stage Greatly.
(2) ash content
Ash content contained by composite carbonaceous material is preferably below 1 mass %, more relative to the gross mass of composite carbonaceous material Preferably below 0.5 mass %, particularly preferably below 0.1 mass %, are used as its lower limit, preferably more than 1ppm.If super Above range is crossed, then the deterioration of battery performance can not be ignored during discharge and recharge and caused by the reaction of electrolyte.Should if be less than Scope, then need long period and energy and the equipment for preventing pollution in manufacture, and cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of composite carbonaceous material is the flat of the volume reference tried to achieve by laser diffraction/scattering method Equal particle diameter (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, 7 μm More than.In addition, its upper limit is usually less than 100 μm, and preferably less than 50 μm, more preferably less than 40 μm, more preferably Less than 30 μm, particularly preferably less than 25 μm.If less than above range, irreversible capacity increase occasionally results in electricity at initial stage The loss of tankage.In addition, if more than above range, then uneven coated face is easily formed when electrode pad is made, Sometimes it is undesirable in battery production process.
(4) Raman R value, Raman half value are wide
The R values of the composite carbonaceous material determined using argon laser Raman spectroscopy are usually more than 0.03, are preferably More than 0.10, more preferably more than 0.15, its upper limit is usually less than 0.60, preferably less than 0.50 scope.If R values are low In the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, charging Reduced sometimes by property.In addition, after coating on the current collector, when making negative pole densification by compacting, crystallization is easily oriented to The direction parallel with battery lead plate, occasionally results in part throttle characteristics reduction.On the other hand, if it exceeds the scope, then particle surface Crystallinity is reduced, and is increased with the reactivity of electrolyte, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, composite carbonaceous material is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and is usually 15cm-1More than, preferably 20cm-1More than, its upper limit is usually 70cm-1Hereinafter, preferably 60cm-1Hereinafter, more preferably 50cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, with discharge and recharge The site that Li enters interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.In addition, after coating on the current collector, passing through pressure When system makes negative pole densification, crystallization is easily oriented to the direction parallel with battery lead plate, occasionally results in part throttle characteristics reduction.It is another Aspect, if it exceeds the crystallinity reduction of the scope, then particle surface, increases with the reactivity of electrolyte, occasionally result in efficiency Reduction or the gas increase produced.
(5) BET specific surface area
The specific surface area of the composite carbonaceous material of the invention determined using BET method usually 0.1m2/ more than g, be preferably 0.7m2/ more than g, more preferably 1m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ below g, Preferably 25m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area is low In above range, then in the case where being used as negative material, the acceptance of lithium is deteriorated during charging, and lithium is easily in electrode surface Separate out.On the other hand, if it exceeds above range, then as negative material in use, increase with the reactivity of electrolyte, produce Gas become it is many, be difficult to obtain preferred battery sometimes.
(6) micropore is distributed
As complex class carbonaceous material, by mercury, Hg porosimeter (mercury penetration method) try to achieve equivalent to 0.01 μm of diameter Space in~1 μm of particle, due to the concavo-convex amount that causes of being uneven of particle surface be usually more than 0.01mL/g, it is excellent Elect more than 0.05mL/g, more preferably more than 0.1mL/g as, its upper limit is usually below 0.6mL/g, preferably 0.4mL/g with Under, more preferably below 0.3mL/g scope.If it exceeds the scope, then need substantial amounts of adhesive when pole plate is made.If Less than the scope, then high current density charge-discharge characteristic is reduced, also, electrode expansion when can not obtain discharge and recharge sometimes shrinks Alleviation effects.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then sometimes for Substantial amounts of adhesive.And if less than the scope, then can not obtain the scattered of thickener or binding agent sometimes when pole plate is made Effect.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 80 μm, preferably less than 50 μm, more preferably less than 20 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.And if less than the scope, then high current density charge-discharge characteristic is reduced sometimes.
(7) circularity
Using circularity as the spherical degree of composite carbonaceous material, the particle diameter of composite carbonaceous material is 3~40 μm of models The circularity of the particle enclosed is preferably more than 0.85, more preferably more than 0.87, more preferably more than 0.9.Circularity is big When, high current density charge-discharge characteristic is improved, therefore preferably.
(8) real density
The real density of composite carbonaceous material is usually 1.9g/cm3More than, preferably 2g/cm3More than, more preferably 2.1g/ cm3More than, more preferably 2.2g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theoretical value of graphite.If Less than the scope, then the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
(9) tap density
The tap density of composite carbonaceous material is usually 0.1g/cm3More than, preferably 0.5g/cm3More than, more preferably 0.7g/cm3More than, particularly preferably 1g/cm3More than.In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3 Hereinafter, particularly preferably 1.6g/cm3Below.If tap density be less than the scope, as negative pole in use, filling it is close Degree is difficult to improve, and the battery of high power capacity can not be obtained sometimes.On the other hand, if it exceeds the scope, then between the particle in electrode Space it is very few, it is difficult to ensure interparticle electric conductivity, be difficult to obtain preferred battery behavior sometimes.Tap density by with it is upper State method identical method to be measured, and defined according to this method.
(10) orientation ratio (powder)
The orientation ratio of composite carbonaceous material is usually more than 0.005, and preferably more than 0.01, more preferably more than 0.015, Its upper limit is less than 0.67 scope in theory.If less than the scope, high density charge-discharge characteristic is reduced sometimes.
(11) draw ratio (powder)
The draw ratio of composite carbonaceous material is theoretically more than 1, and its upper limit is usually less than 10, and preferably less than 8, it is more excellent Elect less than 5 as.If it exceeds its upper limit, produces striped, can not obtain uniform coated face, high current sometimes when pole plate is made Density charge-discharge characteristic is reduced.
(manufacture method of composite carbonaceous material)
The manufacture method of these composite carbonaceous materials has no particular limits, and can enumerate method as shown below.
The Composite of graphite-like carbonaceous material and low-crystalline carbonaceous material can use following methods：Directly it is used for The carbon precursor of low-crystalline carbonaceous material is obtained, heats the mixture of carbon precursor and graphite-like carbonaceous material powder, obtains The method of composite powder；By above-mentioned carbon precursor carry out partially carbonized, previously prepared low-crystalline carbonaceous material powder, then with graphite Class carbonaceous material powder is mixed, and heats the method to carry out Composite；The above-mentioned low-crystalline carbonaceous material powder of pre-production End, admixed graphite class carbonaceous material powder, low-crystalline carbonaceous material powder and carbon precursor, the method that heating carries out Composite Deng.In addition, in the method that latter two prepares low-crystalline carbonaceous material powder in advance, preferably using average grain diameter for graphite-like The low-crystalline carbonaceous material particle of less than/10th of the average grain diameter of carbonaceous material.Furthermore it is also possible to use with lower section Method：The mechanics energy such as crushing are applied by the low-crystalline carbonaceous material to pre-production and graphite-like carbonaceous material, one is made Kind of material is mingled with the structure in another material, or the structure of electrostatic adherence method.
Preferably, the mixture for being mixed with graphite-like carbonaceous material particle and carbon precursor is heated, obtains centre Material, or, the mixture and carbon precursor of graphite-like carbonaceous material particle and low-crystalline carbonaceous material particle are obtained by mixing To mixture heated, obtain intermediate material, then, carburizing sintering is crushed, and is thus finally given in graphite-like material grain Composite has the composite carbonaceous material of low-crystalline carbonaceous material in son.
It is divided into following 4 processes for obtaining the manufacturing process of composite carbonaceous material.
1st process：Using various commercially available mixers or kneading machine by (graphite-like carbonaceous material particle or (graphite-like carbon The stuff and other stuff of metallic substance particle and low-crystalline carbonaceous material particle)) and low-crystalline carbonaceous material particle carbon precursor And the solvent mixing being added as needed on, obtain mixture.
2nd process：Heat mixture, the intermediate of be removed solvent and the volatile ingredient produced by carbon precursor Matter.Now, as needed, can with while stir said mixture while carry out.Even if in addition, remain volatile ingredient, due to can be Removed in the 3rd follow-up process, so also out of question.
3rd process：Under the non-active gas atmosphere such as nitrogen, carbon dioxide, argon gas, by said mixture or intermediate material 400 DEG C~3200 DEG C are heated to, graphite low-crystalline carbonaceous material compound substance is obtained.
4th process：Above-mentioned compound substance is crushed, crushed as needed, classification processing etc. powder processing.
In these processes, can according to circumstances omit the 2nd process and the 4th process, the 4th process can also the 3rd process it It is preceding to carry out.But, when implementing 4 process before the 3rd process, the powder such as needed, crushed, crushed, is classified again Processing, obtains composite carbonaceous material.
In addition, as the heating condition of the 3rd process, thermal history temperature conditionss are important.The lower limit root of the temperature It is different according to the species of carbon precursor, the thermal history, but usually more than 400 DEG C, preferably more than 900 DEG C.On the other hand, Ceiling temperature can reach the temperature of the basic structural order without the crystalline texture for surmounting graphite-like carbonaceous material particle core. Therefore, as the ceiling temperature of heat treatment, usually less than 3200 DEG C, preferably less than 2000 DEG C, more preferably 1500 DEG C with Under.Under such heat treatment condition, programming rate, cooling velocity, heat treatment time etc. can arbitrarily be set according to purpose.Separately Outside, defined temperature can also be warming up to after being heat-treated than relatively low temperature province.In addition, used in this process Reactor can be batch (-type) or continous way, furthermore it is possible to which it can also be many to be one.
[[auxiliary material mixing]]
In addition to above-mentioned composite carbonaceous material, in the negative electrode active material of the lithium secondary battery of the present invention containing it is a kind of with The upper carbonaceous material (carbonaceous material) different in terms of the physical property of carbonaceous from above-mentioned composite carbonaceous material, it is possible thereby to further scheme Ask the raising of battery performance." physical property of carbonaceous " mentioned here, refers to X-ray diffraction parameter, median particle diameter, draw ratio, BET Specific surface area, orientation ratio, Raman R value, tap density, real density, micropore distribution, circularity, the more than one spy of ash amount Property.In addition, as preferred embodiment, can enumerate, when volume reference size distribution is centered on median particle diameter or so no Symmetrically, it is not equal containing the different carbonaceous material of two or more Raman R value or X-ray parameter.As an example of its effect, It can enumerate by containing graphite such as native graphite, Delaniums；The carbon blacks such as acetylene black；The carbon materials such as the amorphous carbon such as needle coke are made Resistance etc. is reduced for auxiliary material.They can be used alone one kind, can also be applied in combination 2 with arbitrary proportion in any combination More than kind.When being added as auxiliary material, its addition is more than 0.1 mass %, preferably more than 0.5 mass %, is more preferably More than 0.6 mass %, is limited to below 80 mass % thereon, preferably below 50 mass %, more preferably below 40 mass %, enters One step is preferably the scope below 30 mass %.If less than the scope, the effect for obtaining electric conductivity raising is difficult to sometimes.Such as Fruit exceedes above range, then sometimes results in the increase of irreversible capacity at initial stage.
[making negative pole [1] electrode]
Usual way can be used by manufacturing negative pole [1], can form negative pole [1] as described above.Collector, current collection Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of body and active material layer etc. are also same as described above.
<Negative pole [2]>
Below, the negative pole [2] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains amorphous carbonaceous As active material, the amorphous carbonaceous use wide-angle x-ray diffraction determine (002) face interplanar distance (d002) for More than 0.337nm, crystallite size (Lc) is below 80nm, with 1360cm in argon laser Raman spectroscopy-1Peak intensity Relative to 1580cm-1The Raman R value that defines of ratio of peak intensity be more than 0.2.
[negative electrode active material of negative pole [2]]
Below, the negative electrode active material used in negative pole [2] is illustrated.
The negative electrode active material used in the negative pole [2] of the lithium secondary battery of the present invention is at least to contain below satisfaction (a), the amorphous carbonaceous of (b) and (c).
(a) interplanar distance (d002) in (002) face of wide-angle x-ray diffraction measure is used for more than 0.337nm；
(b) the crystallite size Lc in (002) face of wide-angle x-ray diffraction measure is used for below 80nm；
(c) with 1360cm in argon laser Raman spectroscopy-1Peak intensity relative to 1580cm-1Peak intensity The Raman R value (following, sometimes referred to simply as " Raman R value ") that ratio is defined is more than 0.2.
The negative electrode active material used in the present invention is at least containing the amorphous carbonaceous for meeting (a), (b) and (c), these nothings Content of the carbonaceous that shapes in total negative electrode active material is preferably more than 10 mass % more preferably more than 50 mass %, especially Preferably 100 mass %, that is, all active materials are all amorphous carbonaceous.As with amorphous carbonaceous be applied in combination it is negative Pole active material, there is no particular limitation, can use known negative electrode active material, for example, Delanium, native graphite Deng.
[[interplanar distance (d002), Lc]]
The amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] passes through wide-angle The interplanar distance (d002) in (002) face that X-ray diffraction method is determined is more than 0.337nm, preferably more than 0.34nm.Its upper limit is led to It is often below 0.39nm, more preferably preferably below 0.38nm, more preferably below 0.37nm, below 0.36nm, spy You Xuanwei not below 0.35nm.If it exceeds the scope, then crystallinity is significantly reduced, and the reduction of interparticle electric conductivity can not be neglected Depending on being difficult to the raising effect for obtaining short time high current density charge-discharge characteristic sometimes.On the other hand, if being less than the scope, Then crystallinity becomes too high, and the raising effect for obtaining short time high current density charge-discharge characteristic is difficult to sometimes.
The interplanar distance (d002) in (002) face that the use wide-angle x-ray method described in the present invention is determined refers to by using The d values (interfloor distance) in lattice plane (002) face that the X-ray diffraction for method of shaking is tried to achieve.
The crystallite size (Lc) in (002) face for the amorphous carbonaceous tried to achieve by using the X-ray diffraction for learning method measure of shaking For below 80nm, more preferably preferably below 35nm, more preferably below 20nm, below 10nm.Its lower limit is usually More than 0.1nm, preferably more than 1nm.If less than the scope, crystallinity is significantly reduced, sometimes between particle electric conductivity drop It is low to ignore, also, it is difficult to the raising effect that obtains short time high current density discharge and recharge sometimes.On the other hand, if super The scope is crossed, then crystallinity becomes too high, the raising effect for obtaining short time high current density discharge and recharge is difficult to sometimes.
[[Raman R value]]
The Raman R of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] Value is necessary for more than 0.2, preferably more than 0.5, particularly preferably more than 0.7, more preferably more than 0.8.Its upper limit is usually Less than 1.5, more preferably less than 1.2.If Raman R value is less than the scope, the crystallinity of particle surface is too high, charging by Property reduction, therefore, the raising effect for obtaining short time high current density charge-discharge characteristic is difficult to sometimes.On the other hand, if super The scope is crossed, then the crystallinity of particle surface is remarkably decreased, therefore, interparticle contact resistance becomes big, is difficult to obtain short sometimes The raising effect of time high current density discharge and recharge.
Raman spectrum is determined as follows progress：Using raman spectroscopy device (for example, the raman spectroscopy that Japanese light splitting company manufactures Device), sample is naturally fallen in measure container, carry out sample filling, continuous mode is that the specimen surface in container is irradiated Argon laser, while making the container be rotated in the face with laser vertical.For obtained Raman spectrum, 1580cm is determined-1 Peak PAIntensity IAAnd 1360cm-1Peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as amorphous The Raman R value of carbonaceous.In addition, determining obtained Raman spectrum in 1580cm-1Peak PAHalf breadth, be defined as without fixed The Raman half breadth of shape carbonaceous.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
Raman R value, the analysis of Raman half breadth：Background processing
Smooth treatment：Simple average, 5 points of convolution
In addition, the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] exists 1580cm-1Raman half breadth have no particular limits, usually 20cm-1More than, preferably 25cm-1More than, in addition, its The upper limit is usually 150cm-1Hereinafter, preferably 140cm-1Following scope.If Raman half breadth is less than the scope, grain The crystallinity in sublist face becomes too high, charging acceptance reduction, therefore, is difficult to obtain short time high current density discharge and recharge sometimes Raising effect.On the other hand, if it exceeds above range, then the crystallinity of particle surface is significantly reduced, therefore, interparticle Contact resistance becomes big, it is possible to be difficult to the raising effect for obtaining short time high current density discharge and recharge.But, Raman half breadth Sometimes it can not be judged by peak shape.
The amorphous carbonaceous that the present invention is used meets above-mentioned interplanar distance (d002), crystallite size (Lc) and Raman R value Condition, but from the balance of battery on this point for, any one or more bar in following projects is more preferably met simultaneously Part.Among these, particularly preferably real density, H/C values, O/C values, tap density, BET specific surface area, 0.01 μm~1 are met simultaneously Any one or more condition in micropore volume, ash content and the volume average particle size of μ m.
[[real density]]
The real density of amorphous carbonaceous is usually 2.22g/cm3Hereinafter, preferably 2.2g/cm3Hereinafter, more preferably 2.1g/ cm3Hereinafter, more preferably 2.0g/cm3Hereinafter, its lower limit is usually 1.4g/cm3More than, preferably 1.5g/cm3More than, More preferably 1.6g/cm3More than, more preferably 1.7g/cm3More than, particularly preferably 1.8g/cm3Scope above.Such as Fruit is less than the scope, then the crystallinity of carbon is too low, and irreversible capacity at initial stage increases sometimes.If it exceeds the knot of the scope, then carbon Crystalline substance is too high, it is difficult to obtain the raising effect of short time high current density discharge and recharge.
In the present invention, real density is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol.
[[O/C values]]
The upper limit of the atom proportion O/C values of amorphous carbonaceous is usually less than 0.15, and preferably less than 0.1, more preferably Less than 0.05, more preferably less than 0.03, its lower limit is usually more than 0, and preferably more than 0.01.
O/C values represent the ratio of the molar concentration of oxygen atom present in amorphous carbonaceous and the molar concentration of carbon atom, It is the index for the amount for representing the functional groups such as carboxyl, phenolic hydroxyl group, carbonyl.The big amorphous carbonaceous of O/C values is mostly micro- in carbon Brilliant end face etc. is combined with oxygen-containing functional group.O/C values are if it exceeds above range, then irreversible capacity increases sometimes.
[[H/C values]]
The upper limit of the atom proportion H/C values of amorphous carbonaceous is usually less than 0.3, and preferably less than 0.15, more preferably Less than 0.1, more preferably less than 0.08, its lower limit is usually more than 0, and preferably more than 0.01.
So-called H/C values, represent the molar concentration of hydrogen atom present in amorphous carbonaceous and the molar concentration of carbon atom Ratio, is the index of the amount of hydrogen for representing to be present on the crystallite end face of amorphous carbonaceous.The big amorphous carbonaceous of H/C values Material, represents that crystallite end face of particle face carbon etc. is more than the amount of carbon mostly.If H/C values exceed above range, sometimes can not Inverse capacity increase.
Described " O/C values " and " H/C values " is obtained by CHN elementary analyses shown below in the present invention.
[[CHN elementary analyses]]
Amorphous carbonaceous to be determined is dried under reduced pressure about 15 hours at 120 DEG C, the hot plate in drying box is then placed on On at 100 DEG C dry 1 hour.Then, in argon atmosphere, sample is placed in aluminium cup, the titanium dioxide produced by burning The weight of carbon gas obtains carbon content, in addition, the weight for the water for passing through generation obtains hydrogen content, passes through the nitrogen dioxide of generation Weight calculates nitrogen content, and the weight of the residue remained after burning obtains inorganic content.The value of oxygen content is by from gross weight In subtract carbon content, hydrogen content, nitrogen content, inorganic content and draw.Molal quantity is calculated by these values, using each obtained Content molal quantity obtains O/C values, H/C values by following formula.
O/C values=oxygen-containing molal quantity/carbon containing molal quantity
H/C values=hydrogeneous molal quantity/carbon containing molal quantity
[[tap density]]
The tap density of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the active material of negative pole [2] is excellent Elect 0.1g/cm as3More than, more preferably 0.2g/cm3More than, more preferably 0.5g/cm3More than, particularly preferably 0.7g/ cm3More than.In addition, its upper limit is preferably 1.4g/cm3Hereinafter, more preferably 1.2g/cm3Hereinafter, particularly preferably 1.1g/cm3 Below.If tap density is less than the scope, it is difficult to improve packed density, interparticle contact area when using as negative pole Reduce, therefore interparticle impedance increase, short time high current density charge-discharge characteristic is reduced sometimes.On the other hand, if More than the scope, then the interparticle space in electrode is very few, and the stream of nonaqueous electrolytic solution can be reduced, therefore be reduced sometimes short Time high current density charge-discharge characteristic.
In the present invention, tap density is defined as below：Make sieve of the sample by 300 μm of aperture, sample is fallen into 20cm3 Jolt ramming container in, to sample full of container upper surface after, using powder density determination device (for example, seishin enterprise-like corporations The Tap densor of manufacture), carry out 1000 length of stroke 10mm vibration, by thus when volume and the weight of sample obtain Density be used as tap density.
[[BET specific surface area]]
The amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] passes through BET The specific surface area that method is determined is preferably 0.1m2/ more than g, particularly preferably 0.5m2/ more than g, more preferably 0.7m2/ more than g, enters One step is preferably 1.5m2/ more than g.Its upper limit is preferably 100m2/ below g, particularly preferably 50m2/ below g, more preferably 25m2/ below g, more preferably 15m2/ below g.If the value of BET specific surface area is less than the scope, negative pole material is being used as In the case of expecting use, in charging, the acceptance of lithium is easily deteriorated, and lithium can be separated out in electrode surface sometimes.On the other hand, BET The value of specific surface area is if it exceeds the scope, as negative material in use, increasing with the reactivity of nonaqueous electrolytic solution, generation Gas becomes many, cannot get preferred battery sometimes.
The value that BET specific surface area is defined as：Using surface area meter (for example, the full-automatic surface that big storehouse reason development is made Product determines device), nitrogen circulation, sample is carried out at 350 DEG C 15 minutes it is predrying, then, using nitrogen relative to air The relative pressure of pressure is accurately adjusted to 0.3 nitrogen helium mixture, by using the N2 adsorption BET1 point methods of gas flow method The value of measure.
[[volume average particle size]]
The volume of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] is put down Equal particle diameter is defined as the average grain diameter (median particle diameter) for the volume reference tried to achieve by laser diffraction/scattering method, usually 1 μm with On, preferably more than 3 μm, more preferably more preferably more than 5 μm, more than 7 μm.In addition, its upper limit be usually 50 μm with Under, preferably less than 40 μm, more preferably more preferably less than 30 μm, less than 25 μm.If being less than above range, no Reversible capacity increases, and occasionally results in the loss of initial cell capacity.In addition, if more than above range, then the pole of electrode is made During plate, uneven coated face is easily formed, is sometimes undesirable in battery production process.
[[micropore volume]]
The micropore volume of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] Product, the space in particle of 0.01 μm~1 μm equivalent to diameter tried to achieve by mercury, Hg porosimeter (mercury penetration method), due to The concavo-convex amount caused that is uneven of particle surface is more than 0.01mL/g, preferably more than 0.05mL/g, is more preferably More than 0.1mL/g, its upper limit is usually below 0.6mL/g, preferably below 0.4mL/g, more preferably below 0.3mL/g model Enclose.If it exceeds the scope, then need substantial amounts of adhesive when being manufactured into pole plate.And if less than the scope, then the short time is high Current density charge-discharge characteristic is reduced, also, the alleviation effects that electrode expansion when can not obtain discharge and recharge sometimes shrinks.
In addition, preferred more than the 0.1mL/g of total micropore volume, more preferably more than 0.25mL/g, its upper limit is usually 10mL/ Below g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then sometimes for substantial amounts of Adhesive.If less than the scope, the dispersion effect of thickener or binding agent can not be obtained sometimes when pole plate is made.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.On the other hand, if less than the scope, short time high current density discharge and recharge sometimes is special Property reduction.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).About 0.2g samples (negative material) are weighed, are encapsulated into powder container, in room temperature, very (50 μm of below Hg) deaerate within 10 minutes under sky, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, mercury is imported, Boosted to from 4psia (about 28kPa) stage shape after 40000psia (about 280MPa), then be depressurized to 25psia (about 170kPa).Rise Number of stages during pressure more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury intrusion for 80.Use Washburn formulas calculate micropore distribution from the mercury press-in curve so obtained.In addition, the surface tension (γ) of mercury is 485dyne/cm, contact angle (φ) is 140 °.Micropore diameter when mean pore footpath reaches 50% using accumulation micro pore volume.
[[ash content]]
Contained ash content is preferably below 1 mass %, more preferably relative to the gross mass of carbonaceous material in carbonaceous material Below 0.5 mass %, particularly preferably below 0.1 mass %, in addition, being used as lower limit, in mass, preferably more than 1ppm. If it exceeds above range, then the deterioration of battery performance can not be neglected caused by the reaction with nonaqueous electrolytic solution during discharge and recharge Depending on.On the other hand, if less than the scope, long period and energy are needed in manufacture and for preventing setting for pollution Standby, cost can rise sometimes.
[[circularity]]
The circularity of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] Usually more than 0.1, preferably more than 0.8, more preferably more than 0.85, more preferably more than 0.9.It is used as the upper limit, circle Shape degree reaches theoretic proper sphere when being 1.If less than the scope, the fillibility of negative electrode active material is reduced, interparticle Impedance increases, and short time high current density charge-discharge characteristic is reduced sometimes.
The circularity of the present invention is defined with following formula.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
Following value is used as the value of circularity：Using such as flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured, and is determined using it Average value.
[[orientation ratio]]
The orientation ratio of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] Usually more than 0.005, preferably more than 0.01, more preferably more than 0.015, its upper limit is less than 0.67 in theory.Such as Fruit is less than the scope, then short time high density charge-discharge characteristic is reduced sometimes.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.By obtained integrated intensity, calculate strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：
Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
[[draw ratio]]
The draw ratio of the amorphous carbonaceous used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] Theoretically more than 1, the upper limit is usually less than 10, preferably less than 8, more preferably less than 5.If it exceeds its upper limit, then exist Striped is produced when pole plate is made sometimes, uniform coated face can not be obtained, the reduction of short time high current density charge-discharge characteristic.
In addition, during draw ratio three dimensional viewing the most major diameter A of carbonaceous material particle and perpendicular most minor axis B ratio A/B is represented.The observation of carbon particle with the scanning electron microscope of amplifying observation by that can be carried out.Any selection is fixed on Thickness is 50 particles on the end face of less than 50 μm of metallic plate, and rotation, inclination are fixed with the objective table of sample, determined respectively A, B of these particles, obtain A/B average value.
In addition, what is contained in being used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [2] is amorphous Carbonaceous is preferably selected from the amorphous carbonaceous of following (1)~(4).
(1) carbide in coal class coke, petroleum-type coke, furnace black, acetylene black and pitch-based carbon fiber is entered again Material obtained from row heat treatment；
(2) asphalt stock, aromatic hydrocarbon, N cycle compounds, S cycle compounds, polyphenyl, organic synthesis macromolecule, day will be selected from Organic matter and/or its thermal decomposition product in right macromolecule, thermoplastic resin and thermosetting resin and/or further heat treatment and Obtained material；
(3) organic matter of (2) is dissolved in small molecular organic solvent and obtained the pyrolysate and/or further of solution It is heat-treated and obtains material；
(4) carbide of the gas containing organic matter.
For (2), as long as the material that can be carbonized, can be enumerated, asphalt stock, acenaphthylene, decacyclene, The aromatic hydrocarbons such as anthracene, phenanthrene；The N cycle compounds such as azophenlyene or acridine；The S cycle compounds such as thiophene, di- thiophene；Biphenyl, terphenyl etc. Polyphenyl；It is polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, their crosslinking Treatment thing, insoluble processed material, nitrogenous poly- The organic polymers such as acrylonitrile, polypyrrole；The organic polymers such as polythiophene, the polystyrene of sulfur-bearing；With cellulose, lignin, Mannosan, polygalacturonic acid, chitosan, sucrose are the natural polymers such as the polysaccharide of representative；Polyphenylene sulfide, polyphenylene oxide etc. Thermoplastic resin；The thermosetting resins such as furfuryl alcohol resin, phenolic resin, imide resin；Or dissolve them in benzene, toluene, The organic matter such as solution formed by the small molecular organic solvents such as dimethylbenzene, quinoline, n-hexane；Containing these organic matters can carbon Gas of change etc..
Among these, because the carbon yield (carbon yield) of asphalt stock is high, the material of high income can be made, therefore it is preferred that. In addition, in this specification, " asphalt stock " is pitch and belongs to the material of pitch, refer to that carbon can be carried out by appropriate processing Change or graphited material.As the example of specific asphalt stock, tar, heavy oil or pitch etc. can be used.It is used as tar Specific example, coal tar, petroleum-type tar etc. can be enumerated.As the specific example of heavy oil, petroleum-type heavy oil can be enumerated Oil, thermal decomposition oil, atmospheric resids, decompression residual oil etc. are decomposed in contact.In addition, as the specific example of pitch, coal tar can be enumerated Pitch, petroleum-type pitch, synthetic asphalts etc..Wherein, the armaticity of coal tar asphalt is high, therefore it is preferred that.These asphalt stocks can be with Any one is used alone, two or more can also be applied in combination with ratio in any combination.
As the preferred example of (3), it can enumerate and the organic matter of above-mentioned (2) is dissolved in benzene,toluene,xylene, quinoline, just Obtain solution in the small molecular organic solvents such as hexane, then using the pyrolysate of the solution as precursor carbide.
On (4), the hydrocarbon compounds such as methane, ethane, propane, benzene, acetylene, ethene can be enumerated；Carbon monoxide etc..
It is preferred that carrying out crosslinking Treatment.So-called crosslinking Treatment, is in order to which asphalt stock for will carrying out crosslinking Treatment etc. is carried out The carbonaceous material being thermally treated resulting in carries out difficult graphitization and carried out, and is handled by implementing these, can increase unit mass Charging capacity.
As the example of crosslinking Treatment, the processing method that can be listed below：In divinylbenzene, trivinylbenzene, adjacent benzene Work is used in the vinyl monomers such as diformazan diallyl phthalate, ethylene glycol dimethacrylate, N,N methylene bis acrylamide For the α of radical polymerization initiator, α '-azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauroyl peroxide, hydrogen Crosslinking Treatment as dicumyl peroxide, t-butyl hydroperoxide, hydrogen peroxide etc.；Use the oxygen such as oxygen, ozone, nitrogen dioxide The property changed gas, the oxidizing liquid such as sulfuric acid, nitric acid, aqueous hydrogen peroxide solution and the oxidizer treatment carried out.It is used as crosslinking Treatment Method an example, can be set forth in makes the temperature control of asphalt stock in the state of 50 DEG C~400 DEG C, with crosslinking agent Or the method that the mixing such as oxidant is handled again.
[[Li-NMR movements]]
If in the state of full charge is charged to, lived to the negative pole of so-called negative pole [2] in the lithium secondary battery of the present invention Property substance migration amorphous carbonaceous carry out7When Li-NMR is analyzed, the low magnetic of the resonance line to primary standard substance LiCl observed Move 80~200ppm primary resonance peak in field side, then in order to increase the capacity of per unit mass amorphous carbon metallic substance, preferably Use the amorphous carbon metallic substance Jing Guo crosslinking Treatment.
[[preparation method of amorphous carbonaceous]]
As long as the preparation method of above-mentioned amorphous carbonaceous is in the scope of the main points without departing from the present invention, then without special Limitation, can enumerate various methods.In the making of amorphous carbonaceous, it is necessary to by 1 heat treatment step, but it is also possible to by heat Processing is divided into more than 2 times, further preferably before and after heat treatment and/or interstage of heat treatment carries out various processing.It is so-called each Processing is planted, crushing, classification, above-mentioned crosslinking Treatment etc. can be enumerated, as long as crushing, classification processing solid state then can be in heat The front and rear, the interstage of processing one of any is carried out.Crosslinking Treatment is preferably before being heat-treated or the interstage is carried out.It is logical Cross and carry out these processing, the specific surface area of negative electrode active material can be controlled, and increase the capacity of unit mass.
The device used in crushing before heat treatment has no particular limits, for example, as Roughpulverizer, can enumerate and cut Cut mill, jaw crusher, impact type crushing machine, cone crusher etc., as middle pulverizer, can enumerate roll-type crushing Machine, beater grinder etc., as atomizer, can enumerate ball milling, vibromill, sprayer of hammer crusher, Ball-stirring mill, jet mill etc..
As the device used in the heat treatment of raw material, have no particular limits, for example, shuttle-type stove (シ ャ ト Le can be used Stove), car tunnel furnace (ト Application ネ Le stove), electric furnace, coke roaster (リ ー De Ha ン マ ー stoves), rotary furnace, the reaction such as autoclave Device, coke (heat treatment groove of cokes manufactures), direct-electrifying stove etc..When handling raw material, it can be stirred as needed.
Temperature conditionss when being heat-treated have no particular limits, usually more than 600 DEG C, preferably more than 900 DEG C, In addition, its upper limit is usually less than 2500 DEG C, preferably less than 1300 DEG C.When temperature conditionss are less than above range, crystallinity becomes Obtain too low, it is possible to increase irreversible capacity.On the other hand, if it exceeds prescribing a time limit thereon, then crystallinity becomes too high, it is possible to Make the reduction of short time high current density charge-discharge characteristic.
For the amorphous carbonaceous after heat treatment, it can be crushed or be classified according to its block or the size of particle. Crush the device used to have no particular limits, for example, as Roughpulverizer, shearing mill, jaw crusher, punching can be enumerated Formula crushing machine, cone crusher etc. are hit, as middle pulverizer, roll crusher, beater grinder etc. can be enumerated, as micro- Pulverizer, can be enumerated, ball milling, vibromill, sprayer of hammer crusher, Ball-stirring mill, jet mill etc..The device used in classification processing does not have There is special limitation, for example, in the case where dry type is sieved, gyratory sifter, rock type sieve, rotary type sieve (rotation Move can be used Shi Sieve), oscillatory type sieve etc., in the case of dry type air current classifying, can use gravity type grader, inertia force formula grader, Centrifugal force type grader (sizer, cyclone separator) etc., in addition, wet screening can use mechanical wet classifier, water Power grader, settling classifier, centrifugal wet classifier etc..
[electrode for making negative pole [2]]
The manufacture of negative pole [2] can use usual way, can form negative pole [2] as described above.Collector, collection Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of electric body and active material layer etc. are also same as described above.
＜ negative poles [3] ＞
Below, the negative pole [3] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains metal oxide As negative electrode active material, the metal oxide contains being capable of occlusion and the titanium for releasing lithium.
[negative electrode active material of negative pole [3]]
Below, the negative electrode active material used in negative pole [3] is illustrated.
[[composition of negative electrode active material]]
The negative electrode active material used in the negative pole [3] of the lithium secondary battery of the present invention contains metal oxide, the gold Category oxide contains being capable of occlusion and the titanium for releasing lithium.In metal oxide, preferably lithium and titanium composite oxides (it is following, Referred to as " lithium-titanium composite oxide "), in addition, the metal oxide preferably has the titanium-containing metal oxide of spinel structure. In addition, in anode active material for lithium secondary battery using simultaneously meet the metal oxide of these conditions, that is, contain During lithium-titanium composite oxide with spinel structure, output impedance can be greatly reduced, therefore particularly preferably.
Additionally, it is preferred that the lithium or titanium in lithium-titanium composite oxide are by other metallic elements, be selected from Na, K, Co, Al, At least one of Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb element substitution.
The metal oxide be formula (1) represent lithium-titanium composite oxide, from doping/dedoping of lithium ion when knot From the point of view of structure is stable, preferably in formula (1), 0.7≤x≤1.5,1.5≤y≤2.3,0≤z≤1.6.
LixTiyMzO4 (1)
[in formula (1), M is represented selected from least one of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb member Element].
In the composition that above-mentioned formula (1) represents, structure as shown below is good due to the balance of battery performance, therefore especially excellent Choosing.
In formula (1) LixTiyMzO4In,
(a) 1.2≤x≤1.4,1.5≤y≤1.7, z=0
(b) 0.9≤x≤1.1,1.9≤y≤2.1, z=0
(c) 0.7≤x≤0.9,2.1≤y≤2.3, z=0
The particularly preferred composition represented of above-claimed cpd as：(a) it is Li4/3Ti5/3O4, (b) be Li1Ti2O4, (c) be Li4/5Ti11/5O4。
In addition, for the structure of Z ≠ 0, such as Li can be enumerated4/3Ti4/3Al1/3O4It is used as preferred composition.
[[physical property, shape of negative electrode active material etc.]]
The negative electrode active material that uses is preferably in addition to above-mentioned important document in the negative pole [3] of the lithium secondary battery of the present invention, Also meet at least one of following physical property.In addition, particularly preferably in addition to above-mentioned important document, while meeting in following physical property More than at least two kinds of.
[[[BET specific surface area]]]
The metal oxide containing titanium that the negative electrode active material of negative pole [3] in the lithium secondary battery of the present invention is used leads to The specific surface area for crossing BET method measure is preferably 0.5m2/ more than g, more preferably 0.7m2/ more than g, particularly preferably 1.0m2/ g with On, more preferably 1.5m2/ more than g.Its upper limit is preferably 200m2/ below g, more preferably 100m2/ below g, it is especially excellent Elect 50m as2/ below g, more preferably 25m2/ below g.If the value of BET specific surface area is less than the scope, as negative In the case of the materials'use of pole, the response area contacted with nonaqueous electrolytic solution is reduced, and output impedance increases sometimes.On the other hand, The value of BET specific surface area is if it exceeds the scope, then the crystal surface of the metal oxide containing titanium or end face part increase, and And the inequality (askew) of crystallization is thus also produced, irreversible capacity becomes unable to ignore, and cannot get preferred battery sometimes.
The value that BET specific surface area is defined as：Using surface area meter (for example, the full-automatic surface that big storehouse reason development is made Product determines device), nitrogen circulation, sample is carried out at 350 DEG C 15 minutes it is predrying, then, using nitrogen relative to air The relative pressure of pressure is accurately adjusted to 0.3 nitrogen helium mixture, by using the N2 adsorption BET1 point methods of gas flow method The value of measure.
[[[volume average particle size]]]
The metal oxide containing titanium used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [3] Volume average particle size (primary particle condense and be aggregate particle size when forming offspring) be defined as by laser diffraction/dissipate The average grain diameter (median particle diameter) for the volume reference that the method for penetrating is tried to achieve, more preferably more than 0.5 μm, enters one by preferably more than 0.1 μm Step is preferably more than 0.7 μm.In addition, its upper limit is usually less than 50 μm, and preferably less than 40 μm, more preferably less than 30 μm, More preferably less than 25 μm.If less than above range, needing substantial amounts of adhesive when making electrode, as a result sometimes Battery capacity is reduced.In addition, if more than above range, then when the pole plate of electrode is made, uneven coated face is easily formed, Sometimes it is undesirable in battery production process.
[[[average primary particle diameter]]]
When primary particle condenses and forms offspring, the negative electrode active material of the lithium secondary battery as the present invention is used as The average primary particle diameter of the metal oxide containing titanium be preferably more than 0.01 μm, more preferably more than 0.05 μm, further Preferably more than 0.1 μm, most preferably more than 0.2 μm, its upper limit is preferably less than 2 μm, more preferably less than 1.6 μm, enters one Step is preferably less than 1.3 μm, most preferably less than 1 μm.If average primary particle diameter exceedes the above-mentioned upper limit, it is difficult to form spherical Offspring, bring harmful effect, or specific surface area to be greatly reduced powder fillibility, therefore, the battery such as output characteristics The possibility of performance reduction is uprised sometimes.If on the contrary, average primary particle diameter is less than above-mentioned lower limit, being typically due to crystallization endless Entirely, therefore sometimes produce discharge and recharge it is poorly reversible the problems such as.
Primary particle size can be determined by using the observation of SEM (SEM).Specifically, by the following method Obtain：In the photo of 10000~100000 times of multiplying power, arbitrary 50 primary particles are obtained on the straight line of horizontal direction The greatest length of the section produced by the left bounding lines of primary particle, and take its average value.
[[[shape]]]
The shape of particle for being somebody's turn to do the metal oxide containing titanium used in the negative pole [3] of the lithium secondary battery of the present invention can make With the bulk used, polyhedral, spherical, oval spherical, tabular, needle-like, column etc. in the past, wherein, preferably primary particle coagulates It is poly- and form offspring, and the offspring be shaped as it is spherical or oval spherical.Generally, electrochemical element is with its charge and discharge Active mass expansion in electricity, electrode shrinks, therefore easily occurs due to the destruction of active material or conduction caused by the stress The deteriorations such as path cut-out.Therefore, compared with the single particle active material of simply primary particle, preferably primary particle condenses and shape Into the situation of offspring, because the stress of dilation can be relaxed by forming offspring, so as to prevent deterioration.In addition, with The particle of the isometric orientation of tabular is compared, preferably spherical or oval spherical particle, because spherical or oval spherical particle exists Orientation during electrode moulding is few, and the dilation of electrode during discharge and recharge is also few, and when making electrode and conductive agent it is mixed During conjunction, also easily uniform mixing.
[[[tap density]]]
The oxidation of the metal containing titanium that the negative electrode active material as negative pole [3] in the lithium secondary battery of the present invention is used The tap density of thing is preferably 0.05g/cm3More than, more preferably 0.1g/cm3More than, more preferably 0.2g/cm3More than, Particularly preferably 0.4g/cm3More than.In addition, its upper limit is preferably 2.8g/cm3Hereinafter, more preferably 2.4g/cm3Hereinafter, especially Preferably 2g/cm3Below.If tap density is less than the scope, it is difficult to improve packed density when using as negative pole, and Interparticle contact area is reduced, therefore interparticle impedance increase, increases output resistance sometimes.On the other hand, if super The scope is crossed, then the interparticle space in electrode is very few, the stream of nonaqueous electrolytic solution can be reduced, therefore increase output sometimes Resistance.
In the present invention, tap density is defined as below：Make sieve of the sample by 300 μm of aperture, sample is fallen into 20cm3 Jolt ramming container in, to sample full of container upper surface after, using powder density determination device (for example, seishin enterprise-like corporations The Tap densor of manufacture), carry out 1000 length of stroke 10mm vibration, by thus when volume and the weight of sample obtain Density be used as tap density.
[[[circularity]]]
The metal oxide containing titanium used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [3] Circularity be usually more than 0.10, preferably more than 0.80, more preferably more than 0.85, more preferably more than 0.90. As the upper limit, turn into theoretic proper sphere when circularity is 1.If less than the scope, the fillibility of negative electrode active material drops It is low, interparticle impedance increase, sometimes short time high current density charge-discharge characteristic reduction.
The circularity of the present invention is defined with following formula.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
Following value is used as the value of circularity：Using such as flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range, value obtained from being measured to the particle of the μ m of particle diameter 3~40 to specify 0.6~400 μm.
[[[draw ratio]]]
The metal oxide containing titanium used in the lithium secondary battery of the present invention as the negative electrode active material of negative pole [3] Draw ratio be theoretically more than 1, the upper limit be less than 5, preferably less than 4, more preferably less than 3, more preferably 2 with Under.If it exceeds its upper limit, then produce striped, can not obtain uniform coated face sometimes when pole plate is made, the short time is high Current density charge-discharge characteristic is reduced.
In addition, the most major diameter of particle during three dimensional viewing is set as A and by perpendicular when most minor axis is set as B, it is long Footpath ratio is represented with A/B.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.Any selection is solid 50 graphite particles on the end face for the metallic plate that thickness is less than 50 μm are scheduled on, rotation, inclination are fixed with the objective table of sample, A, B of these particles are determined respectively, obtain A/B average value.
[[autofrettage of negative electrode active material]]
As the autofrettage of the negative electrode active material of the negative pole [3] in the lithium secondary battery of the present invention, no more than this hair Be not particularly limited in the range of bright main idea, several method can be enumerated, can use as inorganic compound autofrettage it is logical Normal method.The titanium material material such as can enumerate titanium oxide, the raw material of the other elements used as needed and LiOH、Li2CO3、LiNO3Uniformly mixed Deng Li sources, the method for sintering at high temperature and obtaining active material.Particularly making During spherical or oval spherical active material, it is contemplated that various methods, for example, it can be listed below method：By titanium materials such as titanium oxide Material, the raw material dissolving of the other elements used as needed or grinding dispersion are adjusted while stirring in water equal solvent PH, makes and obtains spherical precursor, after being dried as needed, adds LiOH, Li2CO3、LiNO3Deng Li sources, in high temperature Lower sintering and the method that obtains active material；By the titanium material such as titanium oxide material, the raw material of the other elements used as needed Material dissolves or grinding dispersion is dried shaping in water equal solvent, then by spray dryer etc., and spherical or ellipse is made Spherical precursor, then adds LiOH, Li wherein2CO3、LiNO3Deng Li sources, sinter at high temperature and obtain active material Method；And by the titanium material such as titanium oxide material and LiOH, Li2CO3、LiNO3Deng Li sources and other yuan used as needed The raw material dissolving of element or grinding dispersion are dried shaping in water equal solvent, then by spray dryer etc., and ball is made Shape or oval spherical precursor, are then sintered and are obtained method of active material etc. at high temperature.
In addition, in these processes, can also in the metal oxide structures containing titanium and/or with the oxygen containing titanium There is element in addition to Ti in the form of compound contact, such as Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga、Zr、C、Si、Sn、Ag.By the way that containing these elements, operating voltage, the capacity of battery can be controlled.
[electrode for making negative pole [3]]
The manufacture of negative pole [3] can use usual way, can form negative pole [3] as described above.Collector, collection Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of electric body and active material layer etc. are also same as described above.
＜ negative poles [4] ＞
Below, the negative pole [4] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains carbonaceous material work For negative electrode active material, the circularity of the carbonaceous material is that more than 0.85, surface functional group amount O/C values are 0~0.01.
[negative electrode active material of negative pole [4]]
Below, the negative electrode active material used in negative pole [4] is illustrated.
The negative electrode active material used in the negative pole [4] of the lithium secondary battery of the present invention, which at least contains, meets following condition (a) with the carbonaceous material of (b).
(a) circularity is more than 0.85；
(b) surface functional group amount O/C values are 0~0.01.
Below, the details of the carbonaceous material to being used in the present invention is illustrated.
[[circularity]]
The circularity of carbonaceous material is usually more than 0.85, and preferably more than 0.87, more preferably more than 0.89, it is especially excellent Elect more than 0.92 as.As the upper limit, turn into theoretic proper sphere when circularity is 1.If less than the scope, negative electrode active material The fillibility reduction of matter, the compacting of negative electrode becomes difficult, and the destruction of particle is caused during compacting, and inside particles are deep in low charging The surface of High temperature storage patience difference under degree may easily expose.
Described circularity is defined with following formula in the present invention.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
Following value is used as the value of circularity：Using such as flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range, value obtained from being measured to the particle of the μ m of particle diameter 3~40 to specify 0.6~400 μm.
[[O/C values]]
The surface functional group amount O/C values of carbonaceous material are necessary for 0~0.01.The upper limit of O/C values is preferably less than 0.005, It is more preferred closer to 0.
Described O/C values are to use the ratio between surface functional group amount of X-ray photoelectricity optical spectroscopy (XPS) measure in the present invention, Surface functional group amount O/C values are if it exceeds, there is specific compound in the amount of functional groups increase of above range, then particle surface Under the conditions of when being charged, the stability of the SEI cover layers of Surface Creation is insufficient, occasionally results in the high temperature under low depth of charge The reduction of preservation characteristics.
Surface functional group amount O/C values represent the molar concentration and carbon atom of oxygen atom present in the surface of graphite material etc. Molar concentration ratio, be the index for representing the functional groups such as carboxyl, phenolic hydroxyl group, carbonyl in the amount on surface.Surface official The big carbon material of energy group amount O/C values is combined with surface oxygen functional group in crystallite end face of particle face carbon etc. mostly.In addition, conduct The surface functional group amount O/C values of graphite material, use following value：In the analysis of X-ray photoelectricity optical spectroscopy, C1s and O1s are obtained Spectrum peak area, thus calculate C and O atomic concentration ratio (O atom concentration/C atomic concentrations).Specific mensuration program It is not particularly limited, as the example, as described below.
That is, using X-ray photoelectricity optical splitter (for example, what ulvac-phi (ア Le バ ッ Network Off ァ イ) company manufactured ESCA) determined as X-ray photoelectricity optical spectroscopy, measure object (being here graphite material) is placed on sample platform and makes surface It is flat, using the K alpha rays of aluminium as x-ray source, by multiplex determine determine C1s (280~300eV) and O1s (525~ Spectrum 545eV).Obtained C1s summit is set as that 284.3eV carries out band electronic compensating, C1s and O1s spectrum is obtained Peak area, multiplied by with device sensitivity coefficient, calculates C and O surface atom concentration respectively.Calculate the obtained O and C original Sub- concentration ratio O/C (O atom concentration/C atomic concentrations), is defined as the surface functional group amount O/C values of graphite material.
The carbonaceous material used in the present invention meets the condition of above-mentioned " circularity " and " surface functional group amount O/C values ", But from the point of view of the balance of battery this point, more preferably further meet any one of following projects or multinomial condition simultaneously.This Among a little, preferably any one of tap density, Raman R value and volume average particle size or multinomial condition are met simultaneously.
[[tap density]]
The tap density of carbonaceous material is usually 0.55g/cm3More than, preferably 0.7g/cm3More than, more preferably 0.8g/ cm3More than, particularly preferably 0.9g/cm3More than.In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3With Under, particularly preferably 1.6g/cm3Below.If tap density is less than the scope, it is difficult to improve filling when using as negative pole Density, can not obtain the battery of high power capacity sometimes.On the other hand, if it exceeds the scope, then the interparticle space in electrode It is very few, it is difficult to ensure interparticle electric conductivity, it is difficult to obtain preferred battery behavior sometimes.
In the present invention, tap density is defined as below：Make sieve of the sample by 300 μm of aperture, sample is fallen into 20cm3 Jolt ramming container in, to sample full of container upper surface after, using powder density determination device (for example, seishin enterprise-like corporations The Tap densor of manufacture), 1000 length of stroke 10mm vibration is carried out, volume and weight when thus calculates density, will The value is used as tap density.
[[Raman R value, half breadth]]
The R values of the carbonaceous material determined using argon laser Raman spectroscopy are usually more than 0.001, preferably 0.01 More than, its upper limit is usually less than 0.2, preferably less than 0.18, more preferably less than 0.15 scope.Should if R values are less than Scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, charge acceptance Reduction.On the other hand, if it exceeds the scope, then the crystallinity reduction of particle surface, under conditions of it there is specific compound When being charged, the stability of the SEI cover layers of Surface Creation is insufficient, and the High temperature storage occasionally resulted under low depth of charge is special The reduction of property.
In addition, carbonaceous material is in 1580cm-1Neighbouring Raman half breadth has no particular limits, usually 10cm-1With On, preferably 15cm-1More than, the upper limit is usually 35cm-1Hereinafter, preferably 30cm-1Following scope.If Raman half value is wide Degree is less than the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, fill Electric acceptance is reduced sometimes.On the other hand, if above the scope, then, there is specialization in the crystallinity reduction of particle surface When being charged under conditions of compound, the stability of the SEI cover layers of Surface Creation is insufficient, occasionally results under low depth of charge High temperature storage characteristic reduction.
Raman spectrum is determined as follows progress：Using raman spectroscopy (for example, the raman spectroscopy that Japanese light splitting company manufactures Device), sample is naturally fallen in measure container, carry out sample filling, continuous mode is that the specimen surface in container is irradiated Argon laser, while making the container be rotated in the face with laser vertical.For obtained Raman spectrum, 1580cm is determined-1 Neighbouring peak PAIntensity IAAnd 1360cm-1Neighbouring peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), defined For the Raman R value of carbonaceous material.In addition, determining obtained Raman spectrum in 1580cm-1Neighbouring peak PAHalf breadth, by it It is defined as the Raman half breadth of carbonaceous material.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
R values, half breadth analysis：Background processing
Smooth treatment：Simple average, 5 points of convolution
[[volume reference average grain diameter]]
The volume reference average grain diameter of carbonaceous material is the average grain for the volume reference tried to achieve by laser diffraction/scattering method Footpath (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, more than 7 μm. In addition, its upper limit is usually less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm, more preferably 25 μm with Under.If less than above range, irreversible capacity increase occasionally results in the loss of the battery capacity at initial stage.In addition, if super Above range is crossed, then when the pole plate of electrode is made, easily forms uneven coated face, is sometimes not in battery production process It is preferred that.
In addition, in terms of the particle diameter of volume reference, the ratio between its 90% particle diameter being distributed and 10% particle diameter (d90/d10) for 1.2 with On, preferably more than 1.5, more preferably more than 1.7.The upper limit is less than 8, preferably less than 5, more preferably less than 4, further Preferably less than 3 scope.
In the present invention, volume reference average grain diameter is defined with median particle diameter, and the median particle diameter is by the following method Determine：Carbon dust is set to be dispersed in 0.2 matter of polyoxyethylene (20) Span-20 as surfactant Measure in the % aqueous solution (about 1mL), using laser diffraction/scattering formula particle size distribution meter (for example, what Ku Chang manufacturing companies manufactured LA-700) determine.It is used as the ratio between 90% particle diameter and 10% particle diameter (d90/d10), it can similarly determine volume reference 90% Footpath and 10% particle diameter, and use its ratio (d90/d10)。
[[X-ray parameter]]
Carbonaceous material is preferred by using the d values (interfloor distance) for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve For more than 0.335nm.In addition, the upper limit is below 0.340nm, preferably below 0.337nm.If d values are excessive, crystallinity drop It is low, increase irreversible capacity at initial stage sometimes.On the other hand, 0.335 be graphite theoretical value.In addition, being shaken method by using The crystallite size (Lc) of carbon material tried to achieve of X-ray diffraction be usually more than 30nm, preferably more than 50nm, more preferably More than 80nm scope.If less than the scope, the crystallinity of particle is reduced, it is possible to increase irreversible capacity at initial stage.
[[ash content]]
Contained ash content is below 1 mass %, preferably 0.5 matter relative to the gross mass of carbonaceous material in carbonaceous material Below %, particularly preferably below 0.1 mass % are measured, its lower limit is more than 1ppm.If it exceeds above range, then during discharge and recharge Deterioration with battery performance caused by the reaction of electrolyte can not be ignored.If less than the scope, needed in manufacture compared with For a long time and energy and for prevent pollution equipment, sometimes cost can rise.
[[BET specific surface area]]
The specific surface area of the carbonaceous material determined using BET method usually 0.1m2/ more than g, preferably 0.7m2/ more than g, More preferably 1m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ below g, preferably 25m2/g Hereinafter, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area is less than above range, In the case where being used as negative material, in charging, the acceptance of lithium is deteriorated, and lithium is easily separated out in electrode surface.The opposing party Face, if it exceeds above range, then as negative material in use, increasing with the reactivity of electrolyte, the gas of generation becomes It is many, it is difficult to obtain preferred battery sometimes.
BET specific surface area is defined as the value determined：Using surface area meter (for example, big storehouse reason develops make full-automatic Surface area determination unit), nitrogen circulation, sample is carried out at 350 DEG C 15 minutes it is predrying, then, using nitrogen relative to The relative pressure of atmospheric pressure is accurately adjusted to 0.3 nitrogen helium mixture, by using the N2 adsorption BET1 of gas flow method Point method is determined.
[[micropore distribution]]
Grain of 0.01 μm~1 μm equivalent to diameter of the carbonaceous material tried to achieve by mercury, Hg porosimeter (mercury penetration method) Space in son, because the concavo-convex amount that causes of being uneven of particle surface is usually more than 0.01mL/g, be preferably More than 0.05mL/g, more preferably more than 0.1mL/g, the upper limit are usually below 0.6mL/g, preferably below 0.4mL/g, more excellent Elect below 0.3mL/g scope as.If it exceeds the scope, then sometimes for substantial amounts of adhesive when being manufactured into pole plate.It is another Aspect, if less than the scope, the reduction of high current density charge-discharge characteristic, also, electricity when can not obtain discharge and recharge sometimes The alleviation effects of pole dilation.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.On the other hand, if being less than the scope, high current density charge-discharge characteristic drops sometimes It is low.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).About 0.2g samples (negative material) are weighed, are encapsulated into powder container, in room temperature, very (50 μm of below Hg) deaerate within 10 minutes under sky, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, mercury is imported, 40000psia (about 280MPa) is boosted to from 4psia (about 28kPa) stage shape, 25psia (about 170kPa) is then depressurized to.Rise Number of stages during pressure more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury intrusion for 80.Use Washburn formulas calculate micropore distribution from the mercury press-in curve so obtained.In addition, the surface tension (γ) of mercury is 485dyne/cm, contact angle (φ) is 140 °.Micropore diameter when mean pore footpath reaches 50% using accumulation micro pore volume.
[[real density]]
The real density of carbonaceous material is usually 2g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3With On, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theoretical value of graphite.If be less than The scope, then the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.In the present invention, real density is defined as passing through The value determined using the Liquid displacement methods (hydrometer method) of butanol.
[[orientation ratio]]
The orientation ratio of carbonaceous material is usually more than 0.005, preferably more than 0.01, more preferably more than 0.015, the upper limit Scope in theory for less than 0.67.If less than the scope, sometimes high density charge-discharge characteristic reduction.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
[[draw ratio]]
The draw ratio of carbonaceous material is theoretically more than 1, and the upper limit is less than 10, preferably less than 8, more preferably less than 5. If it exceeds its upper limit, can produce striped, can not obtain uniform coated face, high current density charge-discharge characteristic when pole plate is made Sometimes reduce.
In addition, draw ratio with the most major diameter A of particle during three dimensional viewing and perpendicular most minor axis B ratio A/B come table Show.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection be fixed on 50 microns of thickness with Under metal end face on any 50 graphite particles, rotation, tilt and be fixed with the objective table of sample, these grains are determined respectively A, B of son, obtain A/B average value.
[[autofrettage and raw material of carbonaceous material]]
The carbonaceous material used in the present invention can be the material or made material naturally produced, but Come preferably from the material of native graphite.In addition, the material or made material naturally produced can also apply specifically Processing.Manufacture method (also comprising method for separating) is not particularly limited, for example, it may be using the classification such as screening or air classification The material that method sorting has the carbonaceous material of above-mentioned characteristic and obtained.
Among these, from being readily available, in process above from the point of view of this point of handling ease, preferably by naturally producing Carbonaceous material obtained from carbon material (natural graphite starting material) is heat-treated.In addition, from the point of view of the viewpoints such as fillibility are improved, it is excellent Select the carbonaceous material being obtained as below：To the carbon material (natural graphite starting material) naturally produced or made carbon material applying power Learn energy process and be modified, spheroidization, then obtained spheroidization carbonaceous is heat-treated.In addition, from lithium secondary battery The viewpoint such as the balance of performance from the point of view of, the carbonaceous material particularly preferably prepared as follows：Mechanics energy is applied to natural graphite starting material Processing, and obtained spheroidization native graphite is heat-treated.Below, sometimes by the heat treatment of above-mentioned natural graphite starting material etc. Preceding carbon material (raw material) is only referred to as " raw material before heat treatment ".
[[natural graphite starting material]]
As described above, being used as the raw material of carbonaceous material, particularly preferred native graphite.
Native graphite is classified as flaky graphite (Flake Graphite), flaky graphite according to its character (Crystalline (Vein) Graphite), soil graphite (Amorphous Graphite) (referring to《Bulk material technology It is integrated》, (strain) industrial technology center, one, the graphite of Showa distribution in 49 years；And " HAND BOOK OF CARBON, GRAPHITE, DIAMOND AND FULLERENES ", Noyes Publications are issued).Degree of graphitization with flaky graphite most Height, is 100%, followed by flaky graphite, is 99.9%, and soil graphite as little as 28%.The main root of quality of native graphite Determined according to the place of production and mineral ore.Flaky graphite mainly originates from Madagascar, China, Brazil, Ukraine, Canada etc.；Squama Shape graphite mainly originates from Sri Lanka, is the Korea peninsula, China, Mexico etc. the main product of soil graphite.These native graphites In, because flaky graphite and flaky graphite have the advantages that degree of graphitization is high, impurity level is few, therefore preferably as carbonaceous material Raw material.
[[[mechanics energy process, spheroidization processing]]]
Carrying out mechanics energy process makes volume average particle size before and after the processing be less than 1.It is so-called that " volume before and after the processing is put down Equal particle diameter ratio " is value obtained from the volume average particle size of volume average particle size after processing divided by before processing.In the present invention, The mechanics energy process carried out to manufacture the raw material before heat treatment preferably makes average grain diameter ratio before and after the processing be less than 1.
Mechanics energy process is to reduce particle size so that the average grain diameter ratio of powder particle before and after the processing is less than 1, together Time control shape of particle and the processing carried out.Crush, classification, mixing, granulation, surface be modified, reaction etc. can be set in particle In the engineering unit operation effectively utilized in meter, mechanics energy process belongs to pulverization process.
It is so-called to crush, refer to material applying power, its size is reduced with the particle diameter or size distribution of Auto-regulator, filling Property.Pulverization process is classified according to species, the processing form of the power applied to material.The power that material applies is roughly divided into Following 4 kinds：(1) power (impulsive force), (2) crushing force (compression stress), (3) grinding forces (grinding forces), (shearing of (4) shaving power are beaten Power).On the other hand, processing form is roughly divided into following 2 kinds：Inside particles produce be cracked and be allowed to propagate volume crush, And cut the surface crushing of particle surface.Volume is crushed and can carried out using impulsive force, compression stress, shearing force；Crush on surface It can be carried out using grinding forces, shearing force.Crushing be the power that these materials will be applied species and processing form carry out it is various The processing of combination.Its combination can suitably be determined according to processing intent.
Although the situation for also having reaction or volumetric expansion using the chemistry such as explosion to carry out is crushed, usually using crushing The mechanical devices such as machine are carried out.The pulverization process used in manufacture as the spheroidization carbonaceous of the raw material of the present invention is preferably final The processing that the shared ratio of surface treatment is uprised, is crushed but regardless of volume is whether there is.Because, remove the angle of particle surface crushing It is important to import circle to shape of particle.Specifically, table can be carried out again after a certain degree of volume crushing is carried out Face is handled, and can also almost be crushed and is only surface-treated without volume, volume crushing and surface can also be carried out simultaneously Processing.It is preferred that finally carrying out surface crushing, the pulverization process of arrisdefect is gone from the surface of particle.
The device for carrying out mechanics energy process is selected from the device that can carry out above-mentioned preferred processing.Mechanics energy Processing can be realized by using the power of one or more of the 4 kinds of power applied to above-mentioned substance, but preferred pair main body is repeatedly The mechanisms such as compression, friction, the shearing force of interaction comprising particle are carried out, so as to assign impulsive force to particle.Therefore, And specifically, it is preferable to following device：The device has the rotor for being provided with multiple blades inside case, and by the rotor at a high speed The effect of the machinery such as impact compress, friction, shearing force is rotated and the carbon material for importeding into inside is assigned, so that side carries out volume Side is crushed to be surface-treated.Mechanism is assigned repeatedly by making carbonaceous material circulation or convection current in addition, more preferably having Mechanism device.
As preferred device, hybrid system (manufacture of nara machinery manufacturing company), Kryptron (Network リ プ ト can be enumerated ロ Application) (manufacture of Earth Technica (ア ー ス テ Network ニ カ) company), CF mill (manufacture of Yu Buxingchan companies), mechanical fusion System (manufacture of hosokawamicron (ホ ソ カ ワ ミ Network ロ Application) company) etc..Among these, preferably nara machinery makes institute's public affairs Take charge of the hybrid system of manufacture.When being handled using the device, the peripheral speed of the rotor of rotation is preferably set as 30~ 100m/ seconds, more preferably it is set as 40~100m/ seconds, is further preferably set as 50~100m/ seconds.In addition, processing can be Only pass through carbonaceous material, but preferably handled in device interior circulation or be detained more than 30 seconds, more preferably in device Interior circulation is detained more than 1 minute to be handled.
By so carrying out mechanics energy process, carbon particle turns into following particle：High crystalline is kept on the whole, simply The near surface of particle becomes coarse, tilts and exposes edge surface.So, the face increase that lithium ion can come in and go out, even in height Also there is high capacity under current density.
In general, flakey, squamous, the carbon material of tabular particle diameter it is smaller, its fillibility more has the tendency of deterioration.This It is regarded as because following reason：Due to particle by crushing more amorphization, or particle surface generation " flash ", The overshooting shape such as " stripping " or " warpage " thing increase, and particle surface with intensity to a certain degree be attached with finer nothing determine The reasons such as shape particle, so, the impedance between adjacent particle become big, deteriorate fillibility.
If the amorphism of these particles is reduced, shape of particle is close to spherical, even if then particle diameter diminishes, fillibility Reduction is also seldom, and in theory, big particle diameter carbon dust, small particle carbon dust should all show the tap density of equal extent.
[[[physical property of the raw material before heat treatment]]]
The physical property of raw material before heat treatment preferably meets any one or many in (1)~(11) shown below simultaneously .In addition, invisible assay method or definition are identical with the situation of above-mentioned carbonaceous material.
(1) X-ray parameter
Raw material before heat treatment is by using the d value (interlamellar spacings for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve From) it is preferably more than 0.335nm.In addition, its lower limit is less than 0.340nm, preferably below 0.337nm.If d values are excessive, Then crystallinity is reduced, and increases irreversible capacity at initial stage sometimes.On the other hand, 0.335 be graphite theoretical value.In addition, passing through The crystallite size (Lc) for the carbon material tried to achieve using the X-ray diffraction for learning method of shaking is usually more than 30nm, preferably more than 50nm, More preferably more than 80nm scope.If less than the scope, crystallinity reduction, it is possible to increase irreversible capacity at initial stage.
(2) ash content
In raw material before heat treatment contained ash content relative to the gross mass of the raw material before heat treatment be usually 1 mass % with Under, preferably below 0.5 mass %, particularly preferably below 0.1 mass %, its lower limit is usually more than 1ppm.If it exceeds Above range, then the deterioration of battery performance can not be ignored during discharge and recharge and caused by the reaction of electrolyte.If less than the model Enclose, then long period and energy and the equipment for preventing pollution are needed in manufacture, cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of raw material before heat treatment is the volume reference tried to achieve by laser diffraction/scattering method Average grain diameter (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, 7 μ More than m.In addition, its upper limit is usually less than 50 μm, and preferably less than 40 μm, more preferably less than 30 μm, more preferably Less than 25 μm.If less than above range, irreversible capacity increase occasionally results in the loss of initial cell capacity.In addition, such as Fruit exceedes above range, then when electrode pad is made, uneven coated face is easily formed, sometimes in battery production process It is undesirable.
(4) Raman R value, Raman half breadth
The R values of raw material before the heat treatment determined using argon laser Raman spectroscopy are usually more than 0.10, preferably For more than 0.15, more preferably more than 0.17, more preferably more than 0.2, its upper limit is usually less than 0.8, and preferably 0.6 Hereinafter, more preferably less than 0.4 scope.If R values are less than the scope, it is likely that without the spheroidization of particle, having can The effect of fillibility raising can be obtained.On the other hand, if it exceeds the scope, then the crystallinity reduction of particle surface, with The reactivity increase of electrolyte, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, the raw material before heat treatment is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and is usually 10cm-1More than, preferably 15cm-1More than, the upper limit is usually 80cm-1Hereinafter, preferably 60cm-1Hereinafter, more preferably 45cm-1 Hereinafter, more preferably 40cm-1Following scope.If Raman half breadth is less than the scope, it is likely that without grain The spheroidization of son, it is possible to the effect of fillibility raising can not be obtained.On the other hand, if above the scope, then particle surface Crystallinity reduction, with electrolyte reactivity increase, occasionally result in efficiency reduction or produce gas increase.
(5) BET specific surface area
The specific surface area of raw material before the heat treatment determined using BET method usually 0.1m2/ more than g, preferably 0.7m2/g More than, more preferably 1m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ below g, be preferably 50m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area is less than above-mentioned Scope, then in the case of being used as negative material, in charging, the acceptance of lithium is deteriorated, and lithium is easily separated out in electrode surface. On the other hand, if it exceeds above range, then reduce specific surface area through Overheating Treatment, more than necessary and electrolyte is produced Reaction, the gas of generation becomes many, is difficult to obtain preferred battery sometimes.
(6) micropore is distributed
Raw material before the heat treatment tried to achieve by mercury, Hg porosimeter (mercury penetration method) equivalent to a diameter of 0.01 μm Space in~1 μm of particle, due to the concavo-convex amount that causes of being uneven of particle surface be usually more than 0.01mL/g, it is excellent Elect more than 0.05mL/g, more preferably more than 0.1mL/g as, its upper limit is usually below 0.6mL/g, preferably 0.4mL/g with Under, more preferably below 0.3mL/g scope.If it exceeds the scope, then need substantial amounts of adhesive when being manufactured into pole plate.Separately On the one hand, if less than the scope, high current density charge-discharge characteristic reduction, also, when can not obtain discharge and recharge sometimes The alleviation effects that electrode expansion shrinks.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.On the other hand, if being less than the scope, high current density charge-discharge characteristic drops sometimes It is low.
(7) circularity
The spherical degree of raw material before using circularity as heat treatment, the particle diameter of the raw material before heat treatment is 3~40 μ The circularity of the particle of m scopes is preferably more than 0.85, and more preferably more than 0.87, particularly preferably more than 0.90, further Preferably more than 0.92.When circularity is big, high current density charge-discharge characteristic is improved, therefore preferably.
The method for improving circularity is not particularly limited, but the preferably above-mentioned energy by mechanics implements spheroidization processing And be made it is spherical because like this, the shape neat and consistent of the inter-particle voids when electrode body is made.
(8) real density
The real density of raw material before heat treatment is usually 2g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
(9) tap density
The tap density of raw material before heat treatment is usually 0.55g/cm3More than, preferably 0.7g/cm3More than, more preferably For 0.8g/cm3More than, particularly preferably 0.9g/cm3More than.In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3Hereinafter, particularly preferably 1.6g/cm3Below.If tap density is less than the scope, as negative pole in use, Packed density is difficult to improve, and the battery of high power capacity can not be obtained sometimes.On the other hand, if above the scope, then in electrode Interparticle space is very few, it is difficult to ensure interparticle electric conductivity, is difficult to obtain preferred battery behavior sometimes.
(10) orientation ratio
The orientation ratio of raw material before heat treatment is usually more than 0.005, preferably more than 0.01, more preferably 0.015 with On, the upper limit is less than 0.67 scope in theory.If less than the scope, sometimes high density charge-discharge characteristic reduction.
(11) draw ratio
The draw ratio of raw material before heat treatment is theoretically more than 1, and the upper limit is usually less than 10, and preferably less than 8, it is more excellent Elect less than 5 as.If it exceeds its upper limit, can produce striped, can not obtain uniform coated face, high current density when pole plate is made Charge-discharge characteristic is reduced sometimes.
[[[heat treatment temperature]]]
It is usually more than 600 DEG C, preferably more than 1200 DEG C, more excellent as the heat treatment temperature of the raw material before heat treatment Elect more than 2000 DEG C, more preferably more than 2500 DEG C, particularly preferably more than 2800 DEG C of scope as.Its upper limit is usually Less than 3200 DEG C, preferably less than 3100 DEG C of scope.If temperature conditionss are less than the scope, handle etc. to enter by spheroidization The crystallization of capable Graphite particle surfaces at random repairs insufficient, and Raman R value and BET specific surface area will not diminish sometimes.It is another Aspect, if it exceeds above range, then the distillation amount of graphite is sometimes prone to become many.
[[[heat treatment method]]]
Heat treatment can be by realizing by once above-mentioned temperature range.Temperature conditionss are remained into above range Retention time is not particularly limited, but is usually the time longer than 10 seconds, and for less than 168 hours.
Heat treatment is generally under the non-active gas atmosphere such as nitrogen or obtained from the gas produced as raw graphite Carried out under non-oxidizing atmosphere.But, in the stove for the type being embedded in coke powder (tiny pitch sinters carbon), sometimes most First mixing air.In this case, complete inactive atmosphere can also be needed not be.
As the device used in heat treatment, have no particular limits, for example, shuttle-type stove, car tunnel furnace, electricity can be used Stove, coke roaster, rotary furnace, direct-electrifying stove, acheson furnace, resistance-heated furnace, induction heater etc..
In addition, except above-mentioned each processing, the various processing such as classification processing can also be carried out.Classification processing is to obtain mesh Mark particle diameter, the processing for removing coarse powder and micro mist and carrying out.The device used in being handled as classification, has no particular limits, example Such as, in the case where dry type is sieved, gyratory sifter, rock type sieve, rotary type sieve, oscillatory type sieve etc. can be used；In dry type gas In the case of flow point level, gravity type grader, inertia force formula grader, centrifugal force type grader (sizer, whirlwind can be used Separator) etc.；In the case of wet screening, can use mechanical wet classifier, hydraulic classifier, settling classifier, Centrifugal wet classifier etc..Classification processing can be carried out before heat treatment, can also be for example heat-treated laggard in other times OK.Further, it is also possible to omit classification processing in itself.But, from the viewpoint of the productivity of powdered graphite negative material, preferably Carry out after spheroidization processing just terminates and before the heat treatment classification processing.
[[auxiliary material mixing]]
In addition to above-mentioned carbonaceous material, by the negative electrode active material that uses in the present invention containing more than one with it is upper Carbonaceous material carbonaceous material different in terms of the physical property of carbonaceous (carbonaceous material) is stated, carrying for battery performance can be further sought It is high." physical property of carbonaceous " mentioned here, refers to X-ray diffraction parameter, median particle diameter, draw ratio, BET specific surface area, orientation Than the characteristic of one or more of, Raman R value, tap density, real density, micropore distribution, circularity, ash amount.In addition, conduct Preferred embodiment, it can enumerate, it is left-right asymmetry when volume reference size distribution is centered on median particle diameter, contain 2 kinds The different carbon material of above Raman R value or X-ray parameter be not equal.As an example of its effect, can enumerate by containing The graphite such as native graphite, Delanium；The carbon blacks such as acetylene black；The carbon materials such as the amorphous carbon such as needle coke are reduced as auxiliary material Resistance etc..They can be used alone one kind, two or more can also be applied in combination with arbitrary proportion in any combination.It is used as pair When material is added, its addition is usually more than 0.1 mass % preferably more than 0.5 mass %, more preferably 0.6 mass % More than, its upper limit is usually preferably below 50 mass %, more preferably below 40 mass % below 80 mass %, especially excellent Elect the scope below 30 mass % as.If less than the scope, the effect for obtaining electric conductivity raising is difficult to sometimes.If it exceeds Above range, then sometimes result in the increase of irreversible capacity at initial stage.
[electrode for making negative pole [4]]
Usual way can be used by manufacturing negative pole [4], can form negative pole [4] as described above.Collector, current collection Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of body and active material layer etc. are also same as described above.
<Negative pole [5]>
Below, the negative pole [5] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains different orientation carbon Compound is as active material, and the different orientation carbon complex contains the different carbonaceous material of two or more orientation.
[negative electrode active material of negative pole [5]]
Below, the negative electrode active material used in negative pole [5] is illustrated.
[[composition of different orientation carbon complex]]
The negative electrode active material used in the negative pole [5] of the lithium secondary battery of the present invention contains different orientation carbon complex, The different orientation carbon complex contains the different carbonaceous material of two or more orientation.
" orientation different " mentioned here, refers to when with polarized light microscope observing powder, visual comparison's optics it is each to During the pattern, the i.e. size of anisotropy unit, direction, quantity etc. of the anisotropy unit of opposite sex tissue, their size, side Into, quantity etc. at least any one be different.It can such as enumerate, in carbonaceous 1 and carbonaceous 2, one has to one The crystallization direction in direction, another has a case that random crystallization direction；Or carbonaceous 1 and carbonaceous 2 all have respectively To the crystallization direction of certain orientation, but the different situation in its direction etc..In addition, the one or both of 2 kinds of carbonaceous 1 and carbonaceous is not Single crystallization, but during the aggregate of multiple crystallizations, using the unit of aggregate as 1 region, contrast its optics it is each to The set pattern of the anisotropy unit of opposite sex tissue.
In addition, the form that the carbonaceous 1, carbonaceous 2 in anisotropy carbon complex coexist preferably is contained in 1 offspring In." being included in 1 offspring " mentioned here, refers to that the different carbonaceous material of orientation is physically constrained, adhered to State；The state for keeping shape by the constraint of electrostatic, attachment；State restrained by bonding etc..It is referred to herein The constraint of physics ", attachment " refer to the state that a kind of carbonaceous material is mixed in another carbonaceous material, connected together；It is so-called " constraint, the attachment of electrostatic " refers to the state that a kind of carbonaceous material is attached to by electrostatic energy in another carbonaceous material. Can be the different state of above-mentioned orientation or original carbonaceous material is same in the constraint, the state of attachment Material.In addition, so-called " state restrained by bonding " refers to that hydrogen bond, covalent bond, ionic bond etc. are chemically bonded.
Wherein, another carbon is made by adhering to and/or being bonded preferably on a kind of at least part surface of carbonaceous material Metallic substance has the state at the different interface of orientation.There is interface compared with without interface, in same shape When particle is compared, in charging lithium ion be mingled with caused by expand and be dispersed in many-side, so as to prevent electricity Pond is deteriorated, and sees it is preferred from this point on.
The orientation it is different be partially forming can be by the material with being externally supplied and/or the key of their modifier Close and formed, or can be formed by the modification of the material of the surface portion of carbonaceous material.Wherein, so-called covering, be With having chemical bond at least part interface on the surface of carbonaceous material, so as to show：(1) state of covering whole surface, (2) Partly cover the state of carbonaceous material, (3) optionally the state on covering part surface, (4) are present in comprising chemical bond The state of atomic zonule.
In addition, near interface, the orientation of carbonaceous material can continuously change, can also discontinuously change.That is, It is preferred that different orientation carbon complex has interface formed by the different carbonaceous material attachment of orientation and/or bonding, and should The orientation of the carbonaceous material at interface is discontinuous and/or continuously changes.
In addition, as the constituent of different orientation carbonaceous compound (A), as long as with crystallinity, without special Limit, but from the point of view of the charging capacity of unit mass uprises this point, more than one of the different carbonaceous material of preferred orientation are Come from the graphite-like carbonaceous material (B) (below, referred to as " native graphite class carbonaceous material (B) ") of native graphite (D).
In addition, the native graphite class carbonaceous material (B) contained in different orientation carbon complex is multiple relative to different orientation carbon The ratio of compound is usually more than 5 mass % preferably more than 20 mass %, more preferably more than 30 mass %, further excellent Elect as more than 40 mass %, particularly preferably more than 50 mass % scope.Its upper limit is usually below 99.9 mass %, preferably For below 99 mass %, more preferably below 95 mass %, more preferably below 90 mass % scope.Should if be less than The loading during calendering of scope, then electrode significantly rises, and the stripping etc. of electrode is caused sometimes.On the other hand, if it exceeds should Scope, then die down as the interface of the complex of orientation different particle when being bonded with.
In addition, as the other constituent of different orientation carbon complex, when being prepared from different orientation carbon complex Interface is generated from the viewpoint of the cohesive raising with interface, and preferably the different carbonaceous material of more than one orientations is under Carbonaceous material (C) in (1) in face~(5).
(1) carbide selected from coal class coke, petroleum-type coke, furnace black, acetylene black and pitch-based carbon fiber；
(2) asphalt stock, aromatic hydrocarbon, N cycle compounds, S cycle compounds, polyphenyl, organic synthesis macromolecule, day will be selected from Organic matter and/or its thermal decomposition product in right macromolecule, thermoplastic resin and thermosetting resin as precursor carbide；
(3) organic matter of (2) is dissolved in the pyrolysate for obtaining solution in small molecular organic solvent and is used as precursor Carbide；
(4) carbide of the gas containing organic matter；
(5) the graphite compound of (1)~(4).
For (2), as long as the material that can be carbonized, is not particularly limited, it can enumerate, asphalt stock, The aromatic hydrocarbons such as acenaphthylene, decacyclene, anthracene, phenanthrene；The N cycle compounds such as azophenlyene, acridine；The S cycle compounds such as thiophene, di- thiophene；Connection The polyphenyl such as benzene, terphenyl；It is polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, their insoluble processed material, nitrogenous poly- The organic polymers such as acrylonitrile, polypyrrole；The organic polymers such as polythiophene, the polystyrene of sulfur-bearing；With cellulose, lignin, Mannosan, polygalacturonic acid, chitosan, sucrose are the natural polymers such as the polysaccharide of representative；Polyphenylene sulfide, polyphenylene oxide etc. Thermoplastic resin；The thermosetting resins such as furfuryl alcohol resin, phenolic resin, imide resin；Or dissolve them in benzene, toluene, The organic matter such as solution formed by the small molecular organic solvents such as dimethylbenzene, quinoline, n-hexane；Gas that can be carbonized etc..
Among these, because the carbon yield of asphalt stock is high, the material of high income can be made, therefore it is preferred that.In addition, this theory In bright book, " asphalt stock " is pitch and belongs to the material of pitch, refers to be carbonized by appropriate processing and/or stone The material of inkization.As the example of specific asphalt stock, tar, heavy oil or pitch etc. can be used.It is used as the specific of tar Example, can enumerate coal tar, petroleum-type tar etc..As the specific example of heavy oil, the contact point of petroleum-type heavy oil can be enumerated Solution oil, thermal decomposition oil, atmospheric resids, decompression residual oil etc..In addition, as the specific example of pitch, coal tar asphalt, stone can be enumerated Oils pitch, synthetic asphalts etc..Wherein, the armaticity of coal tar asphalt is high, therefore it is preferred that.These asphalt stocks can be used alone Any one, can also be applied in combination two or more with ratio in any combination.
As the preferred example of (3), it can enumerate and the organic matter of above-mentioned (2) is dissolved in benzene,toluene,xylene, quinoline, just Obtain solution in the small molecular organic solvents such as hexane, then using the pyrolysate of the solution as precursor carbide.
On (4), the hydrocarbon compounds such as methane, ethane, propane, benzene, acetylene, ethene can be enumerated；Carbon monoxide etc..
The ratio of the carbonaceous material (C) contained in different orientation carbon complex is usually more than 0.1 mass % preferably 1 More than quality %, more preferably more than 5 mass %, more preferably more than 10 mass % scope.Its upper limit is not special Limitation, as long as with the different interface of orientation.If being less than the interface in the scope, different orientation carbon complex Died down when being bonded with.In addition, if more than the scope, then due to containing particle when being suppressed caused by carbonaceous material (C) Deform inhibition to reduce, cycle characteristics reduction.
As the preferred composition of the negative electrode active material used in the lithium secondary battery in the present invention, from electrode calendering When compacting loading viewpoint and as complex interface cohesive balance from the viewpoint of, preferably different orientation carbon Compound native graphite class carbonaceous material (B) and more than one carbonaceous material (C) containing more than one simultaneously.
Due to as described above the reasons why, native graphite class carbonaceous material (B) and carbonaceous in different orientation carbon complex The quality ratio (native graphite class carbonaceous material (B)/carbonaceous material (C)) of material (C) is usually more than 20/80, and preferably 40/ More than 60, more preferably more than 60/40, more preferably more than 70/30 scope.Below 99.9/0.1 is limited to thereon, it is excellent Elect less than 99/1, more preferably less than 95/5 scope as.If it exceeds the scope is (if native graphite class carbonaceous material (B) Ratio it is excessive), then the cohesive at the interface produced by carbonaceous material (C) has the possibility of reduction.On the other hand, if be less than The scope (if the ratio of native graphite class carbonaceous material (B) is too small), compacting loading when electrode rolls significantly becomes big, Peeled off sometimes during calendering.
As the different orientation carbon complex containing native graphite class carbonaceous material (B) and carbonaceous material (C), as long as not surpassing Go out the scope of the purport of the present invention, then can take arbitrary form, be illustrated below one.
(1) whole surface of native graphite class carbonaceous material (B) or part surface adhere to and/or cover and/or be bonded with The form of carbonaceous material (C)；
(2) whole surface or part surface of carbonaceous material (C) and native graphite class carbonaceous material (B) are bonded, more than 2 Native graphite class carbonaceous material (B) and/or carbonaceous material (C) Composite form；
(3) form that above-mentioned (1) and (2) are mixed with arbitrary ratio.
In addition, above-mentioned native graphite class carbonaceous material (B) can also replace with carbonaceous material (C), in addition, different being taken as this The specific complex method of tropism carbon complex, can be set forth in as the surface attachment of the particle of core and/or covering and/or bonding There is the form of carbonaceous material；The surface attachment of multiple particles as core and/or the form of covering and/or bonding；Or conduct State that the particle of core is granulated non-parallelly etc..The state mentioned here granulated non-parallelly, refers to there is certain knot The particle of crystalline substance towards the state in random direction by other carbonaceous materials to be fixed, so as to show different orientation as having Bonding state.
[[preparation of different orientation carbon complex]]
For the preparation of different orientation carbon complex, in " manufacture method 1 of different orientation carbon complex and manufacture below Described in method 2 ", when preparing different orientation carbon complex, can seek to improve crystallinity by applying heat treatment, And the capacity of per unit weight can be increased.As heat treatment temperature, usually more than 400 DEG C, preferably more than 1000 DEG C, more Preferably more than 2000 DEG C, more preferably more than 2400 DEG C, particularly preferably more than 2800 DEG C of scope.Its upper limit is usual For less than 3400 DEG C, preferably less than 3200 DEG C of scope.If less than the scope, can not fully improve crystallinity, and have The increased effect of capacity of per unit weight may not be obtained.On the other hand, if it exceeds the scope, then due to the distillation of carbon Caused loss can not be ignored, it is possible to cause the reduction of yield.
[[property of different orientation carbon complex]]
For the property on different orientation carbon complex, preferably meet any in (1)~(5) shown below simultaneously One or more.
(1) circularity
Using circularity as the spherical degree of different orientation carbon complex, the particle diameter of different orientation carbon complex is 3 The circularity of the particle of~40 μ ms is usually more than 0.1, and preferably more than 0.5, more preferably more than 0.8, it is further excellent Elect more than 0.85, most preferably more than 0.9 as.When circularity is big, high current density charge-discharge characteristic is improved, therefore preferably.Circle Shape degree is defined with following formula, is theoretical proper sphere when circularity is 1.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using such as flow-type particle image analysis device (for example, The FPIA of Sysmex Industrial companies manufacture), about 0.2g samples are scattered in the polyoxyethylene as surfactant (20) in the 0.2 mass % aqueous solution (about 50mL) of Span-20, irradiated 1 minute with 60W power output After 28kHz ultrasonic wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured.
The method for improving circularity has no particular limits, but makes spherical by implementing spheroidization processing and can make The shape of inter-particle voids is neat uniform when electrode body is made, therefore it is preferred that.The example handled as spheroidization, can be enumerated, and be led to Cross and apply the method that shearing force, compression stress carry out mechanically subglobular, the adhesive force having by adhesive or particle itself will Machinery/physical treatment method of multiple particulate granulations etc..
(2) Raman R value, Raman half breadth
The Raman R value of the different orientation carbon complex determined using argon laser Raman spectroscopy be usually 0.01 with On, preferably more than 0.02, more preferably more than 0.04, its upper limit is usually less than 0.35, and preferably less than 0.30, more preferably For less than 0.25 scope.If Raman R value is less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters The site for entering interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if it exceeds the scope, then particle surface Crystallinity reduction, with nonaqueous electrolytic solution reactivity increase, occasionally result in efficiency reduction or produce gas increase.
In addition, the carbon material of the present invention is in 1580cm-1Neighbouring Raman half breadth has no particular limits, but is usually 5cm-1More than, preferably 10cm-1More than, in addition, its upper limit is usually 40cm-1Hereinafter, preferably 35cm-1Hereinafter, more preferably 30cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, with discharge and recharge The site that Li enters interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if above the scope, then particle The crystallinity reduction on surface, increases with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
Raman spectrum is determined as follows progress：Use raman spectroscopy device (such as raman spectroscopy that Japanese light splitting society manufactures Device), sample is fallen and is filled in cell naturally, argon laser is irradiated to the specimen surface in pond, meanwhile, pond is existed With being rotated in the face of laser vertical.For obtained Raman spectrum, 1580cm is determined-1Neighbouring peak PAIntensity IAAnd 1360cm-1Neighbouring peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as the Raman R value of carbon material.In addition, surveying Surely the Raman spectrum obtained is in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the Raman half breadth of carbon material.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
Raman R value, the analysis of Raman half breadth：Background processing
Smooth treatment：Simple average, 5 points of convolution
(3) tap density
The tap density of different orientation carbon complex is usually 0.55g/cm3More than, preferably 0.70g/cm3More than, it is more excellent Elect 0.9g/cm as3More than, particularly preferably 1g/cm3More than.Additionally, it is preferred that being 2.0g/cm3Hereinafter, more preferably 1.8g/cm3 Hereinafter, more preferably 1.7g/cm3Hereinafter, particularly preferably 1.5g/cm3Below.If tap density is less than the scope, As negative pole in use, packed density be difficult improve, the battery of high power capacity can not be obtained sometimes.On the other hand, if above The scope, then the interparticle space in electrode is very few, it is difficult to ensure interparticle electric conductivity, is difficult to obtain preferred electricity sometimes Pond characteristic.
In the present invention, tap density is defined as below：Sample is set to fall by the sieve in 300 μm of aperture in 20cm3Jolt ramming In container, until behind upper surface of the sample full of container, using powder density determination device (for example, seishin enterprise-like corporations manufacture Tap densor) carry out 1000 length of stroke 10mm vibration, by thus when volume and sample weight try to achieve it is close Degree is defined as tap density.
(4) BET specific surface area
The specific surface area of the different orientation carbon complex determined using BET method usually 0.1m2/ more than g, be preferably 0.7m2/ more than g, more preferably 1.0m2/ more than g, more preferably 1.2m2/ more than g.Its upper limit is usually 100m2/ g with Under, preferably 25m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.If the value of specific surface area Less than the scope, then as negative material in use, the acceptance of lithium is easily deteriorated in charging, lithium is easily analysed in electrode surface Go out.On the other hand, if above above range, then when as negative material, increase with the reactivity of nonaqueous electrolytic solution, generation Gas easily becomes many, is difficult to obtain preferred battery sometimes.
BET specific surface area is defined as the value determined：Using surface area meter (for example, big storehouse reason develops make full-automatic Surface area determination unit), nitrogen circulation under, at 350 DEG C to sample carry out 15 minutes it is predrying, then, use nitrogen phase 0.3 nitrogen helium mixture is accurately adjusted to for the relative pressure of atmospheric pressure, by using the N2 adsorption of gas flow method 1 method of BET is determined.
(5) volume reference average grain diameter
The volume reference average grain diameter of different orientation carbon complex is the volume reference tried to achieve by laser diffraction/scattering method Average grain diameter (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more than 5 μm, more preferably More than 7 μm.In addition, its upper limit is usually less than 100 μm, and preferably less than 50 μm, more preferably less than 40 μm, further preferably For less than 30 μm, particularly preferably less than 25 μm.If less than above range, irreversible capacity increase occasionally results in initial stage The loss of battery capacity.In addition, if more than above range, then when electrode pad is made, easily forming uneven coating Face, is sometimes undesirable in battery production process.
In the present invention, volume reference average grain diameter is defined with median particle diameter, and the median particle diameter is by the following method Determine：Carbon dust is set to be dispersed in 0.2 matter of polyoxyethylene (20) Span-20 as surfactant Measure in the % aqueous solution (about 1mL), use laser diffraction formula particle size distribution meter (for example, LA-700 that Ku Chang manufacturing companies manufacture) To determine.
From the viewpoint of the balance of battery behavior, preferably in addition to the item of above-mentioned (1)~(5), also meet following (6)~ (11) more than one in item.
(6) X-ray parameter
Different orientation carbon complex is by using the d value (interlayers for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve Distance) it is preferably more than 0.335nm, and usually below 0.340nm, preferably below 0.337nm.If less than the scope, Then crystallinity is reduced, it is possible to can increase irreversible capacity at initial stage.In addition, the 0.335 of lower limit is the theoretical value of graphite.In addition, The crystallite size (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is usually more than 30nm, preferably 50nm More than, more preferably more than 80nm scope.If less than the scope, crystallinity reduction, it is possible to increase initial stage irreversible Capacity.
(7) ash content
Contained ash content is usually 1 matter relative to the gross mass of different orientation carbon complex in different orientation carbon complex Below %, particularly preferably preferably below 0.5 mass %, below 0.1 mass % are measured, its lower limit is usually more than 1ppm.Such as Fruit exceedes above range, then the deterioration of battery performance can not be ignored during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution.Such as Fruit be less than the scope, then needed in manufacture long period and energy and for prevent pollution equipment, sometimes cost can on Rise.
(8) micropore is distributed
The different orientation carbon complex tried to achieve by mercury, Hg porosimeter (mercury penetration method) equivalent to 0.01 μm of diameter Space in~1 μm of particle, due to the concavo-convex amount that causes of being uneven of particle surface be usually more than 0.001mL/g, Preferably more than 0.002mL/g, its upper limit is usually below 0.6mL/g, preferably below 0.4mL/g, more preferably 0.3mL/g Following scope.If it exceeds the scope, then sometimes for substantial amounts of adhesive when being manufactured into pole plate.On the other hand, if low In the scope, then high current density charge-discharge characteristic is reduced, also, electrode expansion when can not obtain discharge and recharge sometimes shrinks Alleviation effects.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.On the other hand, if being less than the scope, high current density charge-discharge characteristic drops sometimes It is low.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).About 0.2g samples (negative material) are weighed, are encapsulated into powder container, in room temperature, very (50 μm of below Hg) deaerate within 10 minutes under sky, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, mercury is imported, 40000psia (about 280MPa) is boosted to from 4psia (about 28kPa) stage shape, 25psia (about 170kPa) is then depressurized to.Rise Number of stages during pressure more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury intrusion for 80.Use Washburn formulas calculate micropore distribution from the mercury press-in curve so obtained.In addition, the surface tension (γ) of mercury is 485dyne/cm, contact angle (φ) is 140 °.Micropore diameter when mean pore footpath reaches 50% using accumulation micro pore volume.
(9) real density
The real density of different orientation carbon complex is usually 2.0g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.In the present invention, real density It is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol.
(10) orientation ratio (powder)
The orientation ratio of different orientation carbon complex is usually more than 0.005, preferably more than 0.01, more preferably 0.015 More than, the upper limit is less than 0.67 scope in theory.If less than the scope, sometimes high density charge-discharge characteristic reduction.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
(11) draw ratio (powder)
The draw ratio of different orientation carbon complex is theoretically more than 1, and the upper limit is less than 10, preferably less than 8, more preferably For less than 5.If it exceeds its upper limit, can produce striped, can not obtain uniform coated face, high current density fills when pole plate is made Flash-over characteristic is reduced sometimes.
In addition, during draw ratio three dimensional viewing the most major diameter A of carbon material particle and perpendicular most minor axis B ratio A/ B is represented.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.It is micro- that selection is fixed on thickness 50 Any 50 graphite particles on the end face of metal below rice, rotation, inclination are fixed with the objective table of sample, and this is determined respectively A, B of a little particles, obtain A/B average value.
[[raw material of native graphite class carbonaceous material (B)]]
As the raw material of the native graphite class carbonaceous material (B) contained in different orientation carbon complex, can generally enumerate with The interplanar distance (d002) in (002) face determined using X-ray wide-angle diffraction method shows below 0.340nm high natural of crystallinity Graphite is the material of raw material.And specifically, it is preferable to the powder selected from following material：Native graphite adds mechanical crushing thing wherein Product, expansion stone obtained from being heat-treated come product obtained from improving circularity, and/or by them more than 100 DEG C The heat treated article of ink or the high-purity purified product of these graphite.
As the native graphite (D) of the precursor of native graphite class carbonaceous material (B), according to its character, it is classified as scale Shape graphite (Flake Graphite), flaky graphite (Crystalline (Vein) Graphite), soil graphite (Amorphous Graphite) (referring to《Bulk material technology is integrated》, one, the graphite of ((strain) industrial technology center, Showa is issued for 49 years)； And " HAND BOOK OF CARBON, GRAPHITE, DIAMOND AND FULLERENES ", (Noyes Publications Distribution)).Degree of graphitization, with flaky graphite highest, is 100%, followed by flaky graphite, is 99.9%, and soil graphite is low To 28%.Madagascar, China, Brazil, Ukraine, Canada etc. are originated from as the flaky graphite of native graphite；Squamous Graphite mainly originates from Sri Lanka.It is the Korea peninsula, China, Mexico etc. the main product of soil graphite.In these native graphites, Not only usual particle diameter is smaller for soil graphite, and purity is low.Conversely, because flaky graphite and flaky graphite have degree of graphitization Or the low advantage of impurity level, therefore can preferably use in the present invention.
[[preparation of native graphite class carbonaceous material (B)]]
For the preparation of native graphite class carbonaceous material (B), in " the manufacture method 1 of different orientation carbon complex below With manufacture method 2 " in described.
[[property of native graphite class carbonaceous material (B)]]
For native graphite class carbonaceous material (B), preferably any one of (1)~(11) shown below or many are met simultaneously .In addition, respective definition, assay method etc. are identical with definition that different orientation carbon complex part is recorded, assay method.
(1) X-ray parameter
Native graphite class carbonaceous is by using the d value (interlamellar spacings for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve From) it is preferably more than 0.335nm, and usually below 0.340nm, preferably below 0.337nm.If less than the scope, Crystallinity is reduced, it is possible to can increase irreversible capacity at initial stage.In addition, 0.335nm is the theoretical value of graphite.In addition, by adopting The crystallite size (Lc) for the carbon material tried to achieve with the X-ray diffraction for learning method of shaking is usually more than 30nm, preferably more than 50nm, more Preferably more than 90nm scope.If less than the scope, crystallinity reduction, it is possible to increase the increasing of irreversible capacity at initial stage Greatly.
(2) ash content
In native graphite class carbonaceous contained ash content relative to the gross mass of native graphite class carbonaceous be usually 1 mass % with Under, preferably below 0.5 mass %, particularly preferably below 0.1 mass %, its lower limit is usually more than 1ppm.If it exceeds Above range, then the deterioration of battery performance can not be ignored sometimes during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution.If Less than the scope, then long period and energy and the equipment for preventing pollution are needed in manufacture, cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of native graphite class carbonaceous is the volume reference tried to achieve by laser diffraction/scattering method Average grain diameter (median particle diameter), usually more than 1 μm, preferably more than 3 μm, more preferably more preferably more than 5 μm, 7 μ More than m.In addition, its upper limit is usually less than 50 μm, and preferably less than 40 μm, more preferably less than 30 μm, more preferably Less than 25 μm.If less than above range, irreversible capacity increase occasionally results in the loss of initial cell capacity.In addition, such as Fruit exceedes above range, then when electrode pad is made, uneven coated face is easily formed, sometimes in battery production process It is undesirable.
(4) Raman R value, Raman half breadth
The Raman R value of the native graphite class carbonaceous determined using argon laser Raman spectroscopy is usually more than 0.01, Preferably more than 0.02, more preferably more than 0.04, its upper limit is usually less than 0.35, and preferably less than 0.30, more preferably Less than 0.25 scope.If Raman R value is less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters The site of interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if it exceeds the scope, then particle surface Crystallinity is reduced, and is increased with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, the carbon material of the present invention is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and is usually 5cm-1More than, preferably 10cm-1More than, in addition, its upper limit is usually 40cm-1Hereinafter, preferably 35cm-1Hereinafter, more preferably 30cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, with discharge and recharge The site that Li enters interlayer tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if above the scope, then particle The crystallinity reduction on surface, increases with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
(5) BET specific surface area
The specific surface area of the native graphite class carbonaceous determined using BET method usually 0.1m2/ more than g, preferably 0.7m2/g More than, more preferably 1.0m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is usually 100m2/ below g, preferably For 25m2/ below g, more preferably 15m2/ below g, more preferably 10m2/ below g.Should if the value of specific surface area is less than Scope, then as negative material in use, the acceptance of lithium is deteriorated in charging, lithium is easily separated out in electrode surface.The opposing party Face, if above above range, then when as negative material, increases, the gas of generation is easy with the reactivity of nonaqueous electrolytic solution Become many, be difficult to obtain preferred battery sometimes.
(6) micropore is distributed
The native graphite class carbonaceous tried to achieve by mercury, Hg porosimeter (mercury penetration method) equivalent to diameter 0.01 μm~1 μm particle in space, due to the concavo-convex amount that causes of being uneven of particle surface be usually more than 0.01mL/g, preferably For more than 0.05mL/g, more preferably more than 0.1mL/g, its upper limit is usually below 0.6mL/g, preferably below 0.4mL/g, More preferably below 0.3mL/g scope.If it exceeds the scope, then sometimes for substantial amounts of adhesive when being manufactured into pole plate. If less than the scope, the reduction of high current density charge-discharge characteristic, also, electrode expansion when can not obtain discharge and recharge sometimes The alleviation effects of contraction.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, particularly preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.If less than the scope, sometimes high current density charge-discharge characteristic reduction.
(7) circularity
Using circularity as the spherical degree of native graphite class carbon material, the particle diameter of native graphite class carbon material is 3 The circularity of the particle of~40 μ ms is usually more than 0.1, and preferably more than 0.5, more preferably more than 0.8, it is further excellent Elect more than 0.85, most preferably more than 0.9 as.When circularity is big, high current density charge-discharge characteristic is improved, therefore preferably.
(8) real density
The real density of native graphite class carbonaceous is usually 2.0g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
(9) tap density
The tap density of native graphite class carbonaceous is usually 0.1g/cm3More than, preferably 0.5g/cm3More than, more preferably 0.7g/cm3More than, particularly preferably 0.9g/cm3More than.Additionally, it is preferred that being 2.0g/cm3Hereinafter, more preferably 1.8g/cm3With Under, particularly preferably 1.6g/cm3Below.If tap density be less than the scope, as negative pole in use, packed density It is difficult to improve, the battery of high power capacity can not be obtained sometimes.On the other hand, it is if above the scope, then interparticle in electrode Space is very few, it is difficult to ensure interparticle electric conductivity, is difficult to obtain preferred battery behavior sometimes.
(10) orientation ratio (powder)
The orientation ratio of native graphite class carbonaceous is usually more than 0.005, preferably more than 0.01, more preferably 0.015 with On, the upper limit is less than 0.67 scope in theory.If less than the scope, sometimes high density charge-discharge characteristic reduction.
(11) draw ratio (powder)
The draw ratio of native graphite class carbonaceous is theoretically more than 1, and the upper limit is usually less than 10, and preferably less than 8, it is more excellent Elect less than 5 as.If it exceeds its upper limit, can produce striped, can not obtain uniform coated face, high current density when pole plate is made Charge-discharge characteristic is reduced sometimes.
[[raw material of carbonaceous material (C)]]
The raw material of the carbonaceous material (C) contained in different orientation carbon complex as the present invention, as long as it can be carbonized Material, be not particularly limited, can enumerate, the aromatic hydrocarbon such as asphalt stock, acenaphthylene, decacyclene, anthracene, phenanthrene；Azophenlyene, a word used for translation The N cycle compounds such as pyridine；The S cycle compounds such as thiophene, di- thiophene；The polyphenyl such as biphenyl, terphenyl；It is polyvinyl chloride, polyvinyl alcohol, poly- The organic polymers such as vinyl butyral, their insoluble processed material, nitrogenous polyacrylonitrile, polypyrrole；The poly- thiophene of sulfur-bearing The organic polymers such as fen, polystyrene；Using cellulose, lignin, mannosan, polygalacturonic acid, chitosan, sucrose as generation The natural polymers such as the polysaccharide of table；The thermoplastic resins such as polyphenylene sulfide, polyphenylene oxide；Furfuryl alcohol resin, phenolic resin, acid imide tree The thermosetting resins such as fat；Or dissolve them in the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane and The organic matters such as the solution of formation；Gas that can be carbonized etc..
Among these, because the carbon yield of asphalt stock is high, the material of high income can be made, therefore it is preferred that.In addition, this theory In bright book, " asphalt stock " is pitch and belongs to the material of pitch, refers to be carbonized by appropriate processing and/or stone The material of inkization.As the example of specific asphalt stock, tar, heavy oil or pitch etc. can be used.It is used as the specific of tar Example, can enumerate coal tar, petroleum-type tar etc..As the specific example of heavy oil, the contact point of petroleum-type heavy oil can be enumerated Solution oil, thermal decomposition oil, atmospheric resids, decompression residual oil etc..In addition, as the specific example of pitch, coal tar asphalt, stone can be enumerated Oils pitch, synthetic asphalts etc..Wherein, the armaticity of coal tar asphalt is high, therefore it is preferred that.These asphalt stocks can be used alone Any one, can also be applied in combination two or more with ratio in any combination.
In addition, the content of the asphalt stock of above-mentioned quinoline non-soluble composition is not particularly limited, but usually using in 30 with The asphalt stock of lower scope.So-called quinoline non-soluble composition, be in coal tar it is micro containing ultra micro carbon particle or atomic small Greasy filth etc., if these materials are too many, significantly hinders crystallinity to improve, so that after causing graphitization in graphitizing process Discharge capacity significantly reduce.In addition, as the assay method of quinoline non-soluble composition, such as can use in JIS K2425 and advise Fixed method.
As long as in addition, the effect of the without prejudice to present invention, in addition to the above-mentioned asphalt stock as raw material, can also be combined Use various thermosetting resins, thermoplastic resin etc..
[[preparation of carbonaceous material (C)]]
For carbonaceous material (C) preparation, in " the manufacture method 1 and manufacture method of different orientation carbon complex below Described in 2 ".
[[property of carbonaceous material (C)]]
For carbonaceous material (C), preferably meet any one or more in (1)~(4) shown below simultaneously.Separately Outside, their definition, assay method etc. are identical with definition that different orientation carbon complex part is recorded, assay method.
(1) X-ray parameter
Carbonaceous material (C) is by using the d values (interfloor distance) for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve Preferably more than 0.335nm, and usually below 0.345nm, preferably below 0.340nm, more preferably below 0.337nm. In addition, the crystallite size (Lc) for the carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is usually more than 5nm, it is preferably More than 10nm, more preferably more than 50nm, more preferably more than 80nm scope.If less than the scope, crystallinity Reduction, it is possible to increase the increase of irreversible capacity at initial stage.
(2) ash content
In carbonaceous material (C) contained ash content relative to the gross mass of different orientation carbon complex be usually 1 mass % with Under, preferably below 0.5 mass %, particularly preferably below 0.1 mass %, its lower limit is usually more than 1ppm.If it exceeds Above range, then the deterioration of battery performance can not be ignored sometimes during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution.If Less than the scope, then long period and energy and the equipment for preventing pollution are needed in manufacture, cost can rise sometimes.
(3) Raman R value, Raman half breadth
The Raman R value of the carbonaceous material (C) determined using argon laser Raman spectroscopy is usually more than 0.01, preferably For more than 0.03, more preferably more than 0.05, its upper limit is usually less than 0.60, preferably less than 0.30 scope.If drawn Graceful R values are less than the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, Charging acceptance is reduced sometimes.On the other hand, if it exceeds the scope, then the crystallinity reduction of particle surface, with non-aqueous solution electrolysis The reactivity increase of liquid, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, the carbonaceous material (C) of the present invention is in 1580cm-1Neighbouring Raman half breadth has no particular limits, and leads to It is often 5cm-1More than, preferably 10cm-1More than, in addition, its upper limit is usually 60cm-1Hereinafter, preferably 45cm-1Hereinafter, more preferably For 30cm-1Following scope.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, with charge and discharge The site that electric Li enters interlayer tails off sometimes.On the other hand, if above the scope, then the crystallinity reduction of particle surface, with The reactivity increase of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
(4) real density
The real density of carbonaceous material (C) is usually 2.0g/cm3More than, preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, the theoretical upper limit 2.26g/cm of graphite is limited to thereon3Below.If less than the scope, the crystallinity of carbon Too low, initial stage, irreversible capacity increased sometimes.
[manufacture method of the different orientation carbon complex of negative pole [5]]
As manufacture method, it is not particularly limited, without departing from the scope of idea of the invention, it is possible to using any Method, the summary of example preferably such as following (1), (2).
(1) initial feed of carbonaceous material (C) in any one process its all or part of all form the shape of liquid State, and mix and/or mediated with native graphite (D) with the state for turning into liquid；
(2) devolatilization/sintering, graphitization are carried out to the compound obtained in the process, then crushed, be classified and Adjust granularity.Crushing/classification process more than once is may also pass through between these processes.
The concrete example of above-mentioned summary is illustrated below.
[[manufacture method 1 of different orientation carbon complex]]
Different orientation carbon complex preferred natural graphite class carbonaceous material (B) and orientation and native graphite in the present invention Different carbonaceous material (C) Composite of class carbonaceous material (B), by way of example, method can be listed below：In above-mentioned native graphite (D) mix as the asphalt stock of the precursor of above-mentioned carbonaceous material (C) using defined ratio in or heat is carried out to asphalt stock etc. Material obtained from handling and crushing (below, referred to as " heat-treated graphite crystalline precursor "), natural polymer etc., carry out hot place Crushed again after reason A, then carry out heat treatment B (sintering, graphitization) method etc..In addition, if It is not necessary to making intermediate value Particle diameter is fully small, can also be without above-mentioned crushing.
[[[manufacture of heat-treated graphite crystalline precursor]]]
Asphalt stock is implemented in advance to be heat-treated, heat-treated graphite crystalline precursor is obtained.The prior heat treatment is referred to as Pitch is heat-treated.After the heat-treated graphite crystalline precursor is crushed, mixed with native graphite (D), then carry out heat treatment A, this When, one part or all melting, here it is possible to adjust containing for volatile ingredient by prior heat treatment (pitch heat treatment) Amount, thus carrys out suitable control its molten condition.In addition, as the volatile ingredient contained in heat-treated graphite crystalline precursor, generally Hydrogen, benzene, naphthalene, anthracene, pyrene etc. can be enumerated.
Temperature conditionss when pitch is heat-treated are not particularly limited, usually 300 DEG C~550 DEG C of scope.Heat treatment If temperature is less than the scope, volatile ingredient becomes many, therefore is difficult to safely be crushed in atmosphere sometimes.The opposing party Face, if it exceeds its upper limit, then when carrying out heat treatment A, part or all of heat-treated graphite crystalline precursor will not be melted, Sometimes it is difficult to particle (the different orientation carbon for obtaining native graphite class carbonaceous material (B) and heat-treated graphite crystalline precursor Composite Compound).When carrying out pitch heat treatment, the volatile ingredient produced under the non-active gas atmosphere such as nitrogen or by asphalt stock Carried out under atmosphere.
The device used when being heat-treated as pitch, is not particularly limited, for example, shuttle-type stove, car tunnel furnace, electricity can be used The reactors such as stove, autoclave, coka (コ ー カ ー) (cokes (コ ー Network ス) manufacture heat treatment groove) etc..Carry out pitch heat During processing, it can be stirred as needed.
In addition, as heat-treated graphite crystalline precursor, it is usually more than 5 mass % to preferably use volatile ingredient containing ratio Material.By using the graphite crystallization precursor that volatile ingredient containing ratio is the scope, make native graphite class carbon by being heat-treated A Metallic substance (B) and carbonaceous material (C) Composite, so as to obtain the different orientation carbon complex with above-mentioned regulation physical property.
Firstly, for implementing to be heat-treated in advance to asphalt stock, so as to manufacture in the body as the precursor of graphite crystallization Between phase (バ Le Network メ ソ フ ェ ー ズ, bulk mesophase) (the graphite crystallization precursor that is heat-treated in advance, below brief note For " heat-treated graphite crystalline precursor ") method illustrate.
(volatile ingredient of heat-treated graphite crystalline precursor)
The volatile ingredient of graphite crystallization precursor is not particularly limited obtained from being heat-treated by pitch, but usually 5 matter More than %, preferably more than 6 mass % are measured, in addition, usually below 20 mass %, preferably below 15 mass %.If waved Send out composition and be less than above range, then because volatile ingredient is more, therefore be difficult to safely be crushed in atmosphere sometimes, and if More than its upper limit, then when carrying out heat treatment A, part or all of graphite crystallization precursor will not be melted, and be difficult to obtain sometimes Native graphite class carbonaceous material (B) and the particle (different orientation carbon complex) of heat-treated graphite crystalline precursor Composite.In addition, As the assay method of volatile ingredient, such as using method specified in JIS M8812.
(softening point of heat-treated graphite crystalline precursor)
The softening point of graphite crystallization precursor is not particularly limited obtained from being heat-treated by pitch, but usually 250 DEG C More than, preferably more than 300 DEG C, more preferably more than 370 DEG C, in addition, usually less than 470 DEG C, preferably less than 450 DEG C, More preferably less than 430 DEG C of scope.If less than lower limit, the carbonization rate of the graphite crystallization precursor after heat treatment is low, difficult To obtain the uniform mixture with native graphite class carbonaceous material (B), if it exceeds the upper limit, then when carrying out heat treatment A, stone Part or all of black crystalline precursor will not be melted, and be difficult to obtain native graphite class carbonaceous material (B) and heat treatment stone sometimes The particle (different orientation carbon complex) of black crystalline precursor Composite.
As softening point, the value determined as follows is used：Using thermo-mechanical analysis device (for example, bruke-axs (Block Le カ ー エ イ エ ッ Network ス) Co., Ltd. manufacture TMA4000), nitrogen circulation under, 10 DEG C/min of programming rate, needlepoint form It is thick to being shaped to 1mm with tablet former using through transmission technique (ペ ネ ト レ ー シ ョ Application method) under conditions of 1mm φ, exacerbation 20gf Sample be measured.
(crushing of heat-treated graphite crystalline precursor)
Then, heat-treated graphite crystalline precursor is crushed obtained from being heat-treated by pitch.Because, pass through Heat treatment, by the crystallization miniaturization of big unit and the heat-treated graphite crystalline precursor of arrangement in the same direction, and/or equably Carry out mixing, the Composite of native graphite (D) and heat-treated graphite crystalline precursor.
The crushing of graphite crystallization precursor is not particularly limited obtained from being heat-treated by pitch, but the heat treatment after crushing The granularity of graphite crystallization precursor is usually more than 1 μm, preferably more than 5 μm, and usually below 10mm, preferably 5mm with Under, more preferably less than 500 μm, more preferably particularly preferably less than 200 μm, less than 50 μm.Above-mentioned granularity is less than 1 μm When, aoxidized in crushing or after crushing due to surface and the air contact of heat treated heat-treated graphite crystalline precursor, resistance Hinder the crystalline raising in graphitizing process, occasionally result in the reduction of the discharge capacity after graphitization.On the other hand, if Above-mentioned granularity is more than 10mm, then the micronized effect brought due to crushing is weakened, and crystallization is easily orientated, and carbonaceous material (C) is held Easily orientation, uses the active material orientation ratio step-down of the electrode of different orientation carbonaceous compound (A), it is difficult to when suppressing electrode charge Electrode expansion.And/or because the particle diameter difference of native graphite (D) and heat-treated graphite crystalline precursor becomes big, therefore, it is difficult to uniform Mixing, Composite is sometimes prone to become uneven.
Device for crushing has no particular limits, for example, as Roughpulverizer, can enumerate shearing mill, jaw and break Broken machine, impact type crushing machine, cone crusher etc.；As middle pulverizer, roll crusher, beater grinder can be enumerated Deng；As atomizer, ball milling, vibromill, sprayer of hammer crusher, Ball-stirring mill, jet mill, turbine mill can be enumerated (turbomill) etc..
[[[heat treatment of native graphite (D) and heat-treated graphite crystalline precursor]]]
Native graphite (D) and heat-treated graphite crystalline precursor (raw material of carbonaceous material (C)) are mixed with defined ratio, And heat treatment A, crushing, heat treatment B (sintering, graphitization) are carried out, thus make different orientation carbon complex.
(mixing of native graphite (D) and heat-treated graphite crystalline precursor)
The native graphite (D) and the mixed proportion of heat-treated graphite crystalline precursor carried out before heat treatment A be not special Limitation, native graphite (D) is usually more than 20 mass % preferably more than 30 mass % relative to the ratio of mixture, more excellent Elect as more than 40 mass %, in addition, usually below 95 mass %, preferably below 90 mass %.If less than its lower limit, Due to the ratio increase of the carbonaceous material (C) in different orientation carbon complex (A), it is difficult to improve when electrode is made and fills close The compacting loading, it is necessary to excessive is spent, can not be obtained the effect of native graphite class carbonaceous material (B) Composite sometimes.If super Its upper limit is crossed, then increase, different orientation are exposed in native graphite class carbonaceous material (B) surface in different orientation carbon complex (A) Property carbon complex (A) specific surface area have and become big possibility, it is sometimes not preferred on powder property.
By native graphite (D) and when being adjusted to the heat-treated graphite crystalline precursor of designated size and being mixed, to using Device be not particularly limited, can for example enumerate V-Mixer, Wtypeofblender, container changeable type mixer, kneading machine, roller Blender, shearing blender etc..
(heat treatment A)
Then, heat treatment A is implemented to the mixture of native graphite (D) and heat-treated graphite crystalline precursor.Because, lead to Cross the heat-treated graphite crystalline precursor after crushing is remelted or fusion, the heat-treated graphite after native graphite (D) and miniaturization The immobilization with No yield point state contacts of crystalline precursor particle.Thus, native graphite (D) and heat-treated graphite crystalline precursor is mixed Compound is not only the mixture of particle, and the mixture that Composite evenly can also be made (is properly termed as that " graphite is multiple below Close mixture ").
Heat treatment A temperature conditionss are not particularly limited, but usually more than 300 DEG C, it is preferably more than 400 DEG C, more excellent More than 450 DEG C are elected as, in addition, usually less than 650 DEG C, preferably less than 600 DEG C.If being heat-treated A temperature less than above-mentioned Scope, then a large amount of volatile ingredients of remaining in the material after heat treatment A, therefore be possible in sintering or graphitization process to draw The fusion between powder is played, must be crushed again sometimes.On the other hand, if it exceeds above range, then remelted Composition is separated into needle-like when crushing, and occasionally results in the reduction of tap density.A is heat-treated under the non-active gas atmosphere such as nitrogen Or carried out under the volatile ingredient atmosphere produced by the heat-treated graphite crystalline precursor of crushing and miniaturization.
The device that heat treatment A is used is not particularly limited, such as usable shuttle-type stove, car tunnel furnace, electric furnace.
(crushing of heat-treated graphite crystalline precursor and heat treatment A replacement processing)
But, handled as above-mentioned crushing and heat treatment A replacement, can make heat-treated graphite crystalline precursor Miniaturization, the processing of No yield point are organized, for example, can be while in the graphite crystallization precursor melt or the temperature of softening of heat treatment Region assign the processing of mechanical energy, while mixing and being heat-treated with native graphite (D).
The heat treatment of processing is replaced as this, is not particularly limited, but generally more than 200 DEG C, preferably 250 DEG C with On, and generally below 450 DEG C, carried out preferably below 400 DEG C.If temperature conditionss are less than above range, instead of processing In graphite crystallization precursor melting, soften insufficient, be difficult to sometimes and the Composite of native graphite (D).In addition, if More than above range, then heat treatment is easily rapidly carried out, the separate particles of carbonaceous heat-treated graphite crystalline precursor etc. when crushing Into needle-like, it is sometimes prone to cause the reduction of tap density.
This replaces processing generally to be carried out under the inactive atmospheres such as nitrogen or under the oxidation atmospheres such as air.But, When being handled under oxidation atmosphere, it is difficult to obtain high crystalline after graphitization sometimes, it is therefore necessary to caused by making oxygen It is non-fusible excessively to carry out.Specifically, make to replace the oxygen amount in the graphite crystallization precursor after processing be usually 8 mass % with Under, preferably below 5 mass %.
In addition, replacing the device used during processing to be not particularly limited, such as usable blender, kneader.
(crushing)
Then, the graphite compound mixture for be heat-treated A is crushed.Because, by be heat-treated A and with Native graphite (D) Composite, to organize the block of graphite compound mixture of miniaturization, the state melting of No yield point or fusion to lead to Cross crushing and reach target grain size.
The granularity of graphite compound mixture after crushing is not particularly limited, but usually more than 1 μm, preferably 3 μm with On, more preferably more than 5 μm, more preferably more than 7 μm, in addition, usually less than 50 μm, preferably less than 35, it is more excellent Elect less than 30 μm as.If granularity is less than above range, the tap density as different orientation carbonaceous compound (A) diminishes, Therefore when electrode is made, it is difficult to improve the packed density of active material, it is difficult to obtain the battery of high power capacity.On the other hand, such as Fruit exceedes above range, then when being coated in the form of different orientation carbonaceous compound (A) to make electrode, is sometimes prone to Produce crawling.
For being not particularly limited for the device crushed, for example, as Roughpulverizer, jaw crusher, punching can be enumerated Hit formula crushing machine, cone crusher etc.；As middle pulverizer, roll crusher, beater grinder etc. can be enumerated；As micro- Pulverizer, can enumerate ball milling, vibromill, sprayer of hammer crusher, Ball-stirring mill, jet mill etc..
(heat treatment B：Sintering)
Heat treatment B refers to sintering and graphitization.Below, the explanation since sintering.But it is also possible to omit sintering.Will be logical The graphite compound mixture crushed and crushed is crossed to be sintered.Because, graphite compound mixture is molten during suppression graphitization Close, and remove by sintering the volatile ingredient of graphite compound mixture.
Temperature conditionss when being sintered are not particularly limited, but usually more than 600 DEG C, preferably more than 1000 DEG C, And the upper limit is usually less than 2400 DEG C, preferably less than 1300 DEG C.If temperature conditionss are less than above range, in graphitization When be sometimes prone to cause the fusion of graphite compound mixture powder.On the other hand, if it exceeds above range, then agglomerating plant need to Expense is wanted, therefore is carried out generally in the range of said temperature condition.
The gas shape for being sintered under the inactive atmospheres such as nitrogen or being produced in the graphite compound mixture after crushing again Into non-oxidizing atmosphere under carry out.In addition, in order to simplify manufacturing process, stone can also be directly carried out without sintering circuit Mo Hua.
As the device for sintering, it is not particularly limited, for example, shuttle-type stove, car tunnel furnace, electric furnace, coke roasting can be used Burn stove, rotary furnace etc..
(heat treatment B：Graphitization)
Then, graphitization is implemented to the graphite compound mixture for carrying out oversintering.Because, in increase cell evaluation Discharge capacity, and improve crystallinity.By graphitization, different orientation carbonaceous compound (A) can be obtained.
Temperature conditionss when carrying out graphitization are not particularly limited, but usually more than 2800 DEG C, preferably 2900 DEG C with On, more preferably more than 3000 DEG C, and usually less than 3400 DEG C, preferably less than 3200 DEG C.If it exceeds above range, Then the reversible capacity of battery diminishes sometimes, and the battery for making high power capacity is difficult to sometimes.In addition, if more than above range, then having Shi Shimo distillation amount easily becomes many.
Graphitization is under the inactive atmospheres such as argon gas or in the gas shape by sintered graphite compound mixture generation Into non-oxidizing atmosphere under carry out.As device used in graphitization, it is not particularly limited, for example, can enumerates direct-electrifying Stove, acheson furnace, the resistance-heated furnace as indirect power on tyupe, induction heater etc..
, i.e., can be with from the process for being heat-treated to sintering in addition, the process in graphitization processing or before it In material (native graphite (D), asphalt stock or graphite crystallization precursor) or surface addition Si, B etc. graphitization catalyst.
(other processing)
As long as in addition, the effect of the without prejudice to present invention, in addition to above-mentioned each processing, can also carry out classification processing etc. each Plant processing.Classification processing is in order that the granularity after graphitization processing is target grain size, and removes corase meal and micropowder.
As the device as classification processing, it is not particularly limited, for example, in the case where dry type is sieved, can use Gyratory sifter, rock type sieve, rotary type sieve, oscillatory type sieve etc.；In the case of dry type air current classifying, gravity type point can be used Level machine, inertia force formula grader, centrifugal force type grader (sizer, cyclone separator) etc.；Wet screening can use machinery Rotating vane type grader, hydraulic classifier, settling classifier, centrifugal wet classifier etc..
Classification processing can immediately continue with progress after the crushing after heat treatment A, can also be in other times, such as powder Carried out after sintering after broken, or after graphitization.Furthermore it is also possible to omit classification processing in itself.But, taken from reduction is different This point of the BET specific surface area of tropism carbonaceous compound (A), and productivity this point from the point of view of, preferably heat treatment A after crushing it After immediately continue with progress.
(processing after the manufacture of different orientation carbonaceous compound (A))
In order to control the BET specific surface area of negative material, improve electrode briquettability, raising discharge capacity and cheap Deng, can also to different orientation carbonaceous compound (A) the Delanium powder that separately manufacture of addition that is manufactured with said sequence or Natural graphite powder is simultaneously mixed.
[manufacture method 2 of the different orientation carbon complex of negative pole [5]]
Different orientation carbon complex can be manufactured according to the methods below.Different orientation carbon complex in the present invention is preferred Native graphite class carbonaceous material (B) carbonaceous material (C) different from native graphite class carbonaceous material (B) with orientation is combined Change, by way of example, method can be listed below：In above-mentioned native graphite (D), the precursor of above-mentioned carbonaceous material (C) will be used as Process of the asphalt stock by " mediate (mixing) ", " shaping ", " sintering ", " graphitization ", " crushing " is manufactured.But, this In a little processes, " shaping ", " sintering ", " crushing " can be omitted and/or implemented simultaneously with other processes.Specifically, it can pass through Manufacture method being exemplified below etc. is obtained.
[[mediating (mixing)]]
Carry out native graphite (D), asphalt stock and the mixing according to raw materials such as the graphitization catalysts for wishing addition.This When, in order to uniformly mix, preferably heated.Thus, as in the raw material not melted at a temperature of native graphite (D) and kneading Add the state of the asphalt stock of liquid.At this point it is possible to all raw materials are added in kneader while being mediated and being heated up, The composition beyond asphalt stock can be loaded in kneader and heated under stirring, temperature is risen to after kneading temperature, Add normal temperature or vulcanize the asphalt stock of molten condition.
Heating-up temperature is generally more than the softening point of asphalt stock, preferably in temperature of high more than 10 DEG C than softening point, more It is preferred that the temperature range at high more than 20 DEG C than softening point is carried out.In addition, the upper limit is usually less than 300 DEG C, preferably 250 DEG C with Under scope.If less than the scope, the viscosity of asphalt stock is uprised, and being mixed with may become difficult.On the other hand, if More than the scope, then due to volatilization and polycondensation, the viscosity of mixed system becomes too high sometimes.
Mixer preferably has a machine of agitator, and agitator can use Z-type, general as マ チ ス ケ ー タ types Agitator.The amount for putting into the raw material in mixer is usually more than the 10 volume % of mixer volume, preferably 15 bodies Product more than %, and be below 50 volume %, preferably below 30 volume %.Incorporation time is necessary for more than 5 minutes, up to directly The time of the change of obvious viscosity, usually 30~120 minutes are brought to the volatilization due to volatile ingredient.Mixer is preferred Kneading temperature is preheating to before mixing.
[[shaping]]
Obtained mixture can be supplied directly to devolatilization/agglomerant for removing volatile ingredient and carbonization Sequence, but in order to easily operate, devolatilization/sintering circuit is preferably available to after formation.
As long as shape can be kept, then forming method is not particularly limited, can be using extrusion molding, mould molding, quiet Hydraulic pressure shaping etc..Wherein, preferably extrusion molding or mould molding, because extrusion molding particle in formed body is easily orientated, and Although mould molding particle orientation keeps random, from productivity, easy operation more molded than hydrostatic, in addition, mixed Randomly-oriented structure will not be made to destroy and obtain formed body during conjunction.
Forming temperature can be a times of (temperature more than high temperature, the softening point of asphalt stock) under room temperature (low temperature), heating It is a kind of.When being molded at low temperature, in order to improve mouldability and obtain the homogeneity of formed body, it is desirable to the mixing that will be cooled down after kneading The advance coarse powder of thing is broken to below full-size 1mm.Shape, the size of formed body are not particularly limited, but in thermoforming, if Formed body is excessive, then carrying out uniform preheating before shaping needs the time, therefore it is usually preferred to which full-size is 150cm left Size below the right side.
If the pressure of briquetting pressure is too high, become difficult by the removing of the volatile ingredient of the micropore of formed body, and And be not that the native graphite (D) of proper circle is orientated, the crushing in subsequent handling becomes difficult, therefore the upper limit of briquetting pressure is led to It is often 3000kgf/cm2(294MPa) below, preferably 500kgf/cm2(49MPa) below, more preferably 10kgf/cm2 (0.98MPa) below.The pressure of lower limit is not particularly limited, but be preferably set in devolatilization/sintering circuit can be with Keep the degree of the shape of formed body.
[[devolatilization/sintering]]
In order to remove the volatile ingredient of native graphite (D) and asphalt stock, and the pollution of filler when preventing graphitization, Bonding of the filler to formed body, devolatilization/sintering is carried out to obtained formed body.Devolatilization/sintering generally exists More than 600 DEG C, preferably more than 650 DEG C, and to carry out 0.1 small for temperature generally below 1300 DEG C, preferably below 1100 DEG C When~10 hours.For anti-oxidation, heating is generally filled with the circulation of the non-active gas such as nitrogen, argon or in gap Is carried out in breeze (breeze), the non-oxidizing atmosphere of filling coke (Packing coke) equigranular carbon material
As long as the equipment electric furnace or gas burner that are used in devolatilization/sintering, electrode material coke roaster etc. The equipment that can be sintered in non-oxidizing atmosphere, is not particularly limited.In order to remove volatile ingredient, heating during heating Speed is preferably low speed, is generally warming up to and only produced with 3~100 DEG C/h of 200 DEG C or so volatilized since low boiling point component Near 700 DEG C of hydrogen.
[[graphitization]]
By carbide formed body obtained from devolatilization/sintering, then heating carries out graphitization at high temperature.It is right It is identical with the record of manufacture method 1 in graphited condition.
For anti-oxidation, graphitization is filled with coke under the circulation of the non-active gas such as nitrogen, argon or in gap Carried out under slag, the non-oxidizing atmosphere of filling coke equigranular carbon material.As long as the equipment electric furnace or coal that are used in graphitization The equipment of the achievable above-mentioned purposes such as steam stove, electrode material acheson furnace, is not particularly limited, programming rate, cold But speed, heat treatment time etc. can arbitrarily be set in the range of the equipment used allows.
[[crushing]]
The graphitization processing thing so obtained is typically block, it is difficult to used as negative electrode active material, therefore carries out powder Broken and/or big particle diameter shape material, the removing of small particle material.The breaking method of graphitization processing thing is not particularly limited, as Reducing mechanism, the device that machinery is ground can for example enumerate ball milling, beater grinder, CF mills, atomizer mill, pulverizer (pulverize), using the reducing mechanism of wind-force such as jet mill.For coarse crushing, middle crushing, jaw can be used to break Broken machine, hammer crusher, edge runner etc. utilize the grinding mode of impulsive force.Here, before grinding time can be graphitization, After can also being graphitization.
[the auxiliary material mixing of negative pole [5]]
In addition to above-mentioned different orientation carbon complex, by containing in the negative electrode active material of the lithium secondary battery of the present invention There are more than one carbonaceous materials (carbonaceous material) different in terms of the physical property of carbonaceous from above-mentioned different orientation carbon complex, can be with Further seek the raising of battery performance." physical property of carbonaceous " mentioned here, refers to X-ray diffraction parameter, median particle diameter, length Footpath is than, BET specific surface area, orientation ratio, Raman R value, tap density, real density, micropore distribution, circularity, one kind of ash amount Characteristic above.In addition, as preferred embodiment, can enumerate, volume reference size distribution is centered on median particle diameter When it is left-right asymmetry, not equal containing the different carbon material of two or more Raman R value or X-ray parameter.It is used as the one of its effect Individual example, can be enumerated by containing graphite such as native graphite, Delaniums；The carbon blacks such as acetylene black；Amorphous carbon such as needle coke etc. Carbon material reduces resistance etc. as auxiliary material.They can be used alone one kind, can also in any combination and arbitrary proportion Two or more is applied in combination.When being added as auxiliary material, its addition is usually more than 0.1 mass % preferably 0.5 mass % More than, more preferably more than 0.6 mass %, its upper limit is usually preferably below 50 mass % below 80 mass %, more preferably For below 40 mass %, more preferably below 30 mass % scope.If less than the scope, being difficult to be led sometimes The effect electrically improved.If it exceeds above range, then sometimes result in the increase of irreversible capacity at initial stage.
[electrode for making negative pole [5]]
Usual way can be used by manufacturing negative pole, can form negative pole [5] as described above.Collector, collector It is also same as described above with the ratio between the thickness of active material layer, electrode density, adhesive, pole plate orientation ratio, impedance etc..
<Negative pole [6]>
Below, the negative pole [6] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains graphite carbon granules Son is as negative electrode active material, and the circularity of the graphite carbon particle is more than 0.85, is determined by wide-angle x-ray diffraction (002) face interplanar distance (d002) be less than 0.337nm, use argon laser Raman spectroscopy determine with 1360cm-1's Peak intensity is relative to 1580cm-1The Raman R value of the ratio between peak intensity definition be 0.12~0.8.
[negative electrode active material of negative pole [6]]
Below, the negative electrode active material used in negative pole [6] is illustrated.
In the negative pole [6] of the lithium secondary battery of the present invention negative electrode active material that uses at least containing meet following (a), (b) with the graphite carbon particle of (c).
(a) circularity is more than 0.85；
(b) interplanar distance (d002) in (002) face that wide-angle x-ray diffraction is determined is less than 0.337nm；
(c) use argon laser Raman spectroscopy determine with 1360cm-1Peak intensity relative to 1580cm-1Peak The Raman R value (following, to be only abbreviated as sometimes " Raman R value ") that intensity ratio is defined is 0.12~0.8.
[[circularity]]
The circularity of graphite carbon particle used as the negative electrode active material of the lithium secondary battery of the present invention is usually More than 0.85, preferably more than 0.87, more preferably more than 0.89, particularly preferably more than 0.92.As the upper limit, circularity is It is theoretical proper sphere when 1.If circularity is less than the scope, the fillibility of negative electrode active material is reduced, heat conductivity reduction, Therefore hinder sometimes early stage output recover, particularly, by low temperature when low output state output recovery it is sometimes slack-off.
Described circularity is defined with following formula in the present invention.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured.
[[interplanar distance (d002)]]
The graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention is using wide The interplanar distance (d002) in (002) face that angle X-ray diffraction method is determined is less than 0.337nm, preferably below 0.336nm.Under Limit, is the theoretical value 0.335 of graphite.If it exceeds the scope, then crystallinity reduction, the heat conductivity as caused by electronics is reduced, The output recovery characteristics of early stage are reduced sometimes, particularly, by low temperature when low output state output recovery it is sometimes slack-off.
The interplanar distance (d002) in (002) face that described use wide-angle x-ray diffraction is determined, is by adopting in the present invention With the d values (interfloor distance) for learning the lattice plane (002 face) that the X-ray diffraction of method that shakes is tried to achieve.
In addition, the crystallite size (Lc) for the graphite carbon material tried to achieve by using the X-ray diffraction for learning method of shaking is without spy Do not limit, but usually more than 10nm, preferably more than 30nm, more preferably more than 80nm scope.If less than the scope, Then crystallinity is reduced, and the heat conductivity as caused by electronics is reduced, and the output recovery characteristics of early stage are reduced sometimes.
[[Raman R value]]
The Raman of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention R values are necessary for more than 0.12, preferably more than 0.15, more preferably more than 0.17, particularly preferably more than 0.2.Its upper limit is excellent Elect less than 0.8, more preferably less than 0.6, particularly preferably less than 0.45 as.If Raman R value is less than the scope, particle table The crystallinity in face is too high, and with the reduction of charge and discharge potential point, output is reduced sometimes.On the other hand, if it exceeds the scope, then grain The crystallinity reduction in sublist face, the heat transfer as caused by electronics is reduced, and the recovery characteristics of output are reduced sometimes.
Raman spectrum is determined as follows progress：Use raman spectroscopy device (such as raman spectroscopy that Japanese light splitting society manufactures Device), sample is fallen and is filled in cell naturally, argon laser is irradiated to the specimen surface in pond, meanwhile, pond is existed With being rotated in the face of laser vertical.For obtained Raman spectrum, 1580cm is determined-1Neighbouring peak PAIntensity IAAnd 1360cm-1Neighbouring peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as the Raman R value of graphite carbon material.Separately Outside, obtained Raman spectrum is determined in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the drawing of graphite carbon material Graceful half breadth.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
Raman R value, half breadth analysis：Background processing
Smooth treatment：Simple average, 5 points of convolution
The graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention exists 1580cm-1Neighbouring Raman half breadth has no particular limits, but usually 10cm-1More than, preferably 15cm-1More than, separately Outside, its upper limit is usually 60cm-1Hereinafter, preferably 50cm-1Hereinafter, more preferably 45cm-1Following scope.If Raman half It is worth width and is less than the scope, then the crystallinity of particle surface is too high, with the reduction of charge and discharge potential point, output is reduced sometimes.Separately On the one hand, if it exceeds the scope, then the crystallinity reduction of particle surface, the heat transfer as caused by electronics is reduced, output it is extensive Multiple characteristic is reduced sometimes.
[[tap density]]
The jolt ramming of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Density is usually 0.55g/cm3More than, preferably 0.7g/cm3More than, more preferably 0.8g/cm3More than, particularly preferably 1g/ cm3More than.In addition, the upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3Hereinafter, particularly preferably 1.6g/cm3Below. If tap density is less than the scope, as negative pole, in use, packed density is difficult to improve, interparticle contact area subtracts Lack, therefore heat conductivity is reduced sometimes.On the other hand, if it exceeds the scope, then the interparticle space in electrode is very few, non- The stream of water electrolysis liquid is reduced, therefore output is reduced sometimes in itself.
In the present invention, tap density is defined as below：Sample is set to fall by the sieve in 300 μm of aperture in 20cm3Jolt ramming In container, until behind upper surface of the sample full of container, using powder density determination device (for example, seishin enterprise-like corporations manufacture Tap densor) carry out 1000 length of stroke 10mm vibration, by thus when volume and sample weight try to achieve it is close Degree is defined as tap density.
[[BET specific surface area]]
The stone used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention determined using BET method The specific surface area of black matter carbon particle is preferably 0.1m2/ more than g, more preferably 0.7m2/ more than g, particularly preferably 1m2/ more than g, More preferably 1.5m2/ more than g.Its upper limit is preferably 100m2/ below g, more preferably 50m2/ below g, particularly preferably 25m2/ below g, more preferably 15m2/ below g.If the value of BET specific surface area is less than the scope, negative material is used as In use, the acceptance of lithium is easily deteriorated in charging, lithium is sometimes prone to separate out in electrode surface.On the other hand, if above Above range, then when as negative material, increase with the reactivity of nonaqueous electrolytic solution, and the gas of generation easily becomes many, sometimes difficult To obtain preferred battery.
BET specific surface area is defined as the value determined：Using surface area meter (for example, big storehouse reason develops make full-automatic Surface area determination unit), nitrogen circulation under, at 350 DEG C to sample carry out 15 minutes it is predrying, then, use nitrogen phase 0.3 nitrogen helium mixture is accurately adjusted to for the relative pressure of atmospheric pressure, by using the N2 adsorption of gas flow method 1 method of BET is determined.
[[volume average particle size]]
The volume of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Average grain diameter is defined as the average grain diameter (median particle diameter) for the volume reference tried to achieve by laser diffraction/scattering method, preferably 1 μm More than, more preferably more than 3 μm, more preferably particularly preferably more than 5 μm, more than 7 μm.In addition, its upper limit is usually Less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm, particularly preferably less than 25 μm.If less than above-mentioned model Enclose, then irreversible capacity increases, and occasionally results in the loss of initial cell capacity.In addition, if more than above range, being then made During electrode pad, uneven coated face is easily formed, is sometimes undesirable in battery production process.
[[micropore volume]]
The micropore of the graphite carbon particle used for the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Volume, the space in particle of 0.01 μm~1 μm equivalent to diameter tried to achieve by mercury, Hg porosimeter (mercury penetration method), by It is usually more than 0.01mL/g in the concavo-convex amount that causes of being uneven of particle surface, preferably more than 0.05mL/g is more excellent Elect more than 0.1mL/g as, its upper limit is usually below 0.6mL/g, preferably below 0.4mL/g, more preferably below 0.3mL/g Scope.If it exceeds the scope, then sometimes for substantial amounts of adhesive when being manufactured into pole plate.If high less than the scope Current density charge-discharge characteristic is reduced, also, the alleviation effects that electrode expansion when can not obtain discharge and recharge sometimes shrinks.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.If less than the scope, sometimes high current density charge-discharge characteristic reduction.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).About 0.2g samples (negative material) are weighed, are encapsulated into powder container, in room temperature, very (50 μm of below Hg) deaerate within 10 minutes under sky, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, mercury is imported, 40000psia (about 280MPa) is boosted to from 4psia (about 28kPa) stage shape, 25psia (about 170kPa) is then depressurized to.Rise Number of stages during pressure more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury intrusion for 80.Use Washburn formulas calculate micropore distribution from the mercury press-in curve so obtained.In addition, the surface tension (γ) of mercury is 485dyne/cm, contact angle (φ) is 140 °.Micropore diameter when mean pore footpath reaches 50% using accumulation micro pore volume.
[[ash content]]
The ash content of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Gross mass relative to graphite carbon particle is preferably particularly preferably below 0.5 mass % below 1 mass %, more preferably Below 0.1 mass %.In addition, its lower limit is preferably more than 1ppm.If it exceeds above range, then during discharge and recharge and non-aqueous solution electrolysis The deterioration of battery performance can not be ignored sometimes caused by the reaction of liquid.On the other hand, if less than the scope, in manufacture Long period and energy and the equipment for preventing pollution are needed, cost can rise sometimes.
The real density of graphite carbon particle is usually 2.0g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.In the present invention, real density It is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol.
[[orientation ratio]]
The orientation of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Than being usually more than 0.005, preferably more than 0.01, more preferably more than 0.015, the upper limit is less than 0.67 model in theory Enclose.If less than the scope, sometimes high density charge-discharge characteristic reduction.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
[[draw ratio]]
The major diameter of the graphite carbon particle used as the negative electrode active material of negative pole [6] in the lithium secondary battery of the present invention Than being theoretically more than 1, the upper limit is less than 10, preferably less than 8, more preferably less than 5.If it exceeds its upper limit, is made pole Striped can be produced during plate, uniform coated face can not be obtained, high current density charge-discharge characteristic is reduced sometimes.
In addition, draw ratio with the most major diameter A of particle during three dimensional viewing and perpendicular most minor axis B ratio A/B come table Show.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection be fixed on 50 microns of thickness with Under metal end face on any 50 graphite particles, rotation, tilt and be fixed with the objective table of sample, these grains are determined respectively A, B of son, obtain A/B average value.
The graphite carbon particle that uses of negative electrode active material as negative pole [6] in the lithium secondary battery of the present invention can be The material or made material naturally produced, but preferably graphite carbon particle contains native graphite.In addition, day The material or made material so produced can also apply specific processing.In addition, manufacture method is (also comprising sorting side Method) it is not particularly limited, it is, for example, possible to use graphite of the stage division sorting such as screening or air classification with above-mentioned characteristic Carbon particle and obtain.
Among these, particularly preferred graphite carbon particle is the carbonaceous particles or made carbonaceous to naturally producing Particle applies mechanics energy process and is modified and manufactures.Contain more preferably as the carbonaceous particles of the raw material of mechanics energy process There is native graphite.
[[mechanics energy process]]
Below, the mechanics energy process is illustrated.It is used as the carbonaceous of the raw material for the object for applying mechanics energy process Particle, is not particularly limited, and is natural or artificial graphite-like carbonaceous particles, as carbonaceous particles of graphite precursor etc..These The characteristic of raw material is as follows.
[[[being used as the raw graphite class carbonaceous particles of mechanics energy process]]]
On the property of raw graphite class carbonaceous particles, any one of (1)~(11) as follows is preferably met simultaneously Or it is multinomial.In addition, physical property measurement method or definition, identical with the situation of above-mentioned graphite carbon particle.
(1) X-ray parameter
Raw graphite class carbonaceous particles are by using the d value (layers for learning the lattice plane (002) that the X-ray diffraction of method that shakes is tried to achieve Between distance) be preferably more than 0.335nm, its upper limit is usually below 0.340nm, preferably below 0.337nm.In addition, passing through The crystallite size (Lc) for the graphite-like carbonaceous particles tried to achieve using the X-ray diffraction for learning method of shaking is usually more than 30nm, is preferably More than 50nm, more preferably more than 100nm scope.If less than the scope, crystallinity reduction, it is possible to increase initial stage not The increase of reversible capacity.
(2) ash content
Contained ash content is below 1 mass % relative to the gross mass of graphite-like carbonaceous in raw graphite class carbonaceous particles, Preferably below 0.5 mass %, particularly preferably below 0.1 mass %, its lower limit is usually more than 1ppm.If it exceeds above-mentioned Scope, then the deterioration of battery performance can not be ignored sometimes during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution.If be less than The scope, then need long period and energy and the equipment for preventing pollution in manufacture, and cost can rise sometimes.
(3) volume reference average grain diameter
The volume reference average grain diameter of raw graphite class carbonaceous particles is defined as the body tried to achieve by laser diffraction/scattering method The average grain diameter (median particle diameter) of product benchmark, usually more than 1 μm, preferably more than 3 μm, more preferably more than 5 μm, further Preferably more than 7 μm.In addition, its upper limit is not particularly limited, usually below 10mm, preferably below 1mm, are more preferably Less than 500 μm, particularly preferably more preferably less than 100 μm, less than 50 μm.If less than above range, by applying Reinforcing learns energy process and particle diameter is become too small, occasionally results in irreversible capacity increase.In addition, if more than above range, The device for then applying mechanics energy process is difficult to effective operating, occasionally results in temporal loss.
(4) Raman R value, Raman half breadth
The Raman R value of the raw graphite class carbonaceous particles determined using argon laser Raman spectroscopy be usually 0.01 with On, preferably more than 0.03, more preferably more than 0.1, its upper limit is usually less than 0.6, and preferably less than 0.4.If Raman R Value is less than the scope, then the crystallinity of particle surface is too high, the increase of Raman value caused by applying mechanics energy process, And due to crystalline reduction, as the discharge and recharge Li sites for entering interlayer tail off sometimes, i.e. charging acceptance drops sometimes It is low.On the other hand, if it exceeds the scope, then make the crystallinity of particle surface further drop due to applying mechanics energy process It is low, increase with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, 1580cm-1Raman half breadth have no particular limits, usually 10cm-1More than, preferably 15cm-1With On, in addition, its upper limit is usually 50cm-1Hereinafter, preferably 45cm-1Hereinafter, more preferably 40cm-1Following scope.If drawn Graceful half breadth is less than the scope, then the crystallinity of particle surface is too high, the Raman caused by applying mechanics energy process The increase of value, and due to crystalline reduction, as the discharge and recharge Li sites for entering interlayer tail off sometimes, i.e. charging by Property is reduced sometimes.On the other hand, if above the scope, then the crystallinity of particle surface is made due to applying mechanics energy process Further reduction, increases with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
(5) BET specific surface area
The specific surface area of the raw graphite class carbonaceous particles determined using BET method usually 0.05m2/ more than g, be preferably 0.2m2/ more than g, more preferably 0.5m2/ more than g, particularly preferably 1m2/ more than g.Its upper limit is usually 50m2/ below g, it is excellent Elect 25m as2/ below g, more preferably 15m2/ below g, particularly preferably 10m2/ below g.If the value of BET specific surface area is less than The scope, then increase BET specific surface area due to applying mechanics energy process, and in charging, the acceptance of lithium is easily deteriorated, Lithium is easily separated out in electrode surface.On the other hand, if above above range, then BET is made due to applying mechanics energy process Specific surface area further increases, during as negative electrode active material, increases with the reactivity of nonaqueous electrolytic solution, the gas of generation is easy Become many, be difficult to obtain preferred battery sometimes.
(7) circularity
The spherical degree of raw graphite class carbonaceous particles, the particle diameter of raw graphite class carbonaceous particles are used as using circularity It is preferably more than 0.1 for the circularity of the particle of 3~40 μ ms, more preferably more than 0.2, particularly preferably more than 0.4, enter One step is preferably more than 0.5, and most preferably more than 0.6.If less than the scope, even if applying mechanics energy process, also not Understand fully spheroidization, high current density charge-discharge characteristic is reduced sometimes.
(8) real density
The real density of raw graphite class carbonaceous particles is usually 2g/cm3More than, preferably 2.1g/cm3More than, more preferably 2.2g/cm3More than, more preferably 2.22g/cm3More than, 2.26g/cm is limited to thereon3Below.The upper limit is the theory of graphite Value.If less than the scope, the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
(9) tap density
The tap density of raw graphite class carbonaceous particles is usually 0.05g/cm3More than, preferably 0.1g/cm3More than, more Preferably 0.2g/cm3More than, particularly preferably 0.5g/cm3More than.Additionally, it is preferred that being 2g/cm3Hereinafter, more preferably 1.8g/ cm3Hereinafter, particularly preferably 1.6g/cm3Below.If tap density is less than the scope, even if applying mechanics energy process, The raising of tap density is also insufficient, as negative electrode active material in use, packed density be difficult improve, can not obtain sometimes The battery of high power capacity.On the other hand, if above the scope, then when applying mechanics energy process, tap density is further up, The interparticle space being made in the electrode after electrode is very few, because the stream of nonaqueous electrolytic solution is not enough, high current density charge and discharge Electrical characteristics are likely to decrease.The tap density of graphite-like carbonaceous particles is also determined and defined using method same as described above.
(10) orientation ratio (powder)
The orientation ratio of raw graphite class carbonaceous particles is usually more than 0.001, and preferably more than 0.005.The upper limit is in theory Upper is less than 0.67.If less than the scope, even if applying mechanics energy process, the raising of orientation ratio is also insufficient, sometimes High density charge-discharge characteristic is reduced.
(11) draw ratio (powder)
The draw ratio of graphite-like carbonaceous particles is theoretically more than 1, and the upper limit is usually less than 10, and preferably less than 8, it is more excellent Elect less than 5 as.If it exceeds its upper limit, even if then applying mechanics energy process, draw ratio can not be reduced fully, and pole plate is made When can produce striped, uniform coated face can not be obtained, high current density charge-discharge characteristic is reduced sometimes.
, can as the high crystalline carbon material that carbon hexagonal net surface structure is flourishing in above-mentioned raw graphite class carbonaceous particles Enumerate the highly oriented graphite for making hexagonal wire side substantially be grown with planar orientation and the direction such as be integrated into highly oriented graphite particle on Isotropism high-density graphite.As preferred highly oriented graphite, the day that Sri Lanka or Madagascar produce can be enumerated Right graphite, the so-called kish separated out by the iron melted in the form of oversaturated carbon, part high graphitization degree it is artificial Graphite etc..
Native graphite is classified as flaky graphite (Flake Graphite), flaky graphite according to its character (Crystalline (Vein) Graphite), soil graphite (Amorphous Graphite) (referring to《Bulk material technology It is integrated》, one, the graphite of ((strain) industrial technology center, Showa is issued for 49 years)；And " HAND BOOK OF CARBON, GRAPHITE, DIAMOND AND FULLERENES ", (Noyes Publications distribution)).Degree of graphitization is with flaky graphite Highest, is 100%, followed by flaky graphite, is 99.9%, and soil graphite as little as 28%.It is used as the scale of native graphite Shape graphite originates from Madagascar, China, Brazil, Ukraine, Canada etc.；Flaky graphite mainly originates from Sri Lanka.Soil It is the Korea peninsula, China, Mexico etc. the main product of graphite.In these native graphites, the usual particle diameter of soil graphite is small, and purity It is low.In contrast, flaky graphite or flaky graphite have the advantages that degree of graphitization height, impurity level are few, therefore can preferably exist Used in the present invention.
Delanium can be under non-oxidizing atmosphere by petroleum-type heavy oil, coal class heavy oil, petroleum-type coke or coal Class coke at 1500~3000 DEG C or more than its temperature at a temperature of heat and manufacture.
In the present invention, as long as showing highly oriented and high power capacity after mechanics energy process and heat treatment is carried out, then may be used To use arbitrary Delanium to be used as raw material.In addition, in above-mentioned Delanium, even the incomplete material of graphitization, Such as graphite precursor, as long as it can turn into the graphite carbon particle for meeting above-mentioned physical property by carrying out mechanics energy process, It can then be used as the raw material of the mechanics energy process of the present invention.
[[[content of mechanics energy process]]]
To these raw graphite class carbonaceous particles carry out mechanics energy process can reduce particle diameter, make after processing with processing The ratio between preceding volume average particle size is less than 1, and improves tap density by the processing, can also make Raman by the processing R values reach more than 1.1 times.
By carrying out such mechanics energy process, turn into as follows as carbonaceous particles such as the graphite-like carbonaceous particles of raw material Particle：High crystalline is kept on the whole, simply the near surface of particle becomes coarse, tilt and expose edge surface.So, lithium The face increase that ion can come in and go out, even if at higher current densities also with high capacity.
Can effectively utilize crushing, classification, mixing, granulation, surface be modified, in the engineering in particle design such as reaction Primitive operation in, the present invention in " mechanics energy process " belong to " pulverization process ", but simultaneously also include by being tied to surface Structure is impacted, rubbed or compressed etc. and produced and be surface-treated as fine fault of construction.
In general, so-called pulverization process, refers to material applying power, make its size reduce with the particle diameter of Auto-regulator or Size distribution, fillibility.Pulverization process is classified according to species, the processing form of the power applied to material.Material is applied Plus power be roughly divided into following 4 kinds：(1) beat power (impulsive force), (2) crushing force (compression stress), (3) grinding forces (grinding forces), Shaving power (shearing force).On the other hand, processing form is roughly divided into following 2 kinds：Produced in inside particles and be cracked and be allowed to propagate Volume crush and cut particle surface surface crush.Volume is crushed using impulsive force, compression stress, shearing force to enter OK；Crush and can be carried out using grinding forces, shearing force in surface.Pulverization process is species and the place for the power that will apply to these materials Manage the processing that form carries out various combinations.Its combination can suitably be determined according to processing intent.Although pulverization process is also used The reaction or volumetric expansion of the chemistry such as explosion are carried out come situation about carrying out usually using mechanical devices such as pulverizers.
The mechanics energy process preferably used in the manufacture of the graphite carbonaceous particles of the present invention is preferably finally comprising at surface The processing that uprises of ratio shared by the crushing (surface crushing) of particle surface part is managed to obtain, and it is unrelated with whetheing there is volume crushing.This It is because the crushing of particle surface is for removing the angle of the carbonaceous particles such as graphite carbonaceous particles so that shape of particle becomes round is Important.Specifically, surface crushing can be carried out again after a certain degree of volume crushing is carried out and carries out mechanics in this wise Energy process, can also almost crush without volume and only carry out surface crushing and carry out mechanics energy process in this wise.Also Volume crushing can be carried out simultaneously and surface is crushed and carries out mechanics energy process in this wise.It is preferred that surface crushing is finally carried out, Remove arrisdefect in this wise to carry out mechanics energy process from the surface of particle.
The mechanics energy process of the present invention can reduce particle diameter, make after processing be with the ratio between the volume average particle size of before processing Less than 1, and tap density is improved by the processing, also Raman R value can be made to reach more than 1.1 times by the processing.
So-called " the ratio between volume average particle size before and after the processing ", be processing after volume average particle size divided by before processing body It is worth obtained from product average grain diameter.The value of (volume average particle size after processing)/(volume average particle size of before processing) be 1 with Under, preferably less than 0.95.If being essentially 1, fillibility obtained from improving circularity by mechanics energy process is carried High effect very little sometimes.Furthermore it is also possible to the ratio between be caused by reducing particle size after processing with the average grain diameter of before processing Shape of particle is controlled for less than 1.
Tap density can be improved by the mechanics energy process in the present invention.Improve tap density and refer to as described later carry The high spheroidization degree by representative of circularity.Therefore, mechanics energy process must be such processing.(the jolt ramming after processing Density)/the value of (tap density of before processing) is more than 1, preferably more than 1.1.If less than 1, circularity improves institute's band The effect very little sometimes that the fillibility come is improved.
By the mechanics energy process in the present invention Raman R value can be made to be more than 1.1 times.Raman R value is improved to refer to as rear Crystallinity near described reduction particle surface, mechanics energy process must be such processing.(the Raman R after processing Value)/the value of (Raman R value of before processing) is more than 1.1, preferably more than 1.4.If less than 1.1, because Raman R value becomes Change the effect of caused charging acceptance raising very little sometimes.
The mechanics energy process of the present invention is to become round particle, so that the tap density of these particles rises.For Improve the tap density of powder particle, it is known that filling can enter the smaller grain in the space formed between particle and particle Son is preferred.If handled it is therefore contemplated that to carbonaceous particles such as graphite-like carbonaceous particles crush etc. to reduce particle diameter, Tap density can be improved, but particle diameter is reduced using such method, in general tap density is reduced on the contrary.It is former as it Cause, it is believed that be due to crush so that shape of particle becomes more amorphous.
On the other hand, the number (ligancy of the particle contacted with the particle (particle of concern) in powder particle group N) more, the ratio shared by the space of packed layer is reduced.That is, as the factor that influence is brought on tap density, particle The ratio and ratio of components of size, i.e. particle diameter distribution are important.But, the research is simply carried out with the spheroidal particle group of model , the carbonaceous particles such as graphite-like carbonaceous particles of before processing used in the present invention are flakey, squamous, tabular, although tasted Try to control particle diameter distribution only with common crushing, classification etc., so as to improve tap density, but can not produce such High occupied state.
In general, the particle diameter of the carbonaceous particles such as graphite-like carbonaceous particles of flakey, squamous, tabular is smaller, its jolt ramming Density more has the tendency of reduction.This is regarded as because following reason：Due to particle by crushing more amorphization, and Overshooting shape thing such as " flash ", " strippings " or " warpage " of particle surface generation increases, and in particle surface with to a certain degree Intensity is attached with the reasons such as finer amorphous particle, so, and the impedance between adjacent particle becomes big, dislikes fillibility Change.
If the amorphism of these particles is reduced, shape of particle is close to spherical, even if then particle diameter diminishes, fillibility Reduction also tails off, and in theory, big particle, small particle particle should all show the tap density of equal extent.
The present inventor etc. confirm following content by research：Real density is of substantially equal, average grain diameter is also of substantially equal Carbonaceous or graphite particle, shape are spherical, and tap density more shows high value.That is, make shape of particle band circular, approach In it is spherical be important.If shape of particle subglobular, the fillibility of powder is also significantly improved simultaneously.In the present invention, by In above-mentioned reason, index when applying mechanics energy uses the tap density of powder.The fillibility of bulk material after processing is than at When rising before reason, it is believed that be by using processing method and the result that makes particle spheroidization and bring.In addition, the present invention In method, processing is carried out so that the tap density of the carbon material obtained when particle diameter is substantially reduced using common crushing with obtaining The tap density of the carbon material of the equal extent particle diameter obtained is compared, if during display high level, it is believed that be the result of spheroidization.
, can as the index of the crystallinity and the roughness of particle surface of particle, that is, the edge surface amount crystallized To use interplanar distance (d002), crystallite dimension (Lc) and the Raman R value in (002) face determined by wide-angle x-ray diffraction.One As for, the material that value is small, crystallite dimension (Lc) is big of the carbon material interplanar distance (d002) in (002) face, its Raman R value is got over It is small.That is, same crystalline state is almost presented in whole carbonaceous particles of graphite-like carbonaceous particles etc..In contrast, it is of the invention The value of the interplanar distance (d002) in graphite carbon particle (although 002) face is small, crystallite dimension (Lc) greatly, Raman R value is taken big Value.That is, although the block crystallinity of graphite carbon particle is high, near surface is (apart from particle surfaceLevel) crystallinity mix Disorderly, show edge surface expose change it is many.
From the viewpoint of fillibility is improved, more preferably reach circularity by the mechanics energy process in the present invention 1.02 times, circularity is particularly preferably set to reach 1.04 times.
[[[device used in mechanics energy process]]]
The device for carrying out mechanics energy process is selected from the device that can carry out above-mentioned preferred processing.This hair A persons of good sense etc. are had found when being studied, although more than one of 4 kinds of power that material applies can also be realized using above-mentioned, but excellent Select following device：Based on impulsive force, and particle is applied repeatedly compression including the interaction of particle, friction, The mechanisms such as shearing force.And specifically, it is preferable to following device：The device has inside case is provided with turning for multiple blades Son, and rotated at a high speed by the rotor and assign the machineries such as impact compress, friction, shearing force to the carbonaceous particles for importeding into inside Effect so that while carry out volume crush while carry out surface crushing.In addition, more preferably having by making carbonaceous particles circulate or right Flow and assign repeatedly the device of the mechanism of mechanism.The quantity of blade inside case preferably more than 3, particularly preferred 5 with On.
As an example of the preferred device for meeting such important document, (strain) nara machinery manufacturing company can be enumerated The hybrid system of manufacture.When being handled using the device, the peripheral speed of the rotor of rotation is preferably set as 30~100m/ Second, more preferably it is set as 40~100m/ seconds, is further preferably set as 50~100m/ seconds.In addition, processing can simply only Pass through carbonaceous particles, but preferably handled in device interior circulation or be detained more than 30 seconds, more preferably followed in device Ring is detained more than 1 minute to be handled.
As raw material graphite-like carbonaceous particles real density be less than 2.25, and crystallinity it is so high when, preferably Further carry out improving crystalline heat treatment after mechanics energy process is carried out.It is such heat treatment preferably 2000 DEG C with It is upper to carry out, carry out, carried out further preferably more than 2800 DEG C more preferably more than 2500 DEG C.
[electrode for making negative pole [6]]
Usual way can be used by manufacturing negative pole, can form negative pole [6] as described above.Collector, collector It is also same as described above with the ratio between the thickness of active material layer, electrode density, adhesive, pole plate orientation ratio, impedance etc..
<Negative pole [7]>
Below, the negative pole [7] used in the lithium secondary battery of the present invention is illustrated, the negative pole contains comprising multielement Negative electrode active material (C) as negative electrode active material, the negative electrode active material (C) comprising multielement contain selected from Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd and Sb lithium occlusion metal (A) and/or lithium occlusion alloy (B) At least one of, and contain C and/or N as element Z.
[negative electrode active material of negative pole [7]]
Below, the negative electrode active material used in negative pole [7] is illustrated.
[[composition]]
The negative electrode active material used in the negative pole [7] of the lithium secondary battery of the present invention is characterised by, at least containing energy The metal (lithium occlusion metal (A)) and/or alloy (lithium occlusion alloy (B)) of enough occlusion lithiums, and contain C and/or N as element Z。
So-called lithium occlusion metal (A), refers to be selected from Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd One or more of with Sb.Wherein, preferably Al, Si, Sn or Pb, more preferably Si or Sn, more preferably Si.As excellent The reasons why selecting Si, the capacity that can enumerate per unit mass is big.
So-called lithium occlusion alloy (B), refers to the alloy containing two or more above-mentioned lithium occlusion metal (A), or in lithium occlusion Alloy containing " element beyond lithium occlusion metal (A) and C, N " in metal (A).As this " lithium occlusion metal (A) and C, N with Outer element ", is preferably selected from the race of periodic table 4,5 races, 6 races, 8 races, 9 races, 10 races, 11 races, 13 races, one kind in 16 races or 2 kinds Element above, more preferably Ti, Zr, V, Cr, W, B, O, Co element, more preferably Ti, Zr, W, O, Co element.Due to These elements easily form high melting compound, thus from the point of view of control reactivity this point it is preferable to use.From the sight of capacity From the point of view of point, the content of " element beyond lithium occlusion metal (A) and C, N " of alloy is formed preferably with respect to lithium occlusion alloy (B) For 50 moles of below %.
In addition, containing mode in the negative electrode active material (C) comprising multielement as element Z C and/or N, it can arrange Lift following manner：
1. the state contained in lithium occlusion metal (A) and/or lithium occlusion alloy (B) (includes element Z lithium occlusion material (D))；
2. state (the external lithium occlusions of element Z being present in around lithium occlusion metal (A) and/or lithium occlusion alloy (B) Matter (F))；
3. the compound state of above-mentioned 1 and 2 state.
As the preferred mode for the lithium occlusion material (D) for including element Z, preferred elements Z (C and/or N) is with non-equilibrium shape State is present in lithium occlusion metal (A) and/or lithium occlusion alloy (B), and particularly preferably lithium occlusion metal (A) is Si.
As the preferred mode of the external lithium occlusion materials (F) of element Z, preferred elements Z is C, and C can show conduction The state of property.
The negative electrode active material (C) comprising multielement as negative electrode active material used in the present invention, inhales containing lithium Metal (A) and/or lithium occlusion alloy (B) are stayed, and is essential component containing C and/or N, preferably further containing selected from periodic table 4 Race, 5 races, 6 races, 8 races, 9 races, 10 races, 11 races, 13 races, one kind in 16 races or element of more than two kinds.As such element, More preferably Ti, Zr, V, Cr, W, B, O, Co element, more preferably Ti, Zr, W, O, Co element.
1. include element Z lithium occlusion material (D)
In the lithium occlusion metal (A) of the present invention, because Si is readily available effect, therefore, the lithium occlusion for including element Z is used as Material (D), preferably using element Z it is non-equilibrium be present in the compound of phase in Si as the formula SiZ of principal componentxMy(in formula, Z, Shown in for example following condition (1)~(4) of M, x, y) material that represents.
(1) element Z is to include C and/or N element；
(2) element M be one kind in the element beyond Si and element Z or two or more；
(3) x is the value for making Z concentration ratios Q (Z) reach 0.10~0.95, and the Z concentration ratios Q (Z) is relative to closest The compound SiaZp (in formula, a, p are integer) existed in Si Compositional balance Z concentration (p/ (a+p)), by formula Q (Z)=[x/ (1+x)]/[p/ (a+p)] and calculate；
(4) y is the number of the scope of 0≤y≤0.50.
(on SiZxMy)
((element Z))
SiZxMyIn element Z be to include C and/or N element.Additionally, it is preferred that reasons of the C and/or N as the element Z included By as follows：
(1) compound higher than Si fusing point can be formed；
(2) covalent radius is smaller than Si；
(3) diffusion coefficient in Si is small；
(4) even if being reacted with lithium, its Volume Changes is also small etc..
Specifically, Elements C, N can form SiC, Si3N4The compound existed Deng the fusing point balance higher than Si.Also, Gao Rong The free energy that point compound is generally produced is negative, is highly stable compound, therefore from can effectively reduce Si activity, is pressed down From the viewpoint of system and the reactivity of nonaqueous electrolytic solution, preferably C and/or N are used as element Z.
Further, since the covalent bond atomic radius of Elements C, N than Si is small, it can thus be assumed that being difficult to be formed in SiZxMyChemical combination The compound of presence is balanced in thing, it is effective to be evenly distributed for element Z in higher concentrations, although its details is not bery It is clear, but from can effectively reduce Si activity, suppress from the viewpoint of the reactivity with nonaqueous electrolytic solution, be preferred.
In addition, the diffusion coefficient of Elements C, N in Si is small, therefore Elements C, N are when being dispersed in Si, are produced along with discharge and recharge Raw Si cohesion or crystallization are suppressed, and are from the viewpoint of the reaction from suppression Si micronizing or with nonaqueous electrolytic solution It is preferred that.Further, since even if Elements C, N react with lithium, its Volume Changes is also small, therefore is difficult the conductive path cut-out to Si Bring influence, therefore it is preferred that.
In addition, as the elements such as Cu, Ni, Cu3Si、Ni2When Si etc. can balance the compound of presence than Si low melting points, Si activity can not be made effectively to reduce and be difficult to suppress the reactivity with nonaqueous electrolytic solution, and Cu, Ni element are in Si Diffusion coefficient is big, therefore carries out Si cohesion or crystallization along with discharge and recharge, easily causes Si micronizing, cycle characteristics has Shi Buhui is enhanced.In addition, in SiZxMyWhen the compound of presence is balanced in compound as principal component, it is impossible to make Si activity Reduction, and can not suppress the reactivity with nonaqueous electrolytic solution, therefore situations such as there is cycle characteristics deterioration.
((element M))
SiZxMyIn element M be the one kind or two or more element selected from the element beyond Si and element Z, be preferably One kind or element of more than two kinds in the race of periodic table 4,5 races, 6 races, 8 races, 9 races, 10 races, 11 races, 13 races, 16 races, due to High melting compound is easily formed, from the point of view of reactivity this point is suppressed, more preferably Ti, Zr, V, Cr, W, B, O element, further Preferably Ti, Zr, W, O element.
In SiZxMyComposition in, SiZxMyX be the value for making Z concentration ratios Q (Z) reach following scope, the scope is： Usually more than 0.10, it is preferably more than 0.15, more preferably more than 0.30, particularly preferably more than 0.40, in addition, the upper limit is logical Often it is less than 0.95, be preferably less than 0.85, be more preferably less than 0.75, is more preferably less than 0.65；The Z concentration ratios Q (Z) is relative to the compound SiaZp (in formula, a, p are integer) existed closest to Si Compositional balance Z concentration (p/ (a+p)), calculated by formula Q (Z)=[x/ (1+x)]/[p/ (a+p)].In addition, described " with flat closest to Si composition Weigh the compound existed ", refer in SiaZp, p/ (a+p) value takes minimum and balances the compound SiaZp of presence.
In addition, in the present invention with the compound SiaZp that exists closest to Si Compositional balance Si and element Z phase Figure is (for example, " the Desk Handbooks Phase Diagrams for Binary that ASM International companies publish Alloys ") in it is on the books, in the present invention, Z concentration (p/ (a+p)) relative to the SiaZp sets above-mentioned Z concentration ratios Q (Z), and using Z concentration ratios Q (Z) number range x scope is limited.
The compound that so-called balance mentioned here is present, is the change recorded in above-mentioned phasor etc. as the summit of line chart Compound SiaZpDaltonides such as (in formula, a, p are integer), for example, when Z is C, it is known that SiC is stable compound, in this hair In bright, the compound that the compound is existed as balance.Therefore, when Z is C, Sis of the SiC equivalent to the present inventionaZp.In addition, example During such as Z for N, although known Si3N4It is most stable of compound, but it is known that Si2N3, SiN also serve as daltonide presence, In the present invention, the compound these all compounds existed as balance.Therefore, when Z is N, SiN is equivalent to the present invention SiaZp。
On the other hand, the compound of the phase of so-called non-equilibrium presence, refers to the compound beyond the compound that balance is present. In the case of the compound of non-equilibrium presence, specific daltonide is not formed, from macroscopically seeing that Si atoms and Z atoms are uniform It is scattered.
Z concentration ratios Q (Z) is if less than the scope, the effect for reducing Si activity is small, it is impossible to suppress and nonaqueous electrolytic solution Reactivity, electrode expansion becomes big, preferred cycle characteristics can not be obtained sometimes.On the other hand, if it exceeds the scope, then shape The compound Si of the stabilization existed into balanceaZpDeng, even if increase element Z, Si activity also do not reduce, can not suppress sometimes with The reactivity of nonaqueous electrolytic solution.Further, since SiaZpDeng electric conductivity it is low, therefore when forming such compound, active material Electric conductivity deteriorate, the doping of lithium, dedoping become difficult, and discharge and recharge can not be carried out sometimes.
Here, when Z concentration ratios Q (Z) is 1, it is meant that Si forms stable compound SiaZp, not preferably.In addition, if big Width exceedes the scope, then is difficult to obtain the effect containing the Si high capacities brought, preferred battery can not be obtained sometimes special Property.
In addition, as element Z, when at the same time using C and N element, obtaining the Si of each relative to 2 kinds of elementsaZpBase The Z concentration ratios Q (Z) of accurate element Z concentration, and regard its aggregate value as Z concentration ratios Q (Z).
SiZxMyIn y be satisfaction 0≤y≤0.5 real number.Compound SiZxMyIn contain element M, during and y ≠ 0, chemical combination Thing SiZxMyIn the ratio y of element M be usually more than 0.08, preferably more than 0.10, in addition, its upper limit be usually 0.50 with Under, preferably less than 0.40, more preferably less than 0.30.If y exceedes the scope, Si content tails off, is difficult to sometimes To high power capacity.When being substantially free of element M, the ratio y of element M is y=0 or y ≒ 0.In the present invention, so-called y ≒ 0 refer to In manufacturing process of negative electrode active material of the present invention etc., the feelings inevitably containing element M (being substantially free of M) Condition, for example, situations of the y less than 0.08.
The composition of negative electrode active material (C) comprising multielement can be obtained according to usual way, for example, being penetrated using X Linear light electricity optical splitter (for example, " ESCA " of the manufacture of ulvac-phi companies), makes to be placed on examination upward containing negative pole compound side Expect on platform, and make its surface flat, the K alpha rays using aluminium carry out Ar sputterings while carrying out depth curve as x-ray source (デ プ ス プ ロ Off ァ イ Le, depth profile) is determined, and the atomic concentration of Si, element Z, element M etc. is calculated respectively.
(SiCxOyComposition)
When element Z is C and element M is O, in formula SiCxOyIn, x is usually more than 0.053, and preferably more than 0.08, More preferably more than 0.15, particularly preferably more than 0.25, its upper limit is usually less than 0.90, and preferably less than 0.75, it is more excellent Elect less than 0.60, particularly preferably less than 0.45 as.In addition, y is usually more than 0, preferably greater than 0 value, particularly preferably More than 0.08, more preferably more than 0.10, in addition, its upper limit is usually less than 0.50, preferably less than 0.40, particularly preferably Less than 0.30.
(including existences of the element Z in element Z lithium occlusion material (D) in Si)
In the negative pole compound SiZ of the present inventionxMyIn, for existences of the element Z in Si, its X-ray diffraction measure XIsz values be not particularly limited, element Z be C when, preferably less than 1.2, more preferably less than 0.7.When element Z is N, preferably For less than 1.1, more preferably less than 1.0.XIsz values be the scope below, refer to element Z it is non-equilibrium be present in Si It is mutually principal component, and SiaZpThe compound that isoequilibrium is present is not principal component, will not produce following XIsz values more than above-mentioned model The problem of situation about enclosing, therefore it is preferred that.When XIsz values exceed above range, i.e. SiaZpIsoequilibrium exist compound phase based on into When point (element Z is that carborundum, element Z are silicon nitrides when being N when being C), there is situations below：Si activity, which will not be made, to be reduced, The reactivity with nonaqueous electrolytic solution, the situation that cycle characteristics deteriorates can not be suppressed；Due to SiaZpDeng electric conductivity it is low, active material The electric conductivity of film deteriorates, and the doping of lithium, dedoping become difficult, so that the situation of discharge and recharge can not be carried out；Or per unit The situation that the discharge capacity of mass activity material diminishes.The lower limit of XIsz values is usually more than 0.00.
((X-ray diffraction measure method))
The negative electrode active material of the present invention can be for example arranged to by shadow surface by the XIsz values of X-ray diffraction measure, And determined using X-ray diffraction device (for example, " X-ray diffraction device " that (リ ガ Network) company of science manufactures), for determining Condition, shown in embodiment as be described hereinafter.
In addition, XIsz values are defined as follows.
(((XIsz values when element Z is C)))
The peak intensity Isz that 2 θ are 35.7 degree, the peak intensity Is that 2 θ are 28.4 degree are determined, its strength ratio XIsz is calculated (XIsz=Isz/Is), it is defined as the XIsz of active material film.Here, 2 θ think to come from for 35.7 degree of peak SiC peak, 28.4 degree of peak comes from the peak of silicon, and XIsz values refer to almost not detect SiC for less than 1.2.
(((XIsz values when element Z is N)))
The peak intensity Isz that 2 θ are 70.2 degree, the peak intensity Is that 2 θ are 28.4 degree are determined, its strength ratio XIsz is calculated (XIsz=Isz/Is), it is defined as the XIsz of active material film.Here, 2 θ think to come from for 27.1 degree of peak Si3N4Peak, 28.4 degree of peak comes from the peak of silicon, and XIsz values are less than 1.1 to refer to almost not detect Si3N4。
(distribution for including the element Z in element Z lithium occlusion material (D))
The SiZ of the present inventionxMyIn element Z less than 1 μm water such as with atom or molecule or cluster (cluster) Flat size is present, and element Z distribution is preferably in SiZxMyIn be uniformly distributed, more preferably from SiZxMyCentral part to table Face direction makes element Z concentration gradient become highland and tilt (in the case of film-form negative material described later, to connect from collector Contact portion point makes concentration gradient become highland inclination to film surface；In the case of powdered negative material, from particle centre portion to thin Film surface makes concentration gradient become highland inclination) distribution.In negative electrode active material, element Z distribution is unevenly locally lain in When, the Si parts in the absence of element Z are concentrated in along with expansion/contraction caused by Si discharge and recharge, therefore, with circulation Progress, electric conductivity deteriorates sometimes.Element Z dispersity as later shown, can be confirmed by EPMA etc..
(distribution of element M)
The SiZ of the present inventionxMyIn the distribution of element M be not particularly limited, can be uniformly distributed or Uneven distribution.
(Raman RC values, Raman RSC values, Raman RS values)
The Raman RC values that the lithium occlusion material (D) for including element Z in the present invention is determined by Raman spectrum analysis are usual For more than 0.0, its upper limit is preferably less than 2.0.If Raman RC values exceed the scope, it is difficult to obtain what is brought containing Si The effect of high capacity, it is difficult to obtain preferred battery behavior.When particularly element Z contains C, the negative electrode active on the present invention Material SiZxMyRaman RC values, preferably less than 2.0, more preferably less than 1.0, particularly preferably less than 0.5.Due to determining Upper the reason for, the lower limit of Raman RC values is usually more than 0.0.
The Raman RSC values that the lithium occlusion material (D) for including element Z in the present invention is determined by Raman spectrum analysis are usual For more than 0.0, its upper limit is preferably less than 0.25.If Raman RSC values exceed the scope, electric conductivity deteriorates, the doping of lithium, Dedoping becomes difficult, and discharge and recharge can not be carried out sometimes.In addition, when particularly element Z contains C, RSC values be preferably 0.25 with Under, more preferably less than 0.20.Due in measure, the lower limit of Raman RSC values is usually more than 0.0.
The Raman RS values that the lithium occlusion material (D) for including element Z in the present invention is determined by Raman spectrum analysis are preferred For more than 0.40, more preferably more than 0.50, its upper limit is preferably less than 1.00, and more preferably less than 0.90.If Raman RS Value is less than the scope, then cycle characteristics is possible to deteriorate.On the other hand, if it exceeds the scope, it is likely that can not be filled Electric discharge, not preferably.When particularly element Z contains C, RS values are preferably more than 0.40, more preferably more than 0.50；Its upper limit is preferred For less than 0.75, preferably less than 0.65.When particularly element Z contains N, RS values are preferably more than 0.40, more preferably 0.50 More than；Its upper limit is preferably less than 1.00, and preferably less than 0.90.
The Raman RC values determined by Raman spectrum analysis, Raman RSC values, Raman RS values in the present invention is by using following The Raman spectrum analysis of Raman assay method try to achieve, and be defined as below respectively.
((Raman assay method))
Using raman spectroscopy device (for example, " raman spectroscopy device " that Japanese light splitting company manufactures), by the non-water power of the present invention Solve electrolitc secondary cell to be arranged in cell with negative pole, argon laser is irradiated to the specimen surface in pond and is measured.It is logical Cross and background compensation is carried out to the Raman spectrum of measure, obtain Raman RC values, Raman RSC values, Raman RS values.In addition, background is compensated It is carried out as follows：With the whole initial point of straight line connecting peak, background is obtained, then the value is subtracted by peak intensity.
Here Raman condition determination is as follows, is smoothed into the simple average of 15 points of convolution.
Argon laser wavelength：514.5nm
Laser power on sample：15~40mW
Resolution ratio：10~20cm-1
Measurement range：200cm-1~1900cm-1
(((Raman RC values)))
Determine 1300cm-1~1600cm-1The peak c nearby occurred peak intensity Ic, 300cm-1~500cm-1Nearby occur Peak as peak intensity Ias, calculates its strength ratio RC (RC=Ic/Ias), is defined as the Raman RC values of negative pole.Here, may be used It is the peak for being respectively from carbon and silicon to think peak c and peak as, therefore, and Raman RC values reflect the amount of carbon, and Raman RC values are less than 2.0 Refer to almost not detect carbon.
(((Raman RSC values)))
Determine 650cm-1~850cm-1The peak sc nearby occurred peak intensity Isc, 300cm-1~500cm-1Nearby occur Peak as peak intensity Ias, calculates its strength ratio RSC (RSC=Isc/Ias), is defined as the Raman RSC values of negative pole.
Here, it is believed that peak sc and peak as come from the peak of SiC and silicon respectively, therefore, Raman RSC values reflect SiC's Amount, Raman RSC values refer to almost not detect SiC for less than 0.25.
(((Raman RS values)))
Determine 520cm-1Intensity I s, 300cm-1~500cm-1The peak as nearby occurred peak intensity Ias, calculates it Strength ratio RS (RS=Is/Ias), is defined as the Raman RS values of negative pole.Raman RS values reflect Si state.
(IRsc values)
For the negative pole with negative electrode active material used in the present invention after progress discharge and recharge, pass through infrared external reflection The IRsc values that light analysis is determined are preferably more than 0.90, more preferably more than 1.1, particularly preferably more than 1.2.If IRsc is low In the scope, then the negative pole containing Si and nonaqueous electrolytic solution reaction in the circulating cycle, can substantially carry out the active matter of discharge and recharge Quality is slowly reduced, and is difficult to obtain preferred cycle characteristics sometimes.The higher limit of IRsc values is 3.0 or so.In addition, in the present invention Negative pole the IRsc values that determine of use infrared external reflection light analysis by it is following utilize that infrared spectrophotometer carries out it is infrared instead Penetrate light measurement to try to achieve, and be carried out as follows definition.
((the infrared external reflection light analysis determining method carried out using infrared spectrophotometer))
Infrared spectrophotometer (for example, thermoelectron (サ ー モ エ レ Network ト ロ Application, thermo electron) will be used public Take charge of " Magna560 " of manufacture), the active material face of the negative pole of the lithium secondary battery after progress discharge and recharge is arranged on cell In, it is measured by bounce technique.It is adamantine reflection measurement sample retainer (Off ォ Le ダ to determine using window material ー), carried out under inactive atmosphere.Compensated by the background for the infrared absorption spectrum being measured, obtain IRsc values.Separately Outside, background compensation is carried out as follows：Connect 2000~4000cm-1The minimum value of scope, and straight line is extended, obtains background, then by Each intensity subtracts the value.Determine 1600cm-1Under intensity of reflected light Isc, 1650cm-1Under intensity of reflected light Iaco, calculate Its strength ratio IRsc (IRsc=Isc/Iaco), is defined as the IRsc values after discharge and recharge.
Although details is also indefinite, think that Isc comes from Si epithelium, Iaco comes from alkyl lithium carbonates Epithelium, therefore, IRsc reflect negative pole epithelium (solid electrolyte interface：SEI state and amount) compares, and IRsc value is 0.9 Mean that the epithelium by coming from alkyl lithium carbonates and the epithelium for coming from Si are constituted above.
＜ effects, principle ＞
First, activity is illustrated.In general, so-called activity is a kind of thermodynamics concentration.For including amount of substance n1、n2…ni... multicomponent system, if the chemical potential of component i is set as into μi, the chemical potential of pure material is set as μi 0, Then will be with following formula
μi- μi 0=RTlogai
The a of definitioniReferred to as activity.
In addition, by activity aiAnd concentration ciThe ratio between γiReferred to as activity coefficient.
ai/ci=γi
For example, using a certain system comprising solvent and solute as thermodynamic (al) solution account for when, activity coefficient is It is a certain when regarding real solution as corresponding to the chemical potential that system is regarded as to a certain composition during perfect solution and by system The amount of the difference of the real chemical potential of composition.(1) in the case of real solution of a certain component i for solute, if solute Concentration step-down, then system is close to the perfect solution that component i is solute, and activity coefficient is close to 1.On the contrary, (2) are in a certain composition I for solvent real solution in the case of, if the concentration of solvent is uprised, system close to component i be solvent perfect solution Liquid, activity coefficient is close to 1.In addition, when real solution is more stable than perfect solution, the chemical potential of component i is γi＜ 1.
In the present invention, if the Si for enumerating display superperformance is example, component i is Si, is being counted as solvent By containing the element Z for being counted as solute, solvent Si activity a in SiiReduction, γi＜ 1, the Si compounds containing element Z (solid solution：Regard real solution as) it is more stable than Si (regarding perfect solution as), as a result, can suppress anti-with nonaqueous electrolytic solution Ying Xing.
But, if forming the compound Si that Si and element Z balances are presentaZpDeng, then Si activity can not be effectively reduced, Therefore, it is important that element Z exists non-equilibriumly in Si.
[form of negative pole [7]]
In the present invention, the form of the negative electrode active material used in negative pole [7] is usually film-form or powdered.At this , can be by the current collector by activity using the negative pole of film-form active material described in manufacture method as be described hereinafter in invention Material layer carries out gas phase film forming and obtained, and the negative pole of powdered active agent can be for example, by coated powder shape on the current collector Active material and adhesive etc. and form active material layer.
[[film-form active material]]
[[[structure]]]
As the structure of the film-form active material of film forming on the current collector, for example, it can enumerate column structure, layer structure Deng.
[[[thickness]]]
The thickness of film-form active material is suitable with the thickness of the active material layer using the film-form active material, generally For more than 1 μm, preferably more than 3 μm, in addition, its upper limit is usually less than 30 μm, preferably less than 20 μm, more preferably 15 μm Below.If the thickness of film-form active material is less than the scope, the negative pole of the invention of the film-form active material is used (following, to be sometimes referred to as the negative pole using film-form active material " film cathode ") its each piece capacity is small, in order to obtain The battery of Large Copacity is, it is necessary to substantial amounts of negative pole, therefore, accordingly, it is desirable to positive pole, dividing plate, the collector of film cathode in itself Total measurement (volume) become big, the negative electrode active material that per unit cell volume can be filled is substantially reduced, it is difficult to increase battery capacity. On the other hand, if it exceeds the scope, then due to expansion/contraction caused by discharge and recharge, film-form active material layer is sometimes from collection Peeled off on electric structure base board, cycle characteristics is possible to deteriorate.
[[powdered active agent]]
[[[shape]]]
As the shape of powdered active agent, such as spherical, polyhedron shape can be enumerated, it is amorphous.
[[[volume reference average grain diameter]]]
The volume reference average grain diameter of powdered active agent is not particularly limited, usually more than 0.1 μm, preferably 1 μ More than m, more preferably more than 3 μm, in addition, its upper limit is usually less than 50 μm, preferably less than 30 μm, more preferably 25 μm with Under.If the volume reference average grain diameter of powdered active agent is less than above range, because particle diameter is too small, it is difficult to obtain powder The conductive path between conductive path or powdered active agent and conductive agent described later between last shape active material, cycle characteristics Sometimes deteriorate.On the other hand, if it exceeds above range, then negative pole manufactured by coating on the current collector as hereinafter described During active material layer, produce sometimes uneven.
In addition, as the volume reference average grain diameter of powdered active agent, using the value determined as follows：In measure object The middle 2 volume % aqueous solution (about 1mL) for mixing polyoxyethylene (20) Span-20 as surfactant In, using ion exchange water as decentralized medium, using laser diffraction/scattering formula particle size distribution meter (for example, Ku Chang manufacturing companies " LA-920 " of manufacture), determine the average grain diameter (median particle diameter) of volume reference.In embodiment described later, pass through this method Obtain volume reference average grain diameter.
[[[BET specific surface area]]]
The BET specific surface area of powdered active agent is not particularly limited, but usually 0.1m2/ more than g, be preferably 0.5m2/ more than g, more preferably 1.0m2/ more than g, in addition, usually 100m2/ below g, preferably 30m2/ below g, more preferably For 15m2/ below g scope.If the value of BET specific surface area is less than the lower limit of above range, in the situation for negative pole Under, in the charging of battery, the acceptance of lithium is easily deteriorated, and lithium is easily separated out in electrode surface, therefore unexcellent from the point view of security Choosing.On the other hand, if the value of BET specific surface area exceedes the upper limit of above range, when negative pole is made, with nonaqueous electrolytic solution Reactivity increase, the gas of generation becomes many, is difficult to obtain preferred battery sometimes.
In addition, the BET specific surface area of powdered active agent uses the value determined as follows：Using surface area meter (for example, big Storehouse reason develops the full-automatic surface area determination unit made), 15 points are carried out to powdered active agent at nitrogen circulation, 350 DEG C Clock is predrying, then, is accurately adjusted to 0.3 nitrogen helium mixture relative to the relative pressure of atmospheric pressure using nitrogen, leads to Cross and determined using the N2 adsorption BET1 points method of gas flow method.
[[[tap density]]]
The tap density of powdered active agent is not particularly limited, usually 0.2g/cm3More than, preferably 0.3g/cm3 More than, more preferably 0.5g/cm3More than, in addition, usually 3.5g/cm3Hereinafter, preferably 2.5g/cm3Following scope.Such as Fruit tap density is less than the scope, then is difficult to the packed density for improving negative electrode active material layer, high power capacity can not be obtained sometimes Battery.On the other hand, if it exceeds the scope, then the pore amount in negative electrode active material tails off sometimes, is difficult to obtain excellent sometimes The battery behavior of choosing.
In the present invention, tap density is defined as below：Sample is set to fall by the sieve in 300 μm of aperture in 20cm3Jolt ramming In container, until behind upper surface of the powdered active agent full of container, using powder density determination device (for example, seishin is looked forward to The Tap densor of industry company manufacture), carry out 1000 length of stroke 10mm vibration, the weight of volume and sample when thus Density is obtained, the density is defined as tap density.
2. the external lithium occlusion materials (F) of element Z
The so-called external lithium occlusion materials (F) of element Z, refer to lithium occlusion metal (A) and/or lithium occlusion alloy in negative pole (B) with C (carbon) (carbonaceous material (E)) material obtained from Composite as element Z.In addition, " Composite " mentioned here Represent lithium occlusion metal (A) and/or lithium occlusion alloy (B) state restrained by being bonded with carbonaceous material (E), by physics about The state of beam, state of shape etc. is kept by electrostatic confinement." constraint of physics " mentioned here refers to lithium occlusion metal And/or lithium occlusion alloy (B) state that is mixed in carbonaceous material (E), connects together (A)；So-called " constraint of electrostatic " refers to Lithium occlusion metal (A) and/or lithium occlusion alloy (B) are attached to the state in carbonaceous material (E) by electrostatic energy.In addition, institute Meaning " state restrained by bonding " refers to that hydrogen bond, covalent bond, ionic bond etc. are chemically bonded.
Wherein, from the viewpoint of the reduction impedance, at least one of lithium occlusion metal (A) and/or lithium occlusion alloy (B) surface It is favourable with the state with the interface of the layer of carbonaceous material (E) to divide by bonding.Covering mentioned here, be with carbon There is chemical bond at least part interface on the surface of metallic substance (E), and show that the state of (1) covering whole surface, (2) are local Ground covers the state of carbonaceous particles, (3) optionally the state on covering part surface, (4) are present in containing the atomic of chemical bond The state of zonule.
In addition, crystallinity can continuously change on interface, can also discontinuously it be changed.That is, element Z is external Lithium occlusion material (F) has lithium occlusion metal (A) and/or lithium occlusion alloy (B) by carbonaceous material (E) covering and/or bonding The interface of formation, the crystallinity at the interface is preferably discontinuous and/or continuously changes.
[property of the carbonaceous material (E) of negative pole [7]]
[[composition of carbonaceous material (E)]]
Carbonaceous material (E) particularly preferably (a) or (b) shown below carbide, can also contain simultaneously native graphite, The graphite such as Delanium metallic substance (G).Because the crystallinity of graphite (G) is very high, therefore in general, its electric conductivity compares stone Black matter (E) is high, compared with graphite (E), therefore, excellent from the viewpoint of electric conductivity is improved because the effect for improving electric conductivity is high Choosing with graphite (E) and meanwhile in the presence of.
(a) closed selected from coal class heavy oil, straight run class heavy oil, decomposition class black petroleum products, aromatic hydrocarbon, N cycle compounds, S cyclisation The organic matter being carbonized in thing, polyphenyl, organic synthesis macromolecule, natural polymer, thermoplastic resin and heat reactive resin；
(b) solution obtained from these organic matters that can be carbonized are dissolved in small molecular organic solvent.
Here, as coal class heavy oil, coal tar asphalt or destructive distillation liquefaction oil preferably from maltha to pitch etc.；Make For straight run class heavy oil, preferably atmospheric resids, decompression residual oil etc.；As class black petroleum products is decomposed, the preferably heat such as crude oil, naphtha is divided Ethylene bottom oil of by-product etc. during solution；It is used as aromatic hydrocarbon, preferably acenaphthylene, decacyclene, anthracene, phenanthrene etc.；As N cycle compounds, preferably Azophenlyene, acridine etc.；It is used as S cycle compounds, preferably thiophene, di- thiophene etc.；It is used as polyphenyl, preferably biphenyl, terphenyl etc.；As Organic polymer, preferably polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, their insoluble processed material, polyacrylonitrile, Polypyrrole, polythiophene, polystyrene etc.；It is used as natural polymer, preferred cellulose, lignin, mannosan, polygalacturonic Polysaccharides such as acid, chitosan, sucrose etc.；It is used as thermoplastic resin, preferably polyphenylene sulfide, polyphenylene oxide etc.；As thermosetting resin, It is preferred that furfuryl alcohol resin, phenolic resin, imide resin etc..
Carbonaceous material (E) is preferably the carbide of above-mentioned " organic matter that can be carbonized ", it is also preferable to will be such " organic matter that can be carbonized " is dissolved in molten obtained from the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane The carbide of liquid.
As above-mentioned (a) and (b), particularly preferred liquid.That is, from generation and occlusion metal (A) and/or lithium occlusion alloy (B) from the viewpoint of interface, preferably it is carbonized in the liquid phase.
[[physical property of carbonaceous material (E)]]
As carbonaceous material (E) physical property, any one or many in (1)~(3) shown below is preferably met simultaneously .Furthermore it is possible to a kind of carbonaceous material (E) for showing such physical property is used alone, can also in any combination with ratio group Conjunction uses two or more.
(1) X-ray parameter
For carbonaceous material (E) physical property, by using learning the lattice plane (002 that the X-ray diffraction of method progress that shakes is tried to achieve Face) d values (interfloor distance) (below, be abbreviated as " d002 ") be preferably below 0.38nm, particularly preferably below 0.36nm enters One step is preferably below 0.35nm.If d values are excessive, the obvious low surface of crystallinity, impedance increase, therefore charging are formed The effect improved by property diminishes, so that the effect of the present invention diminishes.In addition, being the 0.335nm of the theoretical value of graphite for lower limit More than.
In addition, the crystallite size (Lc) of carbon material tried to achieve by using the X-ray diffraction for learning method of shaking be usually 1nm with On, preferably more than 1.5nm scope.If less than the scope, impedance increase, the effect that charging acceptance is improved has time-varying It is small.
(2) Raman R value, Raman half breadth
The Raman R value of carbonaceous material (E) part determined using argon laser Raman spectroscopy is usually more than 0.2, Preferably more than 0.3, more preferably more than 0.4, its upper limit is usually less than 1.5, preferably less than 1.2 scope.If drawn Graceful R values are less than the scope, then the crystallinity of particle surface is too high, as the discharge and recharge Li sites for entering interlayer tail off sometimes.That is, Charging acceptance is reduced sometimes.On the other hand, if it exceeds the scope, then the crystallinity reduction of particle surface, with non-aqueous solution electrolysis The reactivity increase of liquid, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, carbonaceous material (E) is partly in 1580cm-1Neighbouring Raman half breadth has no particular limits, and is usually 20cm-1More than, preferably 30cm-1More than, in addition, its upper limit is usually 140cm-1Hereinafter, preferably 100cm-1Following model Enclose.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters the position of interlayer Point tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if it exceeds the crystallinity drop of the scope, then particle surface It is low, increase with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
(3) real density
The real density of carbonaceous material (E) part is usually 1.4g/cm3More than, preferably 1.5g/cm3More than, more preferably 1.6g/cm3More than, more preferably 1.7g/cm3More than, the theoretical value 2.26g/cm of graphite is limited to thereon3Below.If low In the scope, then the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
The negative electrode active for including multielement used in the negative electrode active material of the negative pole [7] of the lithium secondary battery of the present invention Material (C), preferably occlusion metal (A) and/or lithium occlusion alloy (B) with obtained from carbonaceous material (E) Composite outside element Z In lithium occlusion material (F), further preferably further contain the graphite metallic substance (G) beyond carbonaceous material (E) as element Z carbon (C)。
[[composition and physical property of graphite metallic substance (G)]]
As one of the composition of graphite metallic substance (G), native graphite, Delanium can be enumerated and they are implemented to crush Deng material obtained from processing, as graphite metallic substance (G) physical property, preferably meet simultaneously in (1)~(3) shown below It is any one or more.Furthermore it is possible to a kind of graphite metallic substance (G) for showing such physical property is used alone, can also be with any Combination and ratio two or more is applied in combination.
(1) X-ray parameter
For graphite metallic substance (G) part, by using learning the lattice plane (002 that the X-ray diffraction of method progress that shakes is tried to achieve Face) d values (interfloor distance) be graphite more than theoretical value 0.335nm.Its upper limit is preferably below 0.340nm, more preferably Below 0.338nm, particularly preferably below 0.337nm.If d values are excessive, the obvious low surface of crystallinity is formed, impedance increases Greatly, thus charging acceptance improve effect diminish so that the present invention effect diminish.
In addition, the crystallite size (Lc) for the graphite metallic substance (G) tried to achieve by using the X-ray diffraction for learning method of shaking is usually More than 10nm, preferably more than 50nm, more preferably more than 80nm scope.If less than the scope, impedance increases, therefore The effect that charging acceptance is improved diminishes sometimes.
(2) Raman R value, Raman half breadth
The Raman R value of graphite metallic substance (G) part determined using argon laser Raman spectroscopy be usually 0.01 with On, preferably more than 0.10, its upper limit is usually less than 0.40, preferably less than 0.35, more preferably less than 0.25 scope. If Raman R value is less than the scope, the crystallinity of particle surface is too high, as there is time-varying in the discharge and recharge Li sites for entering interlayer It is few.That is, charging acceptance is reduced sometimes.On the other hand, if it exceeds the scope, then the crystallinity reduction of particle surface is and non- The reactivity increase of water electrolysis liquid, the gas increase for occasionally resulting in efficiency reduction or producing.
In addition, graphite metallic substance (G) is partly in 1580cm-1Neighbouring Raman half breadth has no particular limits, generally For 10cm-1More than, preferably 15cm-1More than, in addition, its upper limit is usually 50cm-1Hereinafter, preferably 40cm-1Following model Enclose.If Raman half breadth is less than the scope, the crystallinity of particle surface is too high, as discharge and recharge Li enters the position of interlayer Point tails off sometimes.That is, charging acceptance is reduced sometimes.On the other hand, if it exceeds the crystallinity drop of the scope, then particle surface It is low, increase with the reactivity of nonaqueous electrolytic solution, the gas increase for occasionally resulting in efficiency reduction or producing.
(3) real density
The real density of graphite metallic substance (G) part is usually 2.0g/cm3More than, preferably 2.1g/cm3More than, more preferably For 2.2g/cm3More than, more preferably 2.22g/cm3More than, the theoretical value 2.26g/cm of graphite is limited to thereon3Below.Such as Fruit is less than the scope, then the crystallinity of carbon is too low, and initial stage, irreversible capacity increased sometimes.
The external lithium occlusion materials of element Z used in the negative electrode active material of the negative pole [7] of the lithium secondary battery of the present invention (F) in, occlusion metal (A) and/or lithium occlusion alloy (B) and the mass ratio of carbonaceous material (E) are usually more than 20/80, preferably For more than 50/50, more preferably more than 80/20, particularly preferably more than 90/10, and preferably below 99.9/0.1, more preferably For less than 99/1, particularly preferably less than 98/2 scope.If it exceeds above range, then can not obtain with Carbonaceous matter sometimes The effect of matter (E), and if being less than above range, then the increased effect of the capacity of per unit mass diminishes sometimes.It is preferred that occlusion Metal (A) and/or lithium occlusion alloy (B) are more than 20 mass % relative to the external lithium occlusion materials (F) of whole element Z.
During containing graphite metallic substance (G), relative to carbonaceous material (E) and the total amount of graphite metallic substance (G), graphite metallic substance (G) it is preferably more than 5 mass % more preferably more than 20 mass %, more preferably more than 50 mass %.In addition, thereon Limit is preferably below 99 mass %, more preferably below 95 mass %.If graphite metallic substance (G) is excessively, the bonding at interface Die down, be difficult to obtain the effect that electric conductivity is improved sometimes, and if graphite metallic substance (G) is very few, then be difficult to sometimes containing Graphite metallic substance (G) and effect that the electric conductivity brought is improved.
In the present invention, the form of the external lithium occlusion materials (F) of element Z is usually film-form or powdered.In addition, at this In invention, the negative pole of film-form active material has been used as described in manufacture method below, can be by the current collector will Active material layer carries out gas phase film forming and obtained, and the negative pole of powdered active agent can be for example, by being coated with powder on the current collector Last shape active material and adhesive etc. and form active material layer.
The scope of preferred powder property when the external lithium occlusion materials (F) of element Z are powdered and the lithium for including element Z The scope of the preferred powder property of occlusion material (D) is identical.
[collector of negative pole [7]]
(material)
As the material of collector, copper, nickel, stainless steel etc. can be enumerated, wherein, preferably it is readily processible to film and cheap Copper.Copper foil has using rolled copper foil made from rolling process and using electrolytic copper foil made from electrolysis, and any one can Used as collector.In addition, when the thickness ratio of copper foil is 25 μm thin, can use the copper alloy higher than fine copper intensity (phosphor bronze, Titanium copper, Corson alloy, Cu-Cr-Zr alloys etc.).
In the collector made by the copper foil made using rolling process, because copper crystallization is in rolling direction arrangement, even if will Negative pole closely bending or negative pole is bent it is at an acute angle, it is all not easy to break, it is adaptable to small cylinder shape battery.Electrolytic copper foil is made as follows ：For example, the drum that impregnating metal is manufactured in the nonaqueous electrolytic solution for be dissolved with copper ion, the circulating current when rotating the drum, Thus copper is separated out on bulging surface, then peeled off.Copper can also be separated out by electrolysis on the surface of above-mentioned rolled copper foil. The one or both sides of copper foil can be roughened or are surface-treated (for example, thickness is the chromic acid of a few nm~1 μm or so Salt treatment, Ti etc. bottom layer treatment etc.).
(thickness)
In the current collection structure base board being made up of copper foil etc., thin can manufacture thin film cathode, from can it is identical store Load in the battery case of volume from the point of view of the film cathode of larger surface area this point, be preferred, but if too thin, then intensity is not When foot, winding when manufacturing battery etc., copper foil cut-out, therefore preferably 10~70 μm of thickness are worried.On the two sides of copper foil When forming active material layer, copper foil is preferably thinner, but from the swollen of the active material film for avoiding producing along with charging and discharging From the viewpoint of the generation being cracked caused by swollen/contraction, in this case, the preferred thickness of copper foil is 8~35 μm.Separately When outside, using the metal foil beyond copper foil as collector, various metal foils are can correspond to using preferred thickness, but substantially In the range of 10~70 μm or so.
(physical property)
For current collection structure base board, it is also desirable to following physical property.
(1) average surface roughness (Ra)
The active material film of current collection structure base board forms being averaged for face as defined in the method recorded with JIS B0601-1994 Surface roughness (Ra) has no particular limits, but usually more than 0.01 μm, preferably more than 0.03 μm, and usually 1.5 μ Below m, particularly preferably preferably less than 1.3 μm, less than 1.0 μm.
, can be with by making the average surface roughness (Ra) of current collection structure base board between above-mentioned lower and upper limit Expect good charge/discharge cycle characteristics.That is, by being set as more than above-mentioned lower limit, the interfacial area with active material film Become big, improved with the adaptation of active material film.In addition, the higher limit of average surface roughness (Ra) is not limited particularly System, when average surface roughness (Ra) is more than 1.5 μm, it is difficult to obtain the paper tinsel as battery suitable thickness, therefore preferably 1.5 μm Below.
(2) tensile strength
The tensile strength of current collection structure base board is not particularly limited, usually 50N/mm2More than, preferably 100N/mm2More than, More preferably 150N/mm2More than.So-called tensile strength, refers to that test film reaches maximum pull required during fracture divided by examination Test value obtained from the sectional area of piece.Tensile strength in the present invention, can use the apparatus and method same with determining elongation Determine.If the high current collection structure base board of tensile strength, then when can suppress charge/discharge due to active material film expansion/ The cracking of current collection structure base board caused by shrinking, so as to obtain good cycle characteristics.
(3) 0.2% endurance
0.2% endurance of current collection structure base board has no particular limits, but usually 30N/mm2More than, preferably 100N/mm2 More than, particularly preferably 150N/mm2More than.So-called 0.2% endurance, refers to that (permanent) deformation of the plasticity for producing 0.2% is required Payload, after the load for applying the size, 0.2% deformation can also be kept by removing load.0.2% endurance in the present invention Can be by being determined with determining elongation identical apparatus and method.If the high collector of 0.2% endurance, then can suppress It is good so as to obtain due to the plastic deformation of active material film expansion/current collection structure base board caused by contraction during charge/discharge Good cycle characteristics.
[manufacture method of the negative electrode active material (C) containing multielement of negative pole [7]]
The negative electrode active material (C) containing multielement of the present invention (is included outside element Z lithium occlusion material (D) and element Z In lithium occlusion material (F)) manufacture method be not particularly limited, for example, can be manufactured by the autofrettage being set forth below.
1. include the manufacture method of element Z lithium occlusion material (D)
The ＞ of ＜ autofrettages 1
Vapor deposition source, sputtering source or sputtering source use any of following material：
(i) Si, element Z and element M composition (being wherein, Si and element Z composition during y=0 or y ≒ 0)；
(ii) Si, element Z and element M mixture (being wherein, Si and element Z mixture during y=0 or y ≒ 0)；
(iii) Si, element Z and the respective simple substance of element M (each simple substance can also be the gas containing each element) (wherein, y It is Si and the respective simple substance of element Z during=0 or y ≒ 0)；
(iv) Si and element Z composition or mixture and the simple substance of element M (can also be the gas containing M)；
(v) gas (being wherein, the gas containing Si and element Z during y=0 or y ≒ 0) containing Si, element Z and element M；
(vi) composition or mixture of Si simple substance, element Z and element M；
(vii) simple substance (can also be the gas containing M) of Si and the composition or mixture of element M and element Z,
And using vapour deposition method and/or sputtering method and metallikon simultaneously by Si, element Z and element M (wherein, y=0 or y ≒ When 0 be Si and element Z) on above-mentioned current collection structure base board formed 1~30 μm thickness, be preferably active material film thickness one The film of thickness described in.
(raw material)
It is former as the Si simple substance of vapor deposition source, sputtering source or spraying plating (molten to penetrate) source (being properly termed as sometimes below " raw material ") Material, such as can use crystallinity Si, amorphous Si.As Z raw materials, C, N element can be used.In addition, as long as element Z is full The element of the above-mentioned project of foot, multiple element of more than two kinds can be used simultaneously.
In raw material, as (i) Si, element Z and element M composition (wherein, for Si's and element Z during y=0 or y ≒ 0 Composition), it can use and be combined with Si, element Z and element M, or it is combined with single compound formed by Si and element Z, Or multiple compounds can also be made use.In addition, these Si, Z raw materials, the form of M raw materials, for example can be made into it is powdered, Graininess, coccoid, block, tabular etc. are used.
In formula SiZxMyIn, y ≠ 0 and containing element M when, element M can use beyond Si and element Z be selected from the cycle The race of table 2,4 races, 8 races, 9 races, 10 races, 11 races, 13 races, 14 races, one kind in the element of 15 races and 16 races or two or more, preferably Using Ti, Zr, W, O, Co element, more preferably using O elements.
(membrane formation process)
As the forming method of active material film, gas phase membrane formation process can be enumerated, specifically, vapour deposition method (vacuum can be enumerated Vapour deposition method, CVD, ion plating method), sputtering method, metallikon (flame spraying, plasma spraying process) etc..It will can also splash Penetrate method and vapour deposition method, sputtering method and metallikon are combined to film forming.
The forming method to negative electrode active material film is illustrated below.
A. sputtering method
Sputtering method be under reduced pressure using plasma make the active material that is sent by the target containing above-mentioned raw materials with Collector substrate collides, accumulates and form film.If using sputtering method, the active material film formed and current collection structure base board Interface state it is good, active material film is also high for the adaptation of collector.
As the applying method of the sputtering voltage for target, any one of DC voltage, alternating voltage can be used, this When, negative bias is substantially applied to current collection structure base board, the collision energy of the ion from plasma can be controlled System.The final vacuum for initially forming the intracavitary before film is usually below 0.1Pa to prevent from being mixed into impurity.
As sputter gas, the inert gases such as Ne, Ar, Kr, Xe are used.Wherein, consider in terms of sputtering yield, preferably Use argon gas.In addition, compound SiZxMyIn element Z when being N, there is micro nitrogen simultaneously in above-mentioned inert gas and exist It is preferred in manufacture.Generally, sputter gas pressure is 0.05~70Pa or so.During by sputtering method formation active material film Current collection structure base board temperature can be controlled by water cooling or heater etc..As the temperature range of current collection structure base board, generally For room temperature~900 DEG C, it is preferred that for less than 150 DEG C.It is usual by film forming speed during sputtering method formation active material film For 0.01~0.5 μm/minute.
Moreover, before active material film is formed, the pre-treatment such as reverse sputtering or other corona treatments can be passed through To be etched to collector substrate surface.Such pre-treatment for the copper foil surface as current collection structure base board pollutant or Removing, the raising of the adaptation of active material film of oxide-film are effective.
B. vacuum vapour deposition
Vacuum vapour deposition is to make above-mentioned raw materials melting, the evaporation as active material, so as to be deposited on current collection structure base board Method, in general, this method has the advantages that compared with sputtering method can be with higher film forming speed formation film.From scheme From the viewpoint of the formation time for seeking the active material film for shortening regulation thickness, vacuum vapour deposition is compared with sputtering method, in system Cause present aspect can advantageously flexible Application.As its specific method, can enumerate induction heating, electrical resistance heating, Electron beam heating evaporation etc..Induction heating is by induced-current to heat deposition material in the evaporation crucible of graphite etc. Melt and evaporate and film forming；Electrical resistance heating is to make deposition material heating molten in evaporation boat etc. by the heated current of energization Melt and evaporate and film forming；Electron beam heating evaporation is deposition material heating is melted and is evaporated and film forming by electron beam.
As the atmosphere gas of vacuum vapour deposition, typically using vacuum.In addition, compound SiZxMyIn element Z be N when, can To import and be depressurized micro nitrogen together with inert gas, SiZ is formed simultaneously under vacuoxMy.Initially form film The final vacuum of preceding intracavitary is usually below 0.1Pa to prevent from being mixed into impurity.
Temperature can be controlled by heater etc. by current collection structure base board during vacuum vapour deposition formation active material film. As the temperature range of current collection structure base board, usually room temperature~900 DEG C, it is preferred that for less than 150 DEG C.Pass through vacuum vapour deposition Film forming speed when forming negative electrode active material film is usually 0.1~50 μm/minute.
In addition, in the same manner as the situation of sputtering method, accumulating before active material film, can passing through on current collection structure base board Ion exposure is carried out with ion gun etc. to implement etching process to collector substrate surface., can be with by such etching process Further improve the adaptation of substrate and active material film.In addition, when forming film, by making ion and collector bump substrate Hit, can further improve adaptation of the active material film for current collection structure base board.
C.CVD methods
CVD is to make to be deposited on current collection structure base board as the above-mentioned raw materials of active material by gas-phase chemical reaction.One As for, CVD has following feature：Due to the chemical compound gas flowed into by gas in control reative cell, therefore can be high Synthesize to purity various materials, as its specific method, can enumerate thermal cvd, plasma CVD method, optical cvd method, Cat-CVD methods etc..Thermal cvd be by the unstrpped gas of the high halogen compound of vapour pressure together with carrier gas or reacting gas 1000 DEG C or so imported into heating after reaction vessel in, make its produce thermal chemical reaction and form film.Plasma CVD method is to make The method that heat energy is substituted with plasma；Optical cvd is the method that heat energy is substituted using luminous energy.Cat-CVD methods are catalysisization Vapour deposition process is learned, film is formed by the contact decomposition reaction using unstrpped gas with heatable catalyst.
It is SiH as elements Si source in the unstrpped gas used in CVD4、SiCl4Deng；It is NH as element Z sources3、 N2、BCl3、CH4、C2H6、C3H8Deng.
D. ion plating method
Ion plating method be make as active material above-mentioned raw materials melting, evaporation, under plasma by evaporation particle from Sonization and excite, thus the film forming securely on current collection structure base board.Specifically, can as raw materials melt, the method for evaporation is made To enumerate induction heating, electrical resistance heating, electron beam heating evaporation etc.；It is used as the method for ionizing and exciting, Ke Yiju Go out priming reaction vapour deposition method, many cathode primary electron irradiations, high frequency excitation method, HCD methods, ion cluster beam method (Network ラ ス タ ー イ オ ン ビ ー system method), multi sphere method etc..Furthermore it is possible to which the method for evaporating above-mentioned raw materials and ionization and the method excited is appropriate Selection combines to carry out.
E. metallikon
Metallikon is to make the above-mentioned raw materials melting or softening as active material by heating, forms finely particulate and adds Speed, so that particle solidifies, is deposited on current collection structure base board.As its specific method, flame-spray processes, electric arc can be enumerated Metallikon, direct-current plasma metallikon, RF plasma sprayings method, laser metallikon etc..
F. the combination of sputtering method and vapour deposition method
Using the high film forming speed of vapour deposition method advantage and sputtering method the strong film forming adaptation to current collection structure base board it is excellent Point, for example, by sputtering method the 1st film layer of formation, then the 2nd film layer is formed at a high speed by vapour deposition method, it is possible thereby to be formed With the interface zone of the excellent adhesion of current collection structure base board, while with high film forming speed formation active material film.Using so Film build method mixing combined method, can efficiently manufacture charge/discharge capacity high and excellent charge/discharge cycle characteristics thin Film negative pole.
Sputtering method is combined with vapour deposition method and preferably keeps reduced pressure atmosphere gas to form active material film and continuously carries out. This is due to be continuously formed the 1st film layer and the 2nd film layer by being not exposed under air, can prevent from being mixed into impurity. For example, it is preferable to use following film forming device：In same vacuum environment, move current collection structure base board, while entering successively Row sputtering and evaporation.
In the present invention, when forming active material film on the two sides of current collection structure base board by such membrane formation process, Active material film layer (can also be the combination of above-mentioned 1st film layer and the 2nd film layer) is formed in the one side of current collection structure base board (can also be above-mentioned 1st film layer and the 2nd film layer with active material film layer is formed on the another side of current collection structure base board Combination), preferably it is carried out continuously in the state of reduced pressure atmosphere gas is kept.
<Autofrettage 2>
Mutual-through type SiZ belowxMyManufacture method when middle element Z is C is illustrated.
Vapor deposition source, sputtering source or sputtering source use any of following substances：
(i) Si, C and the composition of element M (wherein, during y=0 or y ≒ 0 for Si and C composition)；
(ii) Si, C and the mixture of element M (wherein, during y=0 or y ≒ 0 for Si and C mixture)；
(iii) Si, C and the respective simple substance of element M (being wherein, Si and C respective simple substance during y=0 or y ≒ 0)；
(iv) Si and C composition or mixture and the simple substance of element M (can also be the gas containing M)；
(v) gas (being wherein, the gas containing Si and C during y=0 or y ≒ 0) containing Si, C and element M；
(vi) Si simple substance and C and the composition or mixture of element M；
(vii) Si and the composition or mixture of element M and C simple substance,
And using vapour deposition method and/or sputtering method and metallikon simultaneously by Si, C and element M (wherein, during y=0 or y ≒ 0 For Si and C) 1~30 μm of thickness is formed on above-mentioned current collection structure base board, is preferably described in the thickness of active material film Thickness film.
(raw material)
As vapor deposition source or the Si raw materials of sputtering source (being properly termed as sometimes below " raw material "), for example, it can use crystallization Property Si, amorphous Si etc..As C raw materials, the carbon material such as can use native graphite, Delanium.As M raw materials, lead to Often it is the member of the race of periodic table 2 beyond Si and element Z, 4 races, 8 races, 9 races, 10 races, 11 races, 13 races, 14 races, 15 races and 16 races Element, preferably uses Ti, Zr, W, O, Co element, particularly preferably uses O elements.
In raw material, as (i) Si, C and the composition of element M, it can use single formed by Si, C and element M combination Compound, or multiple compounds can also be made use.In addition, the form of these Si, C, M raw materials, such as can be made into powder Shape, graininess, coccoid, block, tabular etc. are used.In addition, the oxidation of Si or C nitride, Si or C can be made in element M Thing is used, for O for existing under normal temperature as gas etc., and being co-existed in Si, C film forming as unstrpped gas O etc. in manufacture is It is preferred that.
(membrane formation process)
Use the membrane formation process same with above-mentioned autofrettage 1.
A. sputtering method
As sputter gas, the inert gases such as Ne, Ar, Kr, Xe are used.Wherein, consider in terms of sputtering yield, preferably Use argon gas.In addition, formula SiCxMyIn M element be O when, coexisted respectively in above-mentioned inert gas micro oxygen system It is preferred to make.Generally, sputter gas pressure is 0.05~70Pa or so.
B. vacuum vapour deposition
As the atmosphere gas of vacuum vapour deposition, typically using vacuum.In addition, formula SiCxMyIn element M when being O, can be with Micro oxygen is imported together with inert gas respectively, while being depressurized, so as to form Si/C/M simultaneously under vacuo.
C.CVD methods
It is SiH as elements Si source in the unstrpped gas that CVD is used4、SiCl4Deng；It is CH as Elements C source4、C2H6、 C3H8Deng.
<Autofrettage 3>
Mutual-through type SiZ belowxMyMiddle element Z is that manufacture method when C, element M are O is illustrated.
Vapor deposition source, sputtering source or sputtering source use any of following substances：
(I) Si and C composition；
(II) Si and C mixture；
(III) the respective simple substance of Si and C,
Or
(IV) gas containing Si and C,
The oxygen concentration of (be during film forming in a vacuum residual gas in) is 0.0001~0.125% atmosphere in film forming gas Enclose under gas, Si and C is formed 1~30 on above-mentioned current collection structure base board simultaneously using vapour deposition method and/or sputtering method and metallikon μm thickness, be preferably thickness described in the thickness of active material film film.
(raw material)
As the Si raw materials of the vapor deposition source of raw material, sputtering source or sputtering source, for example, it can use crystallinity Si, amorphous Si Deng.As C raw materials, the carbon material such as can use native graphite, Delanium.As the oxygen in film forming gas, by oxygen It is used alone or is applied in combination with inert gas Deng the gas containing O elements.The form of these Si, C raw materials, for example, can be made into powder Last shape, graininess, coccoid, block, tabular etc. are used.In addition, oxygen co-exists in system as unstrpped gas in Si, C film forming It is preferred to make.
(membrane formation process)
Use the membrane formation process same with above-mentioned autofrettage 1.
(oxygen concentration during film forming)
Oxygen when evaporation and/or sputtering and spraying plating (in residual gas during film forming in vacuum) in film forming gas is dense Degree is usually more than 0.0001%, and usually less than 0.125%, preferably less than 0.100%, more preferably 0.020% with Under.If the element O amounts that the oxygen concentration contained in film forming gas exceedes in the scope, Si/C/O films increase, with non-water power The reactivity increase of liquid is solved, the reduction of efficiency for charge-discharge is occasionally resulted in.If oxygen concentration is very few, Si/C/O can not be formed sometimes Film.
Moreover, as the oxygen concentration in film forming gas, for example, can be by using quadrupole mass filter (tetra- Very Off ィ Le タ) Analyze the mass spectrum of film forming gas and obtain.In addition, using when the argon gas of oxygen coexists as film forming gas, can be analysed by oxygen Meter determines the argon gas and tried to achieve.
<Autofrettage 4>
Mutual-through type SiZ belowxMyManufacture method when middle element Z is N and y=0 or y ≒ 0 is illustrated.
Vapor deposition source, sputtering source or sputtering source use any of following substances：
(I) Si simple substance；
(II) composition containing Si；
(III) mixture containing Si,
Or
(IV) gas containing Si,
The nitrogen concentration of (be during film forming in a vacuum residual gas in) is under 1~22% atmosphere gas in film forming gas, Si and N is formed on above-mentioned current collection structure base board to 1~30 μm of thickness simultaneously using vapour deposition method and/or sputtering method and metallikon The film of thickness described in the thickness of degree, preferably active material film.
(raw material)
As the Si simple substance raw materials of the vapor deposition source of raw material, sputtering source or sputtering source, for example, it can use crystallinity Si, without fixed Shape Si etc..As the N in film forming gas, the gas containing N element such as nitrogen is used alone or is applied in combination with inert gas.This A little Si etc. form, is used such as can be made into powdered, graininess, coccoid, block, tabular.In addition, nitrogen is used as raw material It is preferred that gas, which is co-existed in Si film forming in manufacture,.
(membrane formation process)
Use the membrane formation process same with above-mentioned autofrettage 1.
(nitrogen concentration during film forming)
Nitrogen when evaporation and/or sputtering and spraying plating (in residual gas during film forming in vacuum) in film forming gas is dense Degree is usually more than 1%, and usually less than 22%, preferably less than 15%, more preferably less than 10%.If film forming gas In the nitrogen concentration that contains exceed the scope, then SiNxElement N amounts in film increase, and produce the silicon nitride for being not involved in discharge and recharge, Occasionally result in the reduction of discharge capacity.If nitrogen concentration is very few, the SiN containing N can not be formed sometimesxFilm and cause circulation The reduction of characteristic.In addition, as the nitrogen concentration in film forming gas, for example, film forming gas can be analyzed by using quadrupole mass filter Mass spectrum and obtain.
2. the preparation method of the external lithium occlusion materials (F) of element Z
<Autofrettage 5>
Being carbonized described in the composition item by lithium occlusion metal (A) and/or lithium occlusion alloy (B) with carbonaceous material (E) Organic matter mixing, and organic matter heated, is decomposed, be carbonized by solid phase and/or liquid phase and/or gas phase, form carbon Metallic substance (E), obtains compound.The particle is crushed again, is classified, it is appropriate value to make volume reference average grain diameter.
(raw material)
It is usually 100 μ as the lithium occlusion metal (A) of raw material and/or the volume reference average grain diameter of lithium occlusion alloy (B) Below m, preferably less than 10 μm, more preferably less than 1 μm, its lower limit is more than 1nm scope.If it exceeds the upper limit, then difficult To relax expansion during charging, circulation conservation rate is reduced sometimes.In addition, if less than lower limit, being then difficult to crush, leading sometimes The cause time is upper, loss economically.In addition, as the raw material of carbonaceous material (E) as described above, it is preferred that to be passed through in carbonization Cross the material of liquid phase.
<Autofrettage 6>
Lithium occlusion metal (A) and/or lithium occlusion alloy (B) are mixed with graphite (G), carbonaceous material (E) is remixed The organic matter that can be carbonized described in item is constituted, and organic matter is heated, decomposed, is carbonized with liquid phase, Carbonaceous matter is formed Matter (E), obtains compound.The particle is crushed again, is classified, it is appropriate value to make volume reference average grain diameter.
(raw material)
Raw material with<Autofrettage 5>It is identical.
<Autofrettage 7>
Lithium occlusion metal (A) and/or lithium occlusion alloy (B) are mixed with graphite (G), carbonaceous material (E) is remixed The organic matter that can be carbonized described in item is constituted, and organic matter is heated, decomposed, is carbonized with solid phase, by mutually shape Into carbonaceous material (E), compound is obtained.Further the particle is crushed, is classified, it is appropriate to make volume reference average grain diameter Value.
(raw material)
Raw material with<Autofrettage 5>It is identical.
<Autofrettage 8>
Lithium occlusion metal (A) and/or lithium occlusion alloy (B) are mixed with graphite (G), carbonaceous material (E) is remixed The organic matter that can be carbonized described in item is constituted, and organic matter is heated, decomposed, is carbonized with gas phase, by mutually shape Into carbonaceous material (E), compound is obtained.Further the particle is crushed, is classified, it is appropriate to make volume reference average grain diameter Value.
(raw material)
Raw material with<Autofrettage 5>It is identical.
[electric polarization of the powdered active agent of negative pole [7]]
The manufacture of negative pole can be carried out conventionally, for example, as set forth above, it is possible to by into negative electrode active material Adhesive, solvent are added, thickener, conductive material, packing material etc. is added as needed and slurry is made, be coated on collection On electric body and after being dried, suppressed and formed.Every one side in stage before the electrolyte implantation step of battery The thickness of negative electrode active material layer is usually more than 5 μm, is preferably more than 10 μm, is more preferably more than 15 μm, and 150 are limited to thereon Below μm, be preferably less than 120 μm, be more preferably less than 100 μm.If it exceeds the scope, because nonaqueous electrolytic solution is difficult to soak Thoroughly to collector near interface, therefore high current density charge-discharge characteristic is reduced sometimes.If in addition, less than the scope, collected Electric body increases for the volume ratio of negative electrode active material, and the capacity of battery is reduced sometimes.Furthermore, it is possible to by negative electrode active material roller It is molded and forms plate electrode, or forms by compression forming mosaic electrode.
Adhesive, the thickener that can use etc. are same as described above.
<Negative pole [8]>
The negative pole [8] used in the lithium secondary battery of the present invention is illustrated below, the negative pole [8] contains property not Two or more same negative electrode active material is used as negative electrode active material.
[negative electrode active material of negative pole [8]]
The negative electrode active material used in negative pole [8] is illustrated below.
The negative electrode active material that uses is characterised by the negative pole [8] of the lithium secondary battery of the present invention, containing property not Same negative electrode active material of more than two kinds.
Wherein described " property is different " refer not only to compare surface with X-ray diffraction parameter, median particle diameter, draw ratio, BET Product, orientation ratio, Raman R value, tap density, real density, micropore distribution, circularity, ash amount etc. for representative powder shape and Powder property is different, also comprising " the composite carbonaceous material containing the different carbonaceous material of two or more crystallinity ", " containing 2 kinds with The composition of the materials such as the different orientation carbon complex of the different carbonaceous material of upper orientation " is different, or " real to negative electrode active material The different situation of working process such as heat treatment ", " mechanics energy process is implemented to negative electrode active material ".
[difference of shape, physical property etc.]
Wherein, the negative electrode active material used in the negative pole [8] of lithium secondary battery of the invention is by containing volume reference The different negative electrode active material of more than two kinds of average grain diameter (median particle diameter), can maintain low temperature power output, while can carry High circulation characteristic.As the difference of volume reference average grain diameter (median particle diameter), generally exist more than 1 μm, preferably in the presence of 2 μm with Difference that is upper, being more preferably the presence of more than 5 μm.It is used as the upper limit, usually less than 30 μm, preferably less than 25 μm.If more than the scope, Then the big particle diameter of median particle diameter has excessive trend, therefore the problems such as be possible to when electrode is manufactured to produce the wire drawing of coated face. On the other hand, if less than the scope, it is likely that be difficult to the effect for showing to mix 2 kinds of negative electrode active materials.
In addition, for the negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention, due to above-mentioned phase Same the reasons why, the uneven material of volume reference size distribution can also show good characteristic.So-called " volume reference granularity point Cloth is uneven ", refer to volume reference size distribution when transverse axis is logarithmic scale, be with volume reference average grain diameter (median particle diameter) During center, do not form symmetrical, as non-symmetrical degree, the Z values represented with following formula (1) be usually 0.3 μm with Above, it is preferably more than 0.5 μm, more preferably more than 1 μm.If Z is less than the value, it is likely that be difficult to obtain by size distribution not The effect that the cycle characteristics brought is improved.
Z=∣ (mould footpath)-(median particle diameter) ∣ (1)
In formula (1), the unit of mould footpath and median particle diameter all represents absolute value for " μm " , " ∣ ∣ ".
In the present invention, the value that volume reference average grain diameter (median particle diameter) and mould footpath are defined as：Make negative electrode active Material is dispersed in the 0.2 mass % aqueous solution of polyoxyethylene (20) Span-20 as surfactant In (about 1mL), the value determined using laser diffraction formula particle size distribution meter (LA-700 that Ku Chang manufacturing companies manufacture)." in Value particle diameter " is also commonly referred to as d50, larger side and smaller when referring to that powder is divided into two parts by certain particle diameter under volume reference The particle diameter during equivalent of side, " mould footpath " is referred in the size distribution of volume reference, represents the particle diameter of the maximum of distribution, is appointed It is referred to as " median particle diameter ", the value in " mould footpath " in all simply LA-700 of Ku Chang manufacturing companies manufacture of meaning one, is illustrated respectively in On device.
In addition, by making the negative electrode active material that at least one use median particle diameter of negative electrode active material is less than 10 μm Matter, can maintain low temperature power output, while obtaining the raising effect of cycle characteristics, see it is preferred from this point on.It is especially excellent Elect less than 8 μm as.Median particle diameter is less than 10 μm of negative electrode active material relative to whole negative electrode active materials, is particularly preferably existed Used in the range of 0.5~10 mass %.
In addition, the negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention, by containing using argon from The different negative electrode active material of more than two kinds of Raman R value that sub- laser Raman spectrometry is determined, can maintain cycle characteristics, together Shi Tigao low temperature power outputs.As the difference of Raman R value, usually more than 0.1, be preferably more than 0.2, more preferably 0.3 with On, as the upper limit, usually less than 1.4, be preferably less than 1.3, more preferably less than 1.2 scope.If less than the scope, Then it is difficult to the effect for obtaining bringing due to the difference of Raman R value sometimes.On the other hand, if it exceeds the scope, then due to drawing The high part of graceful R values, irreversible capacity increases sometimes.
In the present invention, Raman spectrum is determined as follows progress：Using raman spectroscopy device (for example, Japanese light splitting company system The raman spectroscopy device made), sample is naturally fallen in measure container, carry out sample filling, continuous mode is, in container Specimen surface irradiates argon laser, while making the container be rotated in the face with laser vertical.For obtained Raman spectrum, Determine 1580cm-1Peak PAIntensity IAAnd 1360cm-1Peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), by its It is defined as the Raman R value of graphite carbon particle.In addition, determining obtained Raman spectrum in 1580cm-1Peak PAHalf breadth, It is defined as the Raman half breadth of graphite carbon particle.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
Raman R value, half breadth analysis：Background processing
Smooth treatment：Simple average, 5 points of convolution
In addition, being used as negative pole used in the negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention Active material, its 1580cm-1Raman half breadth be not particularly limited, but usually 10cm-1Above, it is preferably 15cm-1 More than, in addition, its upper limit is usually 150cm-1Below, it is preferably 140cm-1Following scope.If Raman half breadth is less than The scope, then the crystallinity of particle surface is too high, and low temperature power output is reduced sometimes.On the other hand, if it exceeds the scope, then Because the crystallinity of particle surface is reduced, irreversible capacity increases sometimes.
In addition, being used as negative pole used in the negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention Active material, even if containing the different negative electrode active material of more than two kinds of crystallinity, cycle characteristics can also be maintained and improve low Warm power output.So-called crystallinity, herein refers to thickness, spacing of repetitive structure of laminated body of hexagonal wire side of carbon etc. and folds Rotating fields.Represent that the different specific physics value of crystallinity is not particularly limited, such as having interplanar distance, crystallite dimension, preferably It is different in the negative electrode active material of more than two kinds that they are used in the lithium secondary battery of the present invention.If the difference mistake of crystallinity It is small, then be difficult to obtain sometimes by mixed zone come effect.
The negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention, by containing using wide-angle x-ray Different two or more negative electrode active material of interplanar distance (d002) in (002) face that diffraction approach is determined, can maintain cycle characteristics simultaneously Improve low temperature power output.As interplanar distance (d002) difference, usually more than 0.0005nm, be preferably more than 0.001nm, more Preferably more than 0.003nm, more preferably more than 0.004nm, its upper limit are usually below 0.05nm, are preferably 0.04nm Below, it is more preferably below 0.03nm, more preferably below 0.02nm scope.If sometimes difficult less than the scope To obtain due to the effect that crystallinity is different and brings.On the other hand, if it exceeds the scope, then due to the low portion of crystallinity Point, irreversible capacity increases sometimes.The interplanar distance in (002) face that described use wide-angle x-ray diffraction is determined in the present invention (d002) the d values (interfloor distance) of lattice plane (002 face) tried to achieve by using the X-ray diffraction for learning method progress of shaking are referred to.
In addition, the negative electrode active material used in the negative pole [8] of the lithium secondary battery of the present invention, by being shaken containing use Two or more different negative electrode active material of crystallite dimension (Lc) that method is tried to achieve with X-ray diffraction, can maintain cycle characteristics and carry High/low temperature power output.It is usually more than 1nm, preferably by learning the difference for the crystallite dimension (Lc) that method tried to achieve with X-ray diffraction of shaking For more than 10nm, more preferably more than 50nm.If less than the scope, being difficult to obtain by the different institute's bands of crystallite dimension sometimes The effect come.
In addition, the negative electrode active material that uses in the negative pole [8] of the lithium secondary battery of the present invention, by containing real density not Two or more same negative electrode active material, can maintain cycle characteristics and improve low temperature power output.As the difference of real density, lead to It is often 0.03g/cm3Above, it is preferably 0.05g/cm3Above, more preferably 0.1g/cm3Above, more preferably 0.2g/ cm3More than, its upper limit is usually 0.7g/cm3Below, it is preferably 0.5g/cm3Below, it is more preferably 0.4g/cm3Following model Enclose.If less than the scope, being difficult to obtain due to the effect that real density is different and brings sometimes.On the other hand, if it exceeds The scope, then due to the low part of real density, irreversible capacity increases sometimes.
Alleged real density is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol in the present invention.
In addition, the negative electrode active material used in the present invention is by containing two or more different negative electrode active material of circularity Matter, can also maintain low temperature power output and improve cycle characteristics.As the difference of circularity, usually more than 0.01, it is preferably More than 0.02, more than 0.03 is more preferably, its upper limit is usually less than 0.3, is preferably less than 0.2, is more preferably less than 0.1 Scope.If less than the scope, being difficult to obtain by the effect that circularity difference is brought sometimes.On the other hand, if super Cross the scope, then due to the low part of circularity, during electric polarization, the problems such as producing wire drawing sometimes.
Described circularity is defined with following formula in the present invention.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured.
In addition, the negative electrode active material used in the negative pole [8] of the lithium secondary battery of the present invention, by containing tap density Two or more different negative electrode active materials, can maintain low temperature power output and improve cycle characteristics.As tap density it Difference, usually 0.1g/cm3Above, it is preferably 0.2g/cm3Above, more preferably 0.3g/cm3More than.If less than the scope, Then it is difficult to obtain the effect by mixing the different material of tap density and bringing sometimes.
In the present invention, tap density is defined as below：Make sieve of the sample by 300 μm of aperture, sample is fallen into 20cm3 Jolt ramming container in, to sample full of container upper surface after, using powder density determination device (for example, seishin enterprise-like corporations The Tap densor of manufacture), 1000 length of stroke 10mm vibration is carried out, the weight of volume and sample when thus calculates close Degree, regard the value as tap density.
In addition, the negative electrode active material used in the negative pole [8] of the lithium secondary battery of the present invention, by comparing table containing BET The different negative electrode active material of more than two kinds of area, can maintain cycle characteristics and improve low temperature power output.It is used as BET ratios The difference of surface area, usually 0.1m2/ more than g, preferably 0.5m2/ more than g, more preferably 1m2/ more than g, its upper limit is usually 20m2/ below g, preferably 15m2/ below g, more preferably 12m2/ below g scope.If less than the scope, be difficult to sometimes Obtain by mixing the effect that the different material of BET specific surface area is brought.On the other hand, if it exceeds the scope, then due to The big part of BET specific surface area, irreversible capacity increases sometimes.
In the present invention, the value that BET specific surface area is defined as：Using surface area meter (big storehouse reason develop make it is complete from Dynamic surface area determination unit), at 350 DEG C sample is carried out under nitrogen circulation 15 minutes it is predrying, then using being correctly adjusted to Nitrogen is relative to the nitrogen helium mixture that the relative pressure of atmospheric pressure is 0.3, the N2 adsorption carried out by using gas flow method 1 method of BET and the value determined.
Two or more the different negative electrode active material used in negative pole [8] as the lithium secondary battery of the present invention it is mixed A kind of composition and division in a proportion rate, ratio shared by negative electrode active material is usually more than 0.1 mass % relative to total amount, is preferably 1 mass % More than, more preferably more than 10 mass %, more preferably more than 20 mass %, its upper limit be usually 99.9 mass % with Under, be preferably below 99 mass %, more preferably below 90 mass %, more preferably below 80 mass % scope.Such as Fruit is then difficult to obtain the effect by being brought containing two or more different negative electrode active materials sometimes outside the scope.
In addition, wherein 2 kinds of different negative electrode active materials it is at least one in containing native graphite and/or native graphite Machining object, is preferred from the aspect of cost performance height.
Native graphite is classified as flaky graphite (Flake Graphite), flaky graphite according to its character (Crystalline (Vein) Graphite), soil graphite (Amorphous Graphite) (referring to《Bulk material technology It is integrated》, one, the graphite of ((strain) industrial technology center, Showa is issued for 49 years)；And " HAND BOOK OF CARBON, GRAPHITE, DIAMOND AND FULLERENES ", (Noyes Publications distribution)).Degree of graphitization is with flaky graphite Highest, is 100%, followed by flaky graphite, is 99.9%, and soil graphite as little as 28%.It is used as the scale of native graphite Shape graphite originates from Madagascar, China, Brazil, Ukraine, Canada etc.；Flaky graphite mainly originates from Sri Lanka.Soil It is the Korea peninsula, China, Mexico etc. the main product of graphite.In these native graphites, the general particle diameter of soil graphite is small and purity It is low.In contrast, flaky graphite, flaky graphite, can be in the present invention due to degree of graphitization is high, the low advantage of impurity level In preferably use.
[difference of negative pole [8] processing]
The negative electrode active material used in the present invention is by containing the different negative electrode active material of more than two kinds of working process Matter, can maintain cycle characteristics and improve low temperature power output.As the processing method of native graphite, it can enumerate at application heat The method of reason, the method for applying mechanics energy process etc..One example of heat treatment is as described below.
[[heat treatment temperature]]
As the heat treatment temperature of negative electrode active material, usually more than 600 DEG C, be preferably more than 1200 DEG C, more preferably For more than 2000 DEG C, more preferably more than 2500 DEG C, particularly preferably more than 2800 DEG C.The upper limit be usually 3200 DEG C with Under, be preferably less than 3100 DEG C.If temperature conditionss are less than the scope, the crystallization on the surface of native graphite particle is repaired sometimes It is insufficient.On the other hand, if it exceeds above range, then the distillation amount of graphite is sometimes prone to increase.What is used in the present invention is negative Pole active material preferably comprises two or more different negative electrode active material of heat treatment temperature.
[[heat treatment method]]
Heat treatment by a said temperature scope by realizing.When temperature conditionss to be maintained to the holding of above range Between be not particularly limited, but be usually to be longer than time of 10 seconds, and for less than 168 hours.
What heat treatment was generally formed under the non-active gas atmosphere such as nitrogen or in the gas produced by raw material native graphite Carried out under non-oxidizing atmosphere.But, the stove for being embedded in type in coal dust (thin pitch sinters carbon) is initially mixed sometimes There is air.In this case, it may not be necessary to complete non-active gas atmosphere.As the device used in heat treatment, without spy Do not limit, for example, can use shuttle-type stove, car tunnel furnace, electric furnace, coke roaster, rotary furnace, direct-electrifying stove, Acheson electricity Stove, resistance-heated furnace, induction heater etc..It is different that the negative electrode active material used in the present invention preferably comprises heat treatment method Negative electrode active material of more than two kinds.
In addition, except above-mentioned each processing, the various processing such as classification processing can also be carried out.Classification processing is to obtain mesh Mark particle diameter, the processing for removing coarse powder and micro mist and carrying out.The device used in being handled as classification, has no particular limits, example Such as, in the case where dry type is sieved, gyratory sifter, rock type sieve, rotary type sieve, oscillatory type sieve etc. can be used；In dry type gas In the case of flow point level, gravity type grader, inertia force formula grader, centrifugal force type grader (sizer, whirlwind can be used Separator) etc.；In the case of wet screening, can use mechanical wet classifier, hydraulic classifier, settling classifier, Centrifugal wet classifier etc..Classification processing can be carried out before heat treatment, can also be for example heat-treated laggard in other times OK.Further, it is also possible to omit classification processing in itself.The negative electrode active material used in the present invention preferably comprises classification treatment conditions Different negative electrode active materials of more than two kinds.
The negative electrode active material used in the present invention is by containing different of more than two kinds negative of mechanics energy process described later Pole active material, can maintain cycle characteristics and improve low temperature power output.One example of mechanics energy process is as described below.
[[mechanics energy process]]
Carrying out mechanics energy process makes volume average particle size ratio before and after the processing be less than 1.So-called " volume before and after the processing Average grain diameter ratio " be processing after volume average particle size divided by before processing volume average particle size obtained from value.In the present invention In, in order to manufacture the raw material before heat treatment and the mechanics energy process that carries out preferably make average grain diameter ratio before and after the processing for 1 with Under.Mechanics energy process be reduce particle size so that the average grain diameter ratio of powder particle before and after the processing be less than 1, simultaneously control Shape of particle and the processing carried out.Crush, classification, mixing, granulation, surface be modified, reaction etc. can have in particle design Imitate in the engineering unit operation utilized, mechanics energy process belongs to pulverization process.
It is so-called to crush, refer to material applying power, its size is reduced with the particle diameter or size distribution of Auto-regulator, filling Property.Pulverization process is classified according to species, the processing form of the power applied to material.The power that material applies is roughly divided into Following 4 kinds：(1) power (impulsive force), (2) crushing force (compression stress), (3) grinding forces (grinding forces), (shearing of (4) shaving power are beaten Power).On the other hand, processing form is roughly divided into following 2 kinds：Inside particles produce be cracked and be allowed to propagate volume crush, And cut the surface crushing of particle surface.Volume is crushed and can carried out using impulsive force, compression stress, shearing force；Crush on surface It can be carried out using grinding forces, shearing force.Crushing be the power that these materials will be applied species and processing form carry out it is various The processing of combination.Its combination can suitably be determined according to processing intent.
Although the situation for also having reaction or volumetric expansion using the chemistry such as explosion to carry out is crushed, usually using crushing The mechanical devices such as machine are carried out.The pulverization process used in manufacture as the spheroidization carbonaceous of the raw material of the present invention is preferably final The processing that the shared ratio of surface treatment is uprised, and it is unrelated with whetheing there is volume crushing.Because, remove particle surface crushing Angle is so that it is important that shape of particle, which becomes round,.Specifically, can again it be carried out after a certain degree of volume crushing is carried out Surface treatment, can also almost crush without volume and be only surface-treated, volume crushing and table can also be carried out simultaneously Face is handled.It is preferred that finally carrying out surface crushing, the pulverization process of arrisdefect is gone from the surface of particle.The negative pole used in the present invention is lived Property material, by the different negative electrode active material of more than two kinds of the degree containing above-mentioned surface treatment, can maintain cycle characteristics And improve low temperature power output.
The device for carrying out mechanics energy process is selected from the device that can carry out above-mentioned preferred processing.Mechanics energy Processing can be realized by using the power of one or more of the 4 kinds of power applied to above-mentioned substance, but preferably using impulsive force as It is main, and the mechanisms such as compression, friction, the shearing force including the interaction of particle are applied to particle repeatedly.Therefore, have Body, the device being preferably as follows：The device has the rotor for being provided with multiple blades inside case, and is revolved at a high speed by the rotor Then the effect of the machinery such as impact compress, friction, shearing force is assigned to the carbon material for importeding into inside, so that side carries out volume powder Broken side is surface-treated.Mechanism is assigned repeatedly by making carbonaceous material circulation or convection current in addition, more preferably having The device of mechanism.
As preferred device, hybrid system (manufacture of nara machinery manufacturing company), Kryptron (Earth can be enumerated Technica companies manufacture), CF mill (manufacture of Yu Buxingchan companies), mechanical fusion system (manufacture of hosokawamicron companies) Deng.Among these, the hybrid system that preferably nara machinery manufacturing company manufactures.When being handled using the device, preferably will The peripheral speed of the rotor of rotation is set as 30~100m/ seconds, is more preferably set as 40~100m/ seconds, further preferably setting For 50~100m/ seconds.In addition, processing simply only can pass through carbonaceous material, but preferably in device interior circulation or delay 30 Handled, more preferably handled in device interior circulation or be detained more than 1 minute more than second.
By so carrying out mechanics energy process, carbon particle turns into following particle：High crystalline is kept on the whole, simply The near surface of particle becomes coarse, tilts and exposes edge surface.So, the face increase that lithium ion can come in and go out, even in height Also there is high capacity under current density.
In general, flakey, squamous, the carbon material of tabular particle diameter it is smaller, its fillibility more has the tendency of deterioration.This It is regarded as because following reason：Due to particle by crushing more amorphization, or particle surface generation " flash ", The overshooting shape such as " stripping " or " warpage " thing increase, and particle surface with intensity to a certain degree be attached with finer nothing determine The reasons such as shape particle, so, the impedance between adjacent particle become big, deteriorate fillibility.If these particles is amorphous Property reduce, shape of particle is close to spherical, even if then particle diameter diminishes, and the reduction of fillibility is also seldom, in theory, big particle diameter carbon Powder, small particle carbon dust should all show the tap density of equal extent.
As these native graphites and/or the ratio of the machining object of native graphite, usually more than 0.1 mass %, preferably For more than 1 mass %, more preferably more than 10 mass %, more preferably more than 20 mass %, its upper limit is usually 99.9 Below quality %, preferably below 99 mass %, more preferably below 90 mass %, more preferably below 80 mass %. If less than the scope, being difficult to obtain the property by adding the machining object of native graphite and/or native graphite and bringing sometimes Valency than raising.On the other hand, if it exceeds the scope, then be difficult to obtain the effect that different negative electrode active materials are brought sometimes The raising of fruit.
[[micropore volume etc.]]
The pore volume of the negative electrode active material used as the negative electrode active material of the lithium secondary battery of the present invention, passes through Mercury, Hg porosimeter (mercury penetration method) try to achieve due to the space in the particle equivalent to a diameter of 0.01 μm~1 μm, particle The concavo-convex amount (below, being abbreviated as " micropore volume ") caused that is uneven on surface is usually more than 0.01mL/g, is preferably More than 0.05mL/g, more preferably more than 0.1mL/g, its upper limit are usually below 0.6mL/g, preferably below 0.4mL/g, more Preferably below 0.3mL/g scope.If it exceeds the scope, then need substantial amounts of adhesive when being manufactured into pole plate.If low In the scope, then high current density charge-discharge characteristic is reduced, also, electrode expansion when can not obtain discharge and recharge sometimes shrinks Alleviation effects.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, its upper limit is usually Below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.If it exceeds the scope, then be made base Sometimes for substantial amounts of adhesive during plate.If less than the scope, thickener can not be obtained sometimes when pole plate is made or viscous Tie the dispersion effect of agent.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.If less than the scope, sometimes high current density charge-discharge characteristic reduction.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).0.2g or so sample (negative material) is weighed, is encapsulated into powder container, in room (50 μm of below Hg) deaerate within 10 minutes under temperature, vacuum, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, is imported Mercury, boosts to 40000psia (about 280MPa) from 4psia (about 28kPa) stage shape, is then depressurized to 25psia (about 170kPa).Number of stages during boosting more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury press-in for 80 Amount.Micropore is calculated using Washburn formulas from the mercury press-in curve so obtained to be distributed.In addition, the surface tension of mercury (γ) is 485dyne/cm, and contact angle (φ) is 140 °.Micropore when mean pore footpath reaches 50% using accumulation micro pore volume Footpath.
[[ash content]]
The ash content of the negative electrode active material of the lithium secondary battery of the present invention is preferred relative to the gross mass of graphite carbon particle For below 1 mass %, more preferably below 0.5 mass %, particularly preferably below 0.1 mass %.In addition, its lower limit is preferably More than 1ppm.If it exceeds above range, then during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution battery performance deterioration It can not ignore.On the other hand, if less than the scope, long period and energy are needed in manufacture and for preventing pollution Equipment, sometimes cost can rise.
[[orientation ratio]]
The orientation ratio of graphite carbon particle used as the negative electrode active material of the lithium secondary battery of the present invention is usually More than 0.005, it is preferably more than 0.01, more preferably more than 0.015, is less than 0.67 in upper-bound theory.If less than the model Enclose, then high density charge-discharge characteristic is reduced sometimes.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
[[draw ratio]]
The draw ratio of the graphite carbon particle used as the negative electrode active material of the lithium secondary battery of the present invention is in theory For more than 1, the upper limit is less than 10, preferably less than 8, more preferably less than 5.If it exceeds its upper limit, wire drawing when pole plate is made Or uniform coated face can not be obtained, high current density charge-discharge characteristic is reduced sometimes.
In addition, draw ratio with the most major diameter A of particle during three dimensional viewing and perpendicular most minor axis B ratio A/B come table Show.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection be fixed on 50 microns of thickness with Under metal end face on any 50 graphite particles, rotation, tilt and be fixed with the objective table of sample, these grains are determined respectively A, B of son, obtain A/B average value.
The present invention have negative pole [8] if lithium secondary battery contain the different negative electrode active material of more than two kinds of property Matter, the species of negative electrode active material is not particularly limited.But, for interplanar distance (d002), crystallite dimension (Lc), orientation The property for passing through X-ray diffraction measure than, pole plate orientation ratio etc.；Raman R value, Raman half breadth etc. are related to Raman spectrum Property；And ash content, because above-mentioned numerical value is premised on carbonaceous material, therefore the difference of above-mentioned numerical value is applied to carbonaceous material.Separately On the one hand, for properties related to size distribution such as median particle diameter, mould footpath, Z；BET specific surface area；Micropore volume, total micropore The property that volume, mean pore footpath etc. are determined by mercury voidage meter；Real density；Circularity；Tap density；And major diameter Than above-mentioned numerical value is not limited to carbonaceous material, it is adaptable to all materials that may be used as negative electrode active material, the difference of above-mentioned numerical value Suitable for all substances.However, it is preferred to which the material with above-mentioned 2 kinds of property is carbonaceous material.Now, above-mentioned numerical value regards table as Show the value of the property of carbonaceous material, preferably use the different carbonaceous material of more than two kinds of the property as negative electrode active material.
[mixed method of two or more negative electrode active material of negative pole [8]]
When mixing two or more negative electrode active material, the device used is not particularly limited, can for example enumerate V-Mixer, Wtypeofblender, container changeable type mixer, kneading machine, barrel mixer, shear mixer etc..
[the electrode manufacture of negative pole [8]]
The manufacture of negative pole [8] may be carried out by conventional means, and can form negative pole [8] as described above.Collector, Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of collector and active material layer etc. are also same as described above.
<Negative pole [9] and [10]>
The negative pole [9] (mode A) and negative pole [10] (mode B) that are used in the lithium secondary battery of the present invention are said below Bright, the negative pole [9] is 0.1g/cm containing tap density3More than, and using mercury, Hg porosimeter measure equivalent to diameter The micropore volume of the particle of 0.01 μm~1 μ m is more than 0.01mL/g negative electrode active material；Negative pole [10] charging To the negative pole nominal capacity 60% when, by negative pole opposed battery produce reaction resistance be 500 below Ω.
<<Negative pole [9] (mode A)>>
The mode A of the present invention is related to a kind of lithium secondary battery, wherein, what is wherein contained is used to the negative pole used in the present invention The physical property of negative electrode active material is provided, and the lithium secondary battery includes nonaqueous electrolytic solution and negative pole, the non-aqueous solution electrolysis Liquid contains above-mentioned specific compound, and the negative pole contains the negative electrode active material with following specific physical property.Below to the present invention Mode A illustrate.
[negative electrode active material of negative pole [9]]
Negative electrode active material in the mode A of the present invention in electrochemistry can with occlusion, release lithium ion, and also at least Meet following (a) and (b) important document.
(a) tap density is 0.1g/cm3More than；
(b) micropore volume of 0.01 μm~1 μm of scope of mercury, Hg porosimeter measure is used for more than 0.01mL/g.
[[tap density]]
The tap density preferably 0.1g/ of the negative electrode active material contained in the negative pole [9] of the lithium second electrode of the present invention cm3More than, more preferably 0.5g/cm3More than, more preferably 0.7g/cm3More than, particularly preferably 0.9g/cm3More than. In addition, its upper limit is preferably 2g/cm3Hereinafter, more preferably 1.8g/cm3Hereinafter, particularly preferably 1.6g/cm3Below.If shaken Real density is less than the scope, then particularly can not realize the effect of high-output power.On the other hand, if it exceeds the scope, then Interparticle space in electrode is very few, and the stream in nonaqueous electrolytic solution is reduced, and power output is reduced in itself sometimes.
In the present invention, tap density is defined as below：Make sieve of the sample by 300 μm of aperture, sample is fallen into 20cm3 Jolt ramming container in, to sample full of container upper surface after, using powder density determination device (for example, seishin enterprise-like corporations The Tap densor of manufacture), 1000 length of stroke 10mm vibration is carried out, volume and weight when thus calculates density, will The value is used as tap density.
[[micropore volume]]
The micropore volume of the negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention, passes through mercury hole Gap rate meter (mercury penetration method) try to achieve due to space in the particle equivalent to a diameter of 0.01 μm~1 μm, particle surface The concavo-convex amount (below, being abbreviated as " micropore volume ") caused that is uneven is more than 0.01mL/g, preferably 0.05mL/g with On, more preferably more than 0.1mL/g, its upper limit is usually below 0.6mL/g, preferably below 0.4mL/g, more preferably Below 0.3mL/g scope.If it exceeds the scope, then need substantial amounts of adhesive when being manufactured into pole plate.On the other hand, if Less than the scope, then long-life, high-output power can not be realized.
In addition, total micropore volume is preferably more than 0.1mL/g, more preferably more than 0.25mL/g, more preferably More than 0.4mL/g, its upper limit is usually below 10mL/g, preferably below 5mL/g, more preferably below 2mL/g scope.Such as Fruit exceedes the scope, then when substrate is made sometimes for substantial amounts of adhesive.If less than the scope, when pole plate is made Sometimes the dispersion effect of thickener or binding agent can not be obtained." total micropore volume " mentioned here refers in following condition determinations Four corner in determine micropore volume sum.
In addition, mean pore footpath is preferably more than 0.05 μm, more preferably more than 0.1 μm, more preferably 0.5 μm with On, its upper limit is usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm of scope.If it exceeds the scope, Then sometimes for substantial amounts of adhesive.If less than the scope, sometimes high current density charge-discharge characteristic reduction.
As the device for mercury, Hg porosimeter, mercury, Hg porosimeter (autopore9520 can be used； Micrometritics companies manufacture).0.2g or so sample (negative material) is weighed, is encapsulated into powder container, in room (50 μm of below Hg) deaerate within 10 minutes under temperature, vacuum, implements pre-treatment.Then, 4psia (about 28kPa) is decompressed to, is imported Mercury, boosts to 40000psia (about 280MPa) from 4psia (about 28kPa) stage shape, is then depressurized to 25psia (about 170kPa).Number of stages during boosting more than the stage, in each stage, after the equilibration time of 10 seconds, determines mercury press-in for 80 Amount.Micropore is calculated using Washburn formulas from the mercury press-in curve so obtained to be distributed.In addition, the surface tension of mercury (γ) is 485dyne/cm, and contact angle (φ) is 140 °.Micropore when mean pore footpath reaches 50% using accumulation micro pore volume Footpath.
The mode A of present invention lithium secondary battery, for negative electrode active material, as long as meeting above-mentioned important document (a) and (b) just The effect of the invention described above can be played, performance is given full play to, further, for negative electrode active material, preferably met simultaneously Following physical property it is any one or more.In addition, for negative pole, particularly preferably while meeting the negative pole in mode B described later It is any one or more in physical property or structure.
[[BET specific surface area]]
The ratio table of the negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the invention determined using BET method Area is preferably 0.1m2/ more than g, particularly preferably 0.7m2/ more than g, more preferably 1m2/ more than g, more preferably 1.5m2/ more than g.Its upper limit is preferably 100m2/ below g, particularly preferably 50m2/ below g, more preferably 25m2/ below g, enters One step is preferably 15m2/ below g.If the value of BET specific surface area is less than above range, in the feelings used as negative material Under condition, in charging, the acceptance of lithium is deteriorated, and lithium is easily separated out in electrode surface, and high-output power can not be obtained sometimes.It is another Aspect, if it exceeds above range, then as negative material in use, increasing with the reactivity of electrolyte, the gas of generation Become many, be difficult to obtain preferred battery sometimes.
BET specific surface area is defined as the value determined：Using surface area meter (for example, big storehouse reason develops make full-automatic Surface area determination unit), nitrogen circulation, sample is carried out at 350 DEG C 15 minutes it is predrying, then, using nitrogen relative to The relative pressure of atmospheric pressure is accurately adjusted to 0.3 nitrogen helium mixture, by using the N2 adsorption BET1 of gas flow method Point method is determined.
[[volume average particle size]]
The volume average particle size of the negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention is defined as leading to Cross the average grain diameter (median particle diameter) for the volume reference that laser diffraction/scattering method is tried to achieve, preferably more than 1 μm, particularly preferably 3 More than μm, more preferably more than 5 μm, more preferably more than 7 μm.In addition, its upper limit is usually less than 50 μm, preferably 40 Below μm, more preferably less than 30 μm, more preferably less than 25 μm.If less than above range, irreversible capacity increases Greatly, the loss of initial cell capacity is occasionally resulted in.In addition, if more than above range, then when electrode pad is made, easy shape It is sometimes undesirable in battery production process into uneven coated face.
In the present invention, volume reference average grain diameter is defined with median particle diameter, and the median particle diameter is by the following method Determine：Carbon dust is set to be dispersed in 0.2 matter of polyoxyethylene (20) Span-20 as surfactant Measure in the % aqueous solution (about 1mL), using laser diffraction/scattering formula particle size distribution meter (for example, what Ku Chang manufacturing companies manufactured LA-700) determine.
[[circularity]]
The circularity of the negative electrode active material contained in the negative pole [9] of the lithium second electrode of the present invention is usually more than 0.1, Preferably more than 0.5, more preferably more than 0.8, particularly preferably more than 0.85, more preferably more than 0.9.As upper Limit, circularity forms proper sphere in theory when being 1.If circularity is less than the scope, it is possible to produce wire drawing etc. during electric polarization Problem.
Described circularity is defined with following formula in the present invention.
Circularity=(there is the girth with particle projection of shape equivalent circular of the same area)/(reality of particle projection of shape Border girth)
The value determined as follows is used as the value of circularity：Using flow-type particle image analysis device (for example, Sysmex The FPIA of Industrial companies manufacture), about 0.2g samples are scattered in polyoxyethylene (20) sorb as surfactant In the 0.2 mass % aqueous solution (about 50mL) of sugar alcohol acid anhydride monolaurate, the super of 1 minute 28kHz is irradiated with 60W power output After sound wave, it is detection range to specify 0.6~400 μm, and the particle of the μ m of particle diameter 3~40 is measured.
[[interplanar distance (d002)]]
The negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention is surveyed using wide-angle x-ray diffraction The interplanar distance (d002) in fixed (002) face is usually below 0.38nm, preferably below 0.36nm, more preferably 0.35nm with Under, more preferably below 0.345nm, its lower limit is more than the theoretical value 0.335nm of graphite.If it exceeds the scope, then Crystallinity is significantly reduced, and irreversible capacity increases sometimes.
The interplanar distance (d002) in described (002) face determined by wide-angle x-ray diffraction, refers to pass through in the present invention Learn the d values (interfloor distance) in lattice plane (002) face that method of shaking is tried to achieve with X-ray diffraction.
[[crystallite dimension (Lc)]]
In addition, not limited especially by the crystallite dimension (Lc) for learning the negative electrode active material that method of shaking is tried to achieve with X-ray diffraction Determine, usually more than 0.1nm, preferably more than 0.5nm, more preferably more than 1nm scope.If less than the scope, tied Crystalline substance is significantly reduced, and irreversible capacity increases sometimes.
[[real density]]
The real density of negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention usually 1.5g/cm3 More than, preferably 1.7g/cm3More than, more preferably 1.8g/cm3More than, more preferably 1.85g/cm3More than, its upper limit For 2.26g/cm3Below.The upper limit is the theoretical value of graphite.If less than the scope, the crystallinity of carbon is too low, irreversible capacity Sometimes increase.In the present invention, real density is defined as the value of Liquid displacement methods (hydrometer method) measure by using butanol.
[[Raman R value]]
The Raman R value of negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention be usually 0.01 with On, preferably more than 0.03, more preferably more than 0.1.As the upper limit, preferably less than 1.5, more preferably less than 1.2, especially Preferably less than 0.5.If Raman R value is less than the scope, the crystallinity of particle surface is too high, with subtracting for charge and discharge potential point Few, power output is reduced sometimes.On the other hand, if it exceeds the crystallinity reduction of the scope, then particle surface, irreversible capacity Sometimes increase.
Raman spectrum is determined as follows progress：Use raman spectroscopy device (such as raman spectroscopy that Japanese light splitting society manufactures Device), sample is fallen and is filled in cell naturally, argon laser is irradiated to the specimen surface in pond, meanwhile, pond is existed With being rotated in the face of laser vertical.For obtained Raman spectrum, 1580cm is determined-1Peak PAIntensity IAAnd 1360cm-1's Peak PBIntensity IB, calculate its strength ratio R (R=IB/IA), it is defined as the Raman R value of negative electrode active material.In addition, determining Obtained Raman spectrum is in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the Raman half value of negative electrode active material Width.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~25mW
Resolution ratio：10~20cm-1
Measurement range：1100cm-1~1730cm-1
Raman R value, the analysis of Raman half breadth：Background processing
Smooth treatment：Simple average, 5 points of convolution
In addition, the negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention is in 1580cm-1Raman half Value width has no particular limits, usually 10cm-1More than, preferably 15cm-1More than, in addition, its upper limit is usually 150cm-1 Hereinafter, preferably 100cm-1Hereinafter, more preferably 60cm-1Following scope.If Raman half breadth is less than the scope, The crystallinity of particle surface is too high, and with the reduction of charge and discharge potential point, power output is reduced sometimes.On the other hand, if above The crystallinity reduction of the scope, then particle surface, irreversible capacity increases sometimes.
[[ash content]]
The ash content of negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention be preferably 1 mass % with Under, more preferably below 0.5 mass %, particularly preferably below 0.1 mass %.In addition, as lower limit, preferably 1ppm with On.If it exceeds above range, then the deterioration of battery performance can not be neglected during discharge and recharge and caused by the reaction of nonaqueous electrolytic solution Depending on circulation conservation rate is reduced sometimes.On the other hand, if less than the scope, needed in manufacture long period and energy with And for prevent pollution equipment, sometimes cost can rise.
[[draw ratio]]
The draw ratio of negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention be theoretically 1 with On, as the upper limit, usually less than 10, preferably less than 8, more preferably less than 5.If it exceeds its upper limit, then manufacture negative pole When active material wire drawing or uniform coated face can not be obtained, high current density charge-discharge characteristic is reduced sometimes.
In addition, draw ratio with the most major diameter A of particle during three dimensional viewing and perpendicular most minor axis B ratio A/B come table Show.The observation of particle with the scanning electron microscope of amplifying observation by that can be carried out.Selection be fixed on 50 microns of thickness with Under metal end face on any 50 graphite particles, rotation, tilt and be fixed with the objective table of sample, these grains are determined respectively A, B of son, obtain A/B average value.
[[orientation ratio]]
The orientation ratio of negative electrode active material contained in the negative pole [9] of the lithium secondary battery of the present invention be usually 0.005 with On, preferably more than 0.01, more preferably more than 0.015, it is less than 0.67 in upper-bound theory.If high less than the scope Density charge-discharge characteristic is reduced sometimes.
Orientation ratio passes through X-ray diffraction measure.Using asymmetric Pearson VII as distribution function, fitting passes through X-ray (110) diffraction for the carbon that diffraction is obtained and the peak of (004) diffraction, carry out peak separation, (110) diffraction and (004) are calculated respectively The integrated intensity at the peak of diffraction.Calculated by obtained integrated intensity strong by (110) diffraction integral intensity/(004) diffraction integral The ratio represented is spent, the ratio is defined as negative electrode active material orientation ratio.
Here X-ray diffraction measure condition is as follows.In addition, " 2 θ " represents the angle of diffraction.
Target：Cu (K alpha rays) graphite monochromatic photometer
Slit：Divergent slit=1 degree, by optical slits=0.1mm, scatter slit=1 degree
Measurement range and stepping angle/minute
(110) face：76.5 degree≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 degree≤2 0.01 degree of θ≤56.0 degree/3 seconds
[electrode of manufacture negative pole [9]]
The manufacture of negative pole may be carried out by conventional means, and can form negative pole [9] as described above.Collector, collection Thickness ratio, electrode density, adhesive, pole plate orientation ratio, the impedance of electric body and active material layer etc. are also same as described above.
<<For negative pole [10] (mode B)>>
The negative pole [10] (mode B) of the present invention is related to a kind of lithium secondary battery, wherein, the negative pole used in the present invention is used Negative pole physical property in itself and/or structure regulation, the lithium secondary battery include nonaqueous electrolytic solution and with following specific physical property and/ Or the negative pole of structure, the nonaqueous electrolytic solution contains above-mentioned specific compound.Below to the negative pole [10] (mode B) of the present invention Illustrate.
[physical property, structure of negative pole [10] negative pole]
The physical property of negative pole and structure that are used in mode B lithium secondary battery are illustrated below.Negative pole is in collector It is upper that there is negative electrode active material layer.
[[reaction resistance]]
It is anti-that the opposed impedance (to イ ン ピ ー ダ Application ス) of the negative pole used in the mode B of the present invention is tried to achieve in determining Resistance is answered to be necessary for 500 below Ω, more preferably preferably 100 below Ω, 50 below Ω.Lower limit is not particularly limited.If More than the scope, then when lithium secondary battery is made, the characteristics of output power reduction before and after cyclic test.In addition, sometimes The reduction of circulation conservation rate can be produced due to high resistance.
Illustrate the assay method of opposed impedance below.Typically in the impedance measuring of lithium secondary battery, to the positive pole of battery Implement Based on AC Impedance Measurements between terminal and negative terminal, if but finally representing that positive pole and negative pole are mixed in one using party's rule The impedance risen, it is impossible to clearly determine which which positive and negative electrode resistance produced by.Therefore, in the present invention, determine only by negative pole Opposed battery produce reaction resistance.The assay method of the reaction resistance in the present invention is set forth below.
The lithium secondary battery of measure uses following battery：Can be carried out with the current value of 5 hours charging nominal capacitys After charging, maintain not discharge and recharge in 20 minutes state, then with can with 1 hour electric discharge nominal capacity current value be put Electricity, capacity now is more than the 80% of nominal capacity.For the lithium secondary battery of above-mentioned discharge condition, that can use 5 hours The current value of charging nominal capacity charges to the 60% of nominal capacity, and lithium secondary battery is transferred to the hand under argon atmosphere immediately Cover in work box.Wherein, the lithium secondary battery is not discharged in negative pole or rapidly dismounting is not taken out in the state of short circuit, if It is two sided coatings electrode, then does not damage another side electrode activity thing quality and peel off the electrode active material of one side, by 2 pieces of negative poles Electrode is punching into 12.5mm φ, makes active material face opposed without departing from ground by dividing plate.Battery is added dropwise between dividing plate and two negative poles The middle μ L of nonaqueous electrolytic solution 60 used are simultaneously sealed, and are kept the state not contacted with the external world, are led on the collector of two negative poles Electricity, implements AC impedence method.Measure is at 25 DEG C of temperature, 10-2~105Complex impedance measuring is carried out under Hz frequency band, will be tried to achieve The circular arcs of negative pole resistance components of Ke Li-Ke Li curves (U ー Le U ー Le プ ロ ッ ト) be approximately semicircle, try to achieve anti- Answer resistance (Rct) and double-deck capacity (Cdl).
In the mode B of present invention lithium secondary battery, for negative pole, as long as from opposed battery (to セ Le) production of negative pole Raw reaction resistance meets above-mentioned important document, it is possible to play the effect of the invention described above, so as to give full play to performance, further Ground, preferably simultaneously meet following negative poles physical property or structure it is any one or more.In addition, for negative electrode active material, it is special Preferably while not meeting any one or more of the physical property of the negative electrode active material described in mode A.
[[double-deck capacity (Cdl)]]
The double-deck capacity (Cdl) tried to achieve in the opposed impedance measuring of the negative pole used in the present invention is preferably 1 × 10-6F with Above, particularly preferably 1 × 10-5More than F, more preferably 3 × 10-5More than F.If less than the scope, due to what can be reacted Area is reduced, and as a result power output is reduced sometimes.
[[adhesive]]
As the adhesive for bonding negative electrode active material and collector, as long as manufactured for nonaqueous electrolytic solution or electrode When the material of solvent-stable that uses, be not particularly limited, material, the adhesive that can be used are lived relative to whole negative poles The ratio of property material layer etc. is same as described above.
[manufacture of negative pole [10] electrode]
The manufacture of negative pole [10] may be carried out by conventional means, and can form negative pole [10] as described above.Current collection Body, the thickness ratio of collector and active material layer, electrode density, adhesive, pole plate orientation ratio, impedance etc. are also same as described above.
<Nonaqueous electrolytic solution>
As long as the nonaqueous electrolytic solution used in the present invention containing electrolyte (lithium salts) and dissolve the electrolyte nonaqueous solvents, Specific compound, is not particularly limited, and preferred meet of the nonaqueous electrolytic solution is selected from following electrolyte [1]~electrolyte [9] In either condition electrolyte：
Electrolyte [1]：The nonaqueous solvents for constituting electrolyte is at least mixed solvent containing ethylene carbonate, and carbonic acid Ethyl is the volume % of 1 volume %~25 relative to the ratio of nonaqueous solvents total amount；
Electrolyte [2]：The nonaqueous solvents for constituting electrolyte contains at least one asymmetric linear carbonate, and this is not right Linear carbonate content ratio shared in whole nonaqueous solvents is called the volume % of 5 volume %~90；
Electrolyte [3]：The nonaqueous solvents for constituting electrolyte contains at least one chain carboxylate；
Electrolyte [4]：The nonaqueous solvents for constituting electrolyte contains the solvent that flash-point is more than 70 DEG C, and its content is all non- More than the 60 volume % of aqueous solvent；
Electrolyte [5]：Contain LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) boric acid Lithium is used as the lithium salts for constituting electrolyte；
Electrolyte [6]：The lithium salts for constituting electrolyte is fluorine-containing lithium salts, and contains 10ppm in whole nonaqueous electrolytic solutions ~300ppm hydrogen fluoride (HF)；
Electrolyte [7]：Contain vinylene carbonate in the electrolytic solution, the content of the vinylene carbonate is the total matter of electrolyte The mass % of 0.001 mass %~3 of amount scope；
Electrolyte [8]：Also contain in the electrolytic solution represented selected from above-mentioned formula (4) compound, containing nitrogen and/or sulphur At least one of heterocyclic compound, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound, it is in whole nonaqueous electrolytic solutions Content is the mass % of 0.001 mass %~5 scope；
Electrolyte [9]：In the electrolytic solution, overcharge preventing agent is also contained.
Hereinafter, nonaqueous electrolytic solution usually used in the lithium secondary battery of the present invention is illustrated first.
[lithium salts]
As electrolyte, as long as the known lithium salts that can be used as the electrolyte of non-aqueous electrolytic solution used for lithium secondary batteries It is not particularly limited, for example, can enumerates following lithium salts.
Inorganic lithium salt：LiPF6、LiBF4、LiAsF6、LiSbF6Etc. inorganic fluoride salts；LiClO4、LiBrO4、LiIO4Deng Perhalide；LiAlCl4Deng butter salt etc..
Fluorine-containing organic lithium salt：LiCF3SO3Etc. perfluoroalkanesulfosalt salt；LiN(CF3SO2)2、
LiN(CF3CF2SO2)2、LiN(CF3SO2)(C4F9SO2) etc. perfluoroalkanesulfonyl inferior amine salt；
LiC(CF3SO2)3Deng perfluoroalkanesulfonyl methyl salt dissolving, Li [PF5(CF2CF2CF3)]、
Li[PF4(CF2CF2CF3)2]、Li[PF3(CF2CF2CF3)3]、Li[PF5(CF2CF2CF2CF3)]、
Li[PF4(CF2CF2CF2CF3)2]、Li[PF3(CF2CF2CF2CF3)3] etc. fluoroalkyl fluorinated phosphate salt etc..
Oxalate closes borate：Two (oxalate conjunction) lithium borates, difluoro oxalate root close lithium borate etc..
They can be used alone one kind, can also use two or more with ratio combine in any combination.Wherein, such as Dissolubility of the fruit comprehensive descision in nonaqueous solvents, charge-discharge characteristic when being made secondary cell, characteristics of output power, circulation are special Property etc., then preferably LiPF6。
Preferred example when two or more is applied in combination is that LiPF is applied in combination6With LiBF4, now, LiBF4Account for two The ratio that person amounts to is preferably the mass % of 0.01 mass %~20, the mass % of particularly preferably 0.1 mass %~5.
In addition, is inorganic fluoride salts and perfluoroalkanesulfonyl inferior amine salt are applied in combination in another example, it is now, inorganic The ratio that fluoride salt accounts for both totals is preferably the mass % of 70 mass %~99, the mass % of more preferably 80 mass %~98. Being applied in combination for the rwo has the effect for suppressing to be deteriorated caused by High temperature storage.
The concentration of above-mentioned lithium salts in nonaqueous electrolytic solution is not particularly limited, but usually more than 0.5mol/L, is preferably More than 0.6mol/L, more preferably more than 0.7mol/L.In addition, its upper limit is usually below 2mol/L, preferably 1.8mol/L Hereinafter, more preferably below 1.7mol/L.If concentration is too low, the electrical conductivity of nonaqueous electrolytic solution is sometimes insufficient, the opposing party Face, if excessive concentration, due to viscosity rise, electrical conductivity is reduced sometimes, and the performance of lithium secondary battery is reduced sometimes.
[nonaqueous solvents]
As nonaqueous solvents, it can suitably select to make from the conventional solvent proposed as the solvent of nonaqueous electrolytic solution With.Following nonaqueous solvents can for example be enumerated.
1) cyclic carbonate：
The carbon number for constituting the alkylidene of cyclic carbonate is preferably 2~6, and particularly preferably 2~4.Specifically, example Ethylene carbonate, propylene carbonate, butylene carbonate can such as be enumerated.Wherein, preferably ethylene carbonate, polypropylene carbonate Ester.
2) linear carbonate
As linear carbonate, preferably dialkyl carbonate, the carbon number point of the alkyl of dialkyl carbonate is constituted You Xuanwei not 1~5, particularly preferably 1~4.Specifically, dimethyl carbonate, diethyl carbonate, carbonic acid two can for example be enumerated The dialkyl carbonates such as n-propyl, methyl ethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester.Wherein, it is preferably Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.
3) cyclic ester：
Specifically, such as can enumerate gamma-butyrolacton, gamma-valerolactone.
4) chain ester：
Specifically, such as can enumerate methyl acetate, ethyl acetate, propyl acetate, methyl propionate.
5) cyclic ether
Specifically, such as can enumerate tetrahydrofuran, 2- methyltetrahydrofurans, oxinane.
6) chain ether：
Specifically, such as can enumerate dimethoxy-ethane, dimethoxymethane.
7) sulfur-bearing organic solvent：
Specifically, such as can enumerate sulfolane, diethyl sulfone.
They may be used singly or in combination of two or more, and preferred compositions use compound of more than two kinds.Example Such as, the preferably solvent of the high dielectric constant such as cyclic carbonates or ring-type esters and linear carbonate class or chain esters etc. is low viscous Degree solvent combination is used.
One of preferred compositions of nonaqueous solvents are the combinations based on cyclic carbonates and linear carbonate class.Its In, the total of cyclic carbonates and linear carbonate class is accounted for more than 80 capacity % in nonaqueous solvents, preferably 85 capacity % with On, more preferably more than 90 capacity %.In addition, relative to cyclic carbonates and the total of linear carbonate class, cyclic carbonate The capacity of class is more than 5%, preferably more than 10%, more preferably more than 15%, and usually less than 50%, preferably 35% Hereinafter, more preferably less than 30%.Particularly preferably by the total of carbonates above-mentioned preferred appearance shared in nonaqueous solvents Amount scope, the preferred above-mentioned range of capacity with cyclic carbonates relative to ring-type and linear carbonate class are combined.If made With the combination of the nonaqueous solvents, then due to the cycle characteristics of battery and High temperature storage characteristic that are manufactured using the combination (especially The residual capacity and high load capacity discharge capacity after High temperature storage) balance become excellent, it is advantageous to.
Contain in the in the mixed solvent selected from the cyclic siloxane compound shown in lithium salts and above-mentioned formula (1), above-mentioned logical The compound shown in fluorosilane compounds, above-mentioned formula (3), intramolecular shown in formula (2) have the compound of S-F keys, nitric acid The non-aqueous solution electrolysis of at least one of salt, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate compound Liquid, because the cycle characteristics of battery and High temperature storage characteristic manufactured using the nonaqueous electrolytic solution is (particularly after High temperature storage Residual capacity and high load capacity discharge capacity) and suppress gas produce balance become excellent, it is advantageous to.
As cyclic carbonates and the specific example of the preferred compositions of linear carbonate class, ethylene carbonate can be enumerated And dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate, carbonic acid two Methyl esters and diethyl carbonate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and carbon Sour methyl ethyl ester, ethylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate etc..It can enumerate sub- in these carbonic acid The combination of propylene carbonate is further added in the combination of ethyl ester and linear carbonate as preferred combination.It is sub- containing carbonic acid During propyl ester, the Capacity Ratio of ethylene carbonate and propylene carbonate is usually 99:1~40:60, preferably 95:5~50:50.
Further, if the amount for making propylene carbonate account for whole nonaqueous solvents is more than 0.1 capacity %, is preferably 1 appearance Measure more than %, more preferably more than 2 capacity %, and usually below 10 capacity %, preferably below 8 capacity %, more preferably 5 Below capacity %, then due to can be on the basis of the characteristic of combination of ethylene carbonate and linear carbonate class be maintained, low temperature Characteristic is more excellent, it is advantageous to.
Wherein, further preferably asymmetric linear carbonate class, particularly containing ethylene carbonate, dimethyl carbonate And methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate, carbonic acid diethyl When the ethylene carbonate such as ester and methyl ethyl carbonate, symmetrical linear carbonate class and asymmetric linear carbonate class, because circulation is special The balancing good of property and heavy-current discharge characteristic, it is advantageous to.Wherein, preferably asymmetric linear carbonate class is methyl ethyl carbonate Ester, in addition, the carbon number for constituting the alkyl of dialkyl carbonate is preferably 1~2.
It is preferred that other examples of nonaqueous solvents be the nonaqueous solvents containing chain ester.As chain ester, particularly preferably Methyl acetate, ethyl acetate etc..Chain ester capacity shared in nonaqueous solvents is usually more than 5%, be preferably more than 8%, More preferably more than 15%, and usually less than 50%, be preferably less than 35%, more preferably less than 30%, further preferably For less than 25%.Particularly, from the aspect of the low-temperature characteristics for improving battery, preferably in above-mentioned cyclic carbonates and chain carbon The in the mixed solvent of esters of gallic acid contains chain ester.
The example of other preferred nonaqueous solvents, for selected from ethylene carbonate, propylene carbonate, gamma-butyrolacton and γ-penta A kind of organic solvent in lactone, or the mixed solvent containing two or more organic solvent in the group account for whole solvents More than 60 capacity % nonaqueous solvents.Such preferred flash-point of mixed solvent is more than 50 DEG C, wherein, particularly preferred flash-point is 70 More than DEG C.Even if being used at high temperature using the nonaqueous electrolytic solution of the solvent, the evaporation or leakage of solvent are also reduced.Wherein, such as The solvent that fruit is more than 60 capacity % using gamma-butyrolacton amount shared in nonaqueous solvents, ethylene carbonate and gamma-butyrolacton Total accounted in nonaqueous solvents more than 80 capacity %, be preferably more than 90 capacity % and ethylene carbonate and gamma-butyrolacton Capacity Ratio is 5:95~45:55 solvent, or the total of ethylene carbonate and propylene carbonate account for 80 appearances in nonaqueous solvents More than % is measured, is preferably more than 90 capacity % and the Capacity Ratio of ethylene carbonate and propylene carbonate is 30:70~60:40 it is molten Agent, then the balance of general cycle characteristics and heavy-current discharge characteristic etc. become excellent.
[specific compound]
The nonaqueous electrolytic solution of the present invention, as described above, it is characterised in that contain or add selected from the ring shown in formula (1) The compound shown in fluorosilane compounds, formula (3), intramolecular shown in shape silicone compounds, formula (2) have S-F keys At least one of compound, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate chemical combination They (are referred to as " specific compound ") by thing sometimes.
[[cyclic siloxane compound shown in formula (1)]]
The R in cyclic siloxane compound shown in formula (1)1And R2For the carbon number 1 that can be same to each other or different to each other ~12 organic group, is used as R1And R2, can enumerate methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl group, sec-butyl, The chain-like alkyls such as the tert-butyl group；The cyclic alkyls such as cyclohexyl, norborneol alkyl；Vinyl, 1- acrylic, pi-allyl, cyclobutenyl, 1, The alkenyls such as 3- butadienyls；The alkynyls such as acetenyl, propinyl, butynyl；The haloalkyls such as trifluoromethyl；3- pyrrolidines and third Base etc. has the alkyl of saturated heterocyclyl；There can be the aryl such as the phenyl of alkyl substituent；The virtues such as phenyl methyl, phenylethyl Alkyl；The trialkylsilkls such as trimethyl silyl；Trialkyl silica oxyalkyl such as trimethylsiloxane group etc..
Wherein, the few group of carbon number easily shows the organic group of characteristic, preferably carbon number 1~6.In addition, Alkenyl improves characteristics of output power due to acting on the film of nonaqueous electrolytic solution or electrode surface, and aryl is due to catching charge and discharge The free radical that is produced when electric in battery and with the effect for improving battery overall performance, it is advantageous to.Therefore, as R1And R2, Particularly preferably methyl, vinyl or phenyl.
In formula (1), n represents 3~10 integer, preferably 3~6 integer, particularly preferably 3 or 4.
As the example of the cyclic siloxane compound shown in formula (1), can for example enumerate hexamethyl cyclotrisiloxane, The rings three such as hexaetcycletrisiloxane, hexaphenyl cyclotrisiloxane, 1,3,5- trimethyl -1,3,5- trivinyl cyclotrisiloxane Siloxanes；The cyclotetrasiloxanes such as octamethylcy-clotetrasiloxane；D5s such as decamethylcyclopentaandoxane etc..Wherein, especially It is preferred that cyclotrisiloxane.
[[fluorosilane compounds shown in formula (2)]]
The R in fluorosilane compounds shown in formula (2)3~R5For the carbon number that can be same to each other or different to each other be 1~ 12 organic group, except being used as the R in formula (1)1And R2Example chain-like alkyl, cyclic alkyl, alkenyl, the alkynes enumerated Base, haloalkyl, the alkyl with saturated heterocyclyl, aryl, aralkyl, the trialkylsilyl such as phenyl can with alkyl Outside base, trialkyl silica oxyalkyl, the carbonyls such as ethoxycarbonyl-ethyl can also be enumerated；Acetoxyl group, acetoxy-methyl, trifluoro The carboxyls such as acetoxyl group；The epoxides such as methoxyl group, ethyoxyl, propoxyl group, butoxy, phenoxy group, allyloxy；Allyl amino etc. Amino；Benzyl etc..
In formula (2), x represents 1~3 integer, and p, q and r represent 0~3 integer, and 1≤p+q+r≤3 respectively.This Outside, inevitably, x+p+q+r=4.
As the example of the fluorosilane compounds shown in formula (2), Trimethlyfluorosilane, triethyl group fluorine silicon can be enumerated Alkane, tripropyl silicon fluoride, pheiiyldimetliyl silicon fluoride, triphenylfluorosilane, vinyl-dimethyl base silicon fluoride, vinyl diethyl The list silicon fluoride class such as silicon fluoride, vinyl diphenyl silicon fluoride, trimethoxyfluorosilane, triethoxyfluorosilane, and diformazan The difluoro silanes such as the silicon fluoride of base two, the silicon fluoride of diethyl two, the silicon fluoride of divinyl two, the silicon fluoride of ethyl vinyl two；First The silicofluoroform classes such as base silicofluoroform, ethyl silicofluoroform.
Formula (2) if shown in fluorosilane compounds low boiling point, due to volatilization be difficult to sometimes in nonaqueous electrolytic solution Contain defined amount.In addition, after containing in nonaqueous electrolytic solution, in the heating due to battery caused by discharge and recharge or external environment condition To be possible to volatilization under the conditions of high temperature etc..It is therefore preferable that there is the compound of more than 50 DEG C boiling points under 1 atmospheric pressure, wherein special Preferably there is no the compound of more than 60 DEG C boiling points.
In addition, in the same manner as the compound of formula (1), as organic group, the few group of carbon number easily shows effect Really, carbon number acts on the film of nonaqueous electrolytic solution or electrode surface and improves characteristics of output power for 1~6 alkenyl, Aryl catches the free radical produced during discharge and recharge in battery and has the effect for improving battery overall performance.Therefore, from the sight From the point of view of point, as organic group, preferably methyl, vinyl or phenyl, the example of compound, particularly preferably trimethyl are used as Silicon fluoride, vinyl-dimethyl base silicon fluoride, pheiiyldimetliyl silicon fluoride, vinyl diphenyl silicon fluoride etc..
[[compound shown in formula (3)]]
The R in compound shown in formula (3)6~R8For the organic of the carbon number 1~12 that can be same to each other or different to each other Group, as its example, can similarly be enumerated as the R in formula (2)3~R5Example and enumerate chain-like alkyl, ring-type Alkyl, alkenyl, alkynyl, haloalkyl, the alkyl with saturated heterocyclyl, aryl, the aralkyl such as phenyl can with alkyl Base, trialkylsilkl, trialkyl silica oxyalkyl, carbonyl, carboxyl, epoxide, amino, benzyl etc..
The A in compound shown in formula (3), as long as the group being made up of H, C, N, O, F, S, Si and/or P, It is not particularly limited, is used as the element with oxygen atom Direct Bonding in formula (3), preferably C, S, Si or P.It is former as these The existing way of son, is preferably for example present in chain-like alkyl, cyclic alkyl, alkenyl, alkynyl, haloalkyl, carbonyl, sulphonyl In base, trialkylsilkl, phosphoryl, phosphinyl etc..
In addition, the molecular weight of the compound shown in formula (3) is preferably less than 1000, wherein particularly preferably less than 800, More preferably less than 500.As the example of the compound shown in formula (3), HMDO, 1,3- diethyls can be enumerated The silicone compound species such as base tetramethyl disiloxane, hexaethyldisiloxane, octamethyltrisiloxane；Methoxyl group trimethyl silicane The alkoxyl silicone alkanes such as alkane, ethoxytrimethylsilane；The peroxides such as peroxidating double (trimethyl silyls)；Acetic acid three Methyl silicane base ester, acetic acid triethylsilyl ester, propionate trimethylsilyl silyl ester, methacrylic acid trimethyl first silicon The carboxylic acid esters such as Arrcostab, trifluoroacetic acid trimethyl silyl ester；Methanesulfonic acid trimethyl silyl ester, ethyl sulfonic acid trimethyl The sulfonic acid esterses such as silyl ester, methanesulfonic acid triethylsilyl ester, fluorine methanesulfonic acid trimethyl silyl ester；Double (front threes Base silicyl) sulfuric acid ester such as sulfuric ester；The borate esters such as three (trimethylsiloxy) boron；Three (trimethyl silyls Base) phosphoric acid or phosphorous acid esters etc. such as phosphate, three (trimethyl silyl) phosphite esters.
Wherein, preferably silicone compound species, sulfonic acid esters, sulfuric acid ester, particularly preferred sulfonic acid esters.It is used as siloxanes Compounds, preferably HMDO；It is used as sulfonic acid esters, preferably methanesulfonic acid trimethyl silyl ester；It is used as sulfuric acid Esters, preferably double (trimethyl silyl) sulfuric esters.
[[intramolecular has the compound of S-F keys]]
There is the compound of S-F keys as intramolecular, be not particularly limited, but preferably sulphonyl fluorine class, fluosulfonic acid esters.
It can such as enumerate, Fumette, second sulfuryl fluoride, methane double (sulfuryl fluorides), ethane -1,2- double (sulfuryl fluoride), third Alkane -1,3- double (sulfuryl fluorides), butane -1,4- double (sulfuryl fluorides), difluoromethane double (sulfuryl fluoride), 1,1,2,2- HFC-134a -1, 2- double (sulfuryl fluorides), 1,1,2,2,3,3- HFC-236fas -1,3- double (sulfuryl fluoride), methyl fluorosulfonate, ethyl fluorosulfonates etc..Its In, preferred Fumette, methane double (sulfuryl fluoride) or methyl fluorosulfonates.
[[nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate, propionate]]
As nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate, propionate counter cation, do not have It is particularly limited to, in addition to the metallic elements such as Li, Na, K, Mg, Ca, Fe, Cu, can also enumerates with NR9R10R11R12(in formula, R9 ~R12The organic group that hydrogen atom or carbon number are 1~12 is represented independently of one another) ammonium, the quaternary ammonium that represent.Wherein, as R9 ~R12Carbon number be 1~12 organic group, the alkyl that can be replaced by halogen atom can be enumerated, can be taken by halogen atom The cycloalkyl in generation, the aryl that can be replaced by halogen atom, heterocyclic radical of nitrogen atom etc..It is used as R9~R12, it is respectively preferably hydrogen Atom, alkyl, cycloalkyl, heterocyclic radical of nitrogen atom etc..In these counter cations, from electricity when using in the lithium secondary battery From the aspect of the characteristic of pond, preferably lithium, sodium, potassium, magnesium, calcium or NR9R10R11R12, particularly preferably lithium.In addition, wherein, from output From the aspect of power increase rate or cycle characteristics, preferably nitrate or difluorophosphoric acid salt, particularly preferably difluorophosphate.This Outside, these compounds can substantially be directly used in the compound being synthesized into nonaqueous solvents, can also be to non-aqueous Add and synthesize in addition and substantially separated compound in agent.
Fluorosilane compounds shown in cyclic siloxane compound, formula (2) shown in specific compound, i.e. formula (1), Compound, intramolecular shown in formula (3) have the compounds of S-F keys, nitrate, nitrite, mono-fluor phosphate, difluoro phosphorus Hydrochlorate, acetate or propionate can be used alone one kind, can also be applied in combination in any combination with ratio of more than two kinds Compound.In addition, in specific compound, even in the above-mentioned compound classified respectively, one kind can also be used alone, or Compound of more than two kinds is applied in combination with ratio in any combination.
The ratio of these specific compounds in nonaqueous electrolytic solution, relative to whole nonaqueous electrolytic solutions, in terms of total amount, it is necessary to For more than 10ppm (more than 0.001 mass %), preferably more than 0.01 mass %, more preferably more than 0.05 mass % enter one Step is preferably more than 0.1 mass %.In addition, the upper limit is preferably below 5 mass %, more preferably below 4 mass % are further excellent Elect as below 3 mass %.If the concentration of specific compound is too low, the raising effect for obtaining cell output is difficult to sometimes Or the prolongation effect of battery life, on the other hand, if excessive concentration, occasionally result in the reduction of efficiency for charge-discharge.
If in addition, during these specific compounds are manufactured as nonaqueous electrolytic solution is actual for secondary cell, dismounting should Battery takes out nonaqueous electrolytic solution again, and content therein is significantly reduced mostly.Therefore, the nonaqueous electrolytic solution by being extracted out from battery In can at least detect that above-mentioned specific compound is also within the scope of the invention.Nonaqueous electrolytic solution of the present invention can lead to Cross and dissolve electrolyte lithium salt, specific compound and other compounds as needed in nonaqueous solvents to be prepared.System During standby nonaqueous electrolytic solution, preferably each raw material is dehydrated in advance, makes moisture be usually below 50ppm, be preferably 30ppm Below, it is particularly preferably below 10ppm.
[other compounds]
Nonaqueous electrolytic solution in the present invention contains the lithium salts as electrolyte and specific compound conduct in nonaqueous solvents Essential component, as needed, can also other compounds containing any amount in the range of effect of the present invention is not damaged.As Other compounds, specifically, can enumerate following material, for example：
(1) part hydride, cyclohexyl benzene, tert-butyl benzene, the tertiary pentyl of biphenyl, alkyl biphenyl, terphenyl, terphenyl The aromatic compounds such as benzene, diphenyl ether, dibenzofurans；It is 2- fluorine biphenyl, adjacent cyclohexyl fluorobenzene, above-mentioned to cyclohexyl fluorobenzene etc. The partially fluorinated thing of aromatic compound；2,4 difluorobenzene methyl ether, 2,5- difluoroanisoles, 2,6- difluoroanisoles, 3,5- bis- The overcharge preventing agents such as the fluorine-containing benzyl ether compounds such as fluoroanisole；
(2) vinylene carbonate, vinylethylene carbonate, fluorine ethylene carbonate, trifluoro propylene carbonate, butanedioic acid The negative pole film shape such as acid anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexane dicarboxylic acid acid anhydride Into agent；
(3) the sub- propyl ester of glycol sulfite, sulfurous acid, dimethyl sulfite, propane sultone, butyl sultone, first sulphur Sour methyl esters, 1,4-dimethane sulfonoxybutane, methyl tosylate, dimethyl suflfate, ethyl sulfate, sulfolane, dimethyl sulfone, diethyl Sulfone, dimethyl sulfoxide (DMSO), diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, THIOANISOLE, Diphenyl disulfide ether, two pyridines two Positive pole protective agent such as thioether etc..
It is used as part hydride, the cyclohexyl of overcharge preventing agent, preferably biphenyl, alkyl biphenyl, terphenyl, terphenyl The aromatic compounds such as benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether, dibenzofurans.They can be applied in combination 2 kinds with On.When two or more is applied in combination, particularly preferred cyclohexyl benzene or terphenyl (or part thereof hydride) and tert-butyl benzene or uncle penta Base benzene is applied in combination.
It is used as negative pole film forming agent, preferably vinylene carbonate, vinylethylene carbonate, fluorine ethylene carbonate, amber Amber acid anhydrides, maleic anhydride.Two or more can be applied in combination in they.When two or more is applied in combination, preferably vinylene carbonate With vinylethylene carbonate, fluorine ethylene carbonate, succinic anhydride or maleic anhydride.It is used as positive pole protective agent, preferably sulfurous The sub- propyl ester of sour ethyl, sulfurous acid, propane sultone, butyl sultone, methyl mesylate, methanesulfonic acid butyl ester.They can group Conjunction uses two or more.In addition, particularly preferably negative pole film forming agent and positive pole protective agent are applied in combination, and by overcharge Preventing agent, negative pole film forming agent and positive pole protective agent are applied in combination.
Containing ratio to these other compounds in nonaqueous electrolytic solution is not particularly limited, relative to all non-water power Liquid is solved, is respectively preferably more than 0.01 mass %, more preferably 0.1 mass %, more preferably 0.2 mass %, its upper limit Preferably below 5 mass %, more preferably 3 mass %, more preferably below 2 mass %.By adding these compounds, Can suppress the rupture of battery/on fire when causing exception due to overcharge, or make the capacity maintenance characteristics after High temperature storage, Cycle characteristics is improved.
For the preparation method of the non-aqueous electrolyte for secondary battery of the present invention, it is not particularly limited, can be in non-aqueous Lithium salts, specific compound, other compounds as needed are dissolved in agent according to conventional methods to prepare.
<Electrolyte [1]>
In above-mentioned nonaqueous electrolytic solution, the nonaqueous solvents for preferably comprising electrolyte is mixed at least containing " ethylene carbonate " Bonding solvent, ethylene carbonate is the capacity % (electrolyte [1]) of 1 capacity %~25 relative to the ratio of nonaqueous solvents total amount.
" lithium salts ", " nonaqueous solvents beyond ethylene carbonate (EC) ", " specific chemical combination in (electrolyte [1]) of the invention Thing ", the species of " other compounds " and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
<Electrolyte [2]>
In above-mentioned nonaqueous electrolytic solution, the nonaqueous solvents for preferably comprising electrolyte contains " at least one asymmetric chain Carbonic ester " and the asymmetric linear carbonate containing ratio shared in whole nonaqueous solvents are the volume % of 5 volume %~90 (electrolyte [2]).
" lithium salts ", " nonaqueous solvents beyond asymmetric linear carbonate ", " specialization in (electrolyte [2]) of the invention Compound ", the species of " other compounds " and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
In of the invention (electrolyte [2]), in whole nonaqueous solvents containing 5 volume %~90 volume % it is at least one Asymmetric linear carbonate.Further, the content of the asymmetric linear carbonate of at least one of whole nonaqueous solvents is excellent Elect as more than 8 volume %, be more preferably more than 10 volume %, more preferably more than 15 volume %, particularly preferred 20 body More than % is accumulated, the upper limit is preferably below 85 volume %, is more preferably below 70 volume %, more preferably 60 volume % in addition Below, below 45 volume % are particularly preferably, due to have high low-temperature characteristics and cycle characteristics etc. of the present invention concurrently and it is preferred that.
For asymmetric linear carbonate, it is not particularly limited, but preferably asymmetric alkyl carbonate, preferably alkyl Carbon number is 1~4.As the specific example of such asymmetric alkyl carbonate, for example, it can enumerate, methyl ethyl carbonate, Methyl n-propyl ester, carbonic acid ethyl n-propyl ester, methyl isopropyl base ester, carbonic acid ethyl isopropyl esters, methyl N-butyl, carbonic acid ethyl n-butyl etc..Wherein, preferably methyl ethyl carbonate, methyl n-propyl ester, carbonic acid ethyl be just Propyl diester, methyl n-butyl, carbonic acid ethyl n-butyl, more preferably methyl ethyl carbonate, methyl n-propyl ester, Methyl n-butyl, particularly preferably methyl ethyl carbonate.These asymmetric linear carbonates can be used in mixed way 2 kinds with On.
As described above, nonaqueous solvents can be mixed with two or more.Cycle characteristics, preservation particularly from secondary cell Characteristic considers in terms of improving, preferably in addition to the asymmetric linear carbonate, further containing at least one ring-type carbon Acid esters.During containing cyclic carbonate, cyclic carbonate ratio shared in whole nonaqueous solvents is usually more than 5 volume %, Preferably more than 10 volume %, more preferably more than 15 volume %, in addition the upper limit be usually below 50 volume %, be preferably 35 bodies Product below %, more preferably below 30 volume %, more preferably below 25 volume %.If cyclic carbonate is all non- Shared ratio is very few in aqueous solvent, it is likely that cannot get the raising of the cycle characteristics or preservation characteristics of secondary cell, another Aspect, if excessively, cryogenic discharging characteristic is reduced sometimes.
In addition, being examined in terms of the raising of the cycle characteristics or preservation characteristics of secondary cell and the balance of cryogenic discharging characteristic Consider, preferably in addition to the asymmetric linear carbonate, further containing at least one symmetrical linear carbonate.Containing symmetrical During linear carbonate, symmetrical linear carbonate ratio shared in whole nonaqueous solvents is usually more than 5 volume %, is preferably More than 10 volume %, more preferably more than 15 volume %, in addition, the upper limit is usually below 80 volume %, is preferably 70 volume % Below, below 50 volume %, more preferably below 40 volume % are more preferably.If symmetrical linear carbonate is all non- Shared ratio is very few in aqueous solvent, then the balance that cannot get cycle characteristics or preservation characteristics and cryogenic discharging characteristic sometimes is carried Height, on the other hand, if excessively, cannot get excellent cycle characteristics sometimes.
Furthermore it is preferred that asymmetric linear carbonate and the mixed solvent of nonaqueous solvents of more than two kinds in addition.That is, Preferably comprise mixed solvents more than 3 compositions of the asymmetric linear carbonate.It is used as 2 kinds outside asymmetric linear carbonate The mixed solvent of nonaqueous solvents above, due to all batteries performance such as charge-discharge characteristic, battery life can be improved, therefore it is excellent Select the high dielectric constant solvents such as cyclic carbonate or cyclic ester and the low viscosity solvent group such as symmetrical linear carbonate or chain ester Conjunction is used, the combination of particularly preferred cyclic carbonate and symmetrical linear carbonate.Mixing ratio now is not particularly limited, but from Consideration in terms of cycle characteristics, preservation characteristics is improved, preferably with respect to the asymmetric linear carbonate of 100 parts by volume, cyclic carbonate The high dielectric constant solvent such as ester or cyclic ester is the low viscosity solvents such as 10~400 parts by volume, symmetrical linear carbonate or chain ester For 10~800 parts by volume.
One of preferred compositions of nonaqueous solvents of more than two kinds outside asymmetric linear carbonate be with cyclic carbonate and Symmetrical linear carbonate is the combination of main body.It is used as cyclic carbonate and the concrete example of the preferred compositions of symmetrical linear carbonate Son, can enumerate ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and carbonic acid diformazan Ester and diethyl carbonate etc..Containing ratio in whole nonaqueous solvents is not particularly limited, but preferably asymmetric chain carbon Acid esters is that 8~80 volume %, cyclic carbonate are that 10~35 volume %, symmetrical linear carbonate are 10~70 volume %.
It can enumerate and propylene carbonate is further added in the combination of these ethylene carbonates and symmetrical linear carbonate Combination be used as preferred combination.During containing propylene carbonate, the Capacity Ratio of ethylene carbonate and propylene carbonate is preferably 99: 1~40:60, particularly preferably 95:5~50:50.
The another of the preferred compositions of nonaqueous solvents of more than two kinds outside asymmetric linear carbonate is to contain chain ester Combination.Particularly from the aspect of the low-temperature characteristics of battery is improved, the preferably above-mentioned group containing cyclic carbonate and chain ester Close, be used as chain ester, particularly preferred methyl acetate, ethyl acetate etc..Chain ester ratio shared in whole nonaqueous solvents is excellent Elect as more than 5 volume %, be more preferably more than 8 volume %, particularly preferably more than 15 volume %, its upper limit is preferably 50 bodies Product below %, more preferably below 35 volume %, more preferably below 30 volume %, particularly preferably 25 volume % with Under.Therefore, the containing ratio now in whole nonaqueous solvents is preferably as follows ratio：Asymmetric linear carbonate is 8~85 bodies Product %, cyclic carbonate are that 10~35 volume %, chain ester are 5~50 volume %.
The group that symmetrical linear carbonate is further added in the combination of these cyclic carbonates and chain ester can be enumerated Cooperate as preferred combination.During containing symmetrical linear carbonate, symmetrical linear carbonate in whole nonaqueous solvents contain than Rate is preferably 10~60 volume %.
As the specific example of the preferred compositions of the nonaqueous solvents of the non-aqueous electrolyte for secondary battery of the present invention, for example may be used To enumerate：Methyl ethyl carbonate and ethylene carbonate, methyl n-propyl ester and ethylene carbonate, methyl ethyl carbonate, carbonic acid are sub- Ethyl ester and propylene carbonate, the asymmetric linear carbonate such as methyl n-propyl ester, ethylene carbonate and propylene carbonate and The combination of cyclic carbonate；Methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate and carbon Diethyl phthalate, methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and dimethyl carbonate, methyl n-propyl ester, carbonic acid are sub- Ethyl ester and dimethyl carbonate, methyl n-propyl ester, ethylene carbonate and diethyl carbonate, methyl n-propyl ester, carbon The asymmetric linear carbonate such as sour ethyl, diethyl carbonate and dimethyl carbonate, cyclic carbonate and symmetrical linear carbonate Combination；Methyl ethyl carbonate, ethylene carbonate and methyl acetate, methyl ethyl carbonate, ethylene carbonate and ethyl acetate etc. are non-right Claim the combination of linear carbonate, cyclic carbonate and chain ester；Methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate and acetic acid Methyl esters, the asymmetric linear carbonate such as methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and methyl acetate, cyclic carbonate, The combination of symmetrical linear carbonate and chain ester etc..
Contain lithium salts and relative to the above-mentioned specific compound that electrolyte gross mass is more than 10ppm in the in the mixed solvent Such as difluorophosphoric acid salt, asymmetric linear carbonate containing ratio shared in whole nonaqueous solvents is 5 volume %~90 Volume % nonaqueous electrolytic solution is due to special using the cycle characteristics, cryogenic discharging characteristic, High temperature storage of its secondary cell manufactured Property (residual capacity and high load capacity discharge capacity particularly after High temperature storage) and suppress the balance that gas produces and become excellent, Thus preferably.
<Electrolyte [3]>
In above-mentioned nonaqueous electrolytic solution, the nonaqueous solvents for preferably comprising electrolyte at least contains " more than one chain carboxylic Acid esters " (electrolyte [3]).
" lithium salts ", " nonaqueous solvents beyond chain carboxylate ", " specific compound " in of the invention (electrolyte [3]), The species and its content of " other compounds ", use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
As the chain carboxylate used in (electrolyte [3]) of the invention, it is not particularly limited, preferably comprises the carbon of carboxyl Carbon number inside is the Arrcostab of the carbon number 1~4 of 1~5 carboxylic acid.In addition, not having for first number of above-mentioned carboxylic acid It is particularly limited to, preferably monocarboxylic acid or dicarboxylic acids.
Wherein, the preferably fatty acid ester such as formic acid esters, acetic acid esters, propionic ester, butyrate；Various dicarboxylic acids esters etc., Particularly preferred acetic acid esters or propionic ester.
In particular, it is preferred that methyl acetate, ethyl acetate, propyl acetate, methyl propionate or ethyl propionate, particularly preferred second Sour methyl esters, ethyl acetate or methyl propionate.
In addition, these chain carboxylates can mix two or more to use.The combination of mixing is not particularly limited, as It is preferred that combination, methyl acetate and ethyl acetate, methyl acetate and methyl propionate, ethyl acetate and methyl propionate can be enumerated, Methyl acetate, ethyl acetate and methyl propionate etc..Thus, it is possible to adjust characteristics of output power and High temperature storage characteristic according to purpose Deng balance.
During the mixed solvent of nonaqueous solvents using above-mentioned chain carboxylate and in addition, chain carboxylate is relative to this The containing ratio of whole nonaqueous solvents is preferably more than 3 volume %, is more preferably more than 5 volume %, more preferably 8 bodies Product more than %, particularly preferably more than 10 volume %, in addition, its upper limit is preferably below 50 volume %, is more preferably 35 bodies Product below %, more preferably below 30 volume %, particularly preferably below 25 volume %, due to having the high of the present invention concurrently Low-temperature characteristics and cycle characteristics etc. and it is preferred that.
Although for greatly improving low temperature power output by the way that chain carboxylate and above-mentioned specific compound is applied in combination The reasons why characteristic, is also indefinite, even if but above-mentioned specific compound is also possible to have certain journey when not containing chain carboxylate The low-temperature characteristics of degree improves effect, it is believed that this is due to have certain effect to electrode, and chain carboxylate promotes the effect, changes speech It, it is believed that it is due to that, by there is mobility also high chain carboxylate at low temperature, these specific compounds are impregnated with to electrode Intralamellar part is without lavishly playing effect, or chain carboxylate propagates the interaction of above-mentioned specific compound and electrode.
<Electrolyte [4]>
In above-mentioned nonaqueous electrolytic solution, the 60 capacity % that the nonaqueous solvents for preferably comprising electrolyte contains whole nonaqueous solvents with On more than 70 DEG C of flash-point solvent (electrolyte [4]).
It is " lithium salts ", " nonaqueous solvents beyond the solvent that more than 70 DEG C of flash-point " in of the invention (electrolyte [4]), " specific Compound ", the species of " other compounds " and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
In the present invention, nonaqueous solvents is in terms of total amount, it is necessary to the flash-point 70 of more than the 60 capacity % containing whole nonaqueous solvents Solvent more than DEG C.Further, it is preferable to 80 DEG C of the flash-point of more than 60 capacity % containing whole nonaqueous solvents in terms of total amount with On solvent, the solvent of more than 90 DEG C of the flash-point of more than the 60 capacity % containing whole nonaqueous solvents particularly preferably in terms of total amount.
The solvent that more than 70 DEG C of flash-point is not particularly limited, for example, can enumerate, ethylene carbonate, propylene carbonate, carbon Sour butylene, gamma-butyrolacton, gamma-valerolactone etc. as preferred solvent, wherein, particularly preferred ethylene carbonate, polypropylene carbonate Ester or gamma-butyrolacton.These solvents can use one kind, can also mix two or more and use, and its combination is not particularly limited.
In addition, from the aspect of cycle characteristics raising, containing more than 10 capacity % preferably with respect to whole nonaqueous solvents The composition of ethylene carbonate or propylene carbonate.On the other hand, if containing substantial amounts of ethylene carbonate, due to low-temperature characteristics Reduction, the content of ethylene carbonate is preferably below the 70 capacity % of whole nonaqueous solvents, particularly preferably below 60 capacity %.
In terms of total amount, the nonaqueous solvents for the solvent that more than 70 DEG C of the flash-point of more than the 60 capacity % containing whole nonaqueous solvents Preferred example be：
(1) nonaqueous solvents that gamma-butyrolacton amount shared in whole nonaqueous solvents is more than 60 capacity %；
(2) total of ethylene carbonate and gamma-butyrolacton accounts for more than 80 capacity % in whole nonaqueous solvents, preferably accounts for 85 The Capacity Ratio of more than capacity % and ethylene carbonate and gamma-butyrolacton is 5:95~45:55 nonaqueous solvents；
(3) total of ethylene carbonate and propylene carbonate is accounted for more than 80 capacity % in whole nonaqueous solvents, preferably accounted for The Capacity Ratio of more than 85 capacity % and ethylene carbonate and propylene carbonate is 30:70~60:40 nonaqueous solvents etc..
If becoming excellent using the balance of these nonaqueous solvents, particularly cycle characteristics and heavy-current discharge characteristic etc. It is different.
In addition, the preferred flash-point of nonaqueous electrolytic solution be more than 40 DEG C, more preferably more than 50 DEG C, be more preferably 60 DEG C with Above, particularly preferably more than 70 DEG C.If the flash-point of nonaqueous electrolytic solution is too low, when battery is exposed at high temperature, electricity is worried sometimes Solve igniting for liquid.
In the non-aqueous electrolyte for secondary battery of the present invention nonaqueous solvents that uses can more than 70 DEG C of flash-point solvent In further coordinate the nonaqueous solvents composition (hereinafter simply referred to as " other nonaqueous solvents compositions ") that flash-point is less than 70 DEG C.It is such its Appropriate selection is used in the solvent that its nonaqueous solvents composition can be proposed from the conventional solvent as nonaqueous electrolytic solution.For example may be used To enumerate following nonaqueous solvents.
(1) linear carbonate
As linear carbonate, preferably dialkyl carbonate, the carbon number point of the alkyl of dialkyl carbonate is constituted You Xuanwei 1~5, particularly preferred 1~4.Specifically, dimethyl carbonate, diethyl carbonate, carbonic acid two can for example enumerated just The dialkyl carbonates such as propyl ester, methyl ethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester.Wherein, preferred carbonic acid Dimethyl ester, diethyl carbonate, methyl ethyl carbonate.
(2) chain ester
Specifically, such as can enumerate methyl acetate, ethyl acetate, propyl acetate, methyl propionate.
(3) cyclic ether
Specifically, such as can enumerate tetrahydrofuran, 2- methyltetrahydrofurans, oxinane.
(4) chain ether
Specifically, such as can enumerate dimethoxy-ethane, dimethoxymethane.
Other nonaqueous solvents compositions a kind of can be applied in combination with " solvent that more than 70 DEG C of flash-point ", can also combine 2 kinds Other nonaqueous solvents compositions are used above.Now, particularly from the aspect of cycle characteristics and heavy-current discharge characteristic, preferably will Linear carbonate and/or chain ester are applied in combination with " solvent that more than 70 DEG C of flash-point ".
Flash-point in whole nonaqueous solvents is necessary for more than 60 capacity % for the content of more than 70 DEG C of solvent, and preferably 70 More than capacity %, more preferably more than 75 capacity %, more preferably more than 80 capacity %, particularly preferably 85 capacity % with On.In addition, its upper limit is preferably below 100 capacity %, particularly preferably below 90 capacity %.If flash-point is more than 70 DEG C The content of solvent is very few, then cannot get the internal pressure easily intended effect, the opposing party such as rise when preserving battery at high temperature sometimes Face, if excessively, because viscosity is raised and reduces electrical conductivity, the performance of lithium secondary battery is reduced sometimes.
Although using certain for the rechargeable nonaqueous electrolytic battery of the nonaqueous electrolytic solution (electrolyte [4]) using the present invention The reasons why characteristics of output power is excellent during the flash-point high solvent of kind of the amount above is also indefinite, but is regarded as following reason, but The present invention should be not limited to following reasons.I.e., it is believed that above-mentioned specific compound is acted on electrode, reducing the turnover with lithium ion has The reaction resistance of pass, so as to improve characteristics of output power.Furthermore, it is considered that ethylene carbonate, propylene carbonate, butylene carbonate, The high solvent of the flash-points such as gamma-butyrolacton, gamma-valerolactone is compared with linear carbonate, and dielectric constant is high, exists more than to a certain degree Dielectric constant high solvent when, its effect becomes notable.Further it is considered due to 1 battery case of secondary cell The battery capacity that the battery element of middle storage has be 3 ampere-hours (Ah) more than when and/or secondary cell D.C. resistance Composition be 10 milliohms (Ω) below when, the contribution of DC resistance component is reduced, the big battery phase with the contribution of DC resistance component Than easily showing the original effect of the nonaqueous electrolytic solution.
<Electrolyte [5]>
In above-mentioned nonaqueous electrolytic solution, LiN (C are preferably comprisednF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) lithium borate as constitute electrolyte " lithium salts " electrolyte (electrolyte [5]).
" nonaqueous solvents ", " specific compound ", the species of " other compounds " in of the invention (electrolyte [5]) and its contain Amount, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
The non-aqueous electrolyte for secondary battery (electrolyte [5]) of the present invention is at least dissolved with lithium salts in nonaqueous solvents, makees For such lithium salts, containing selected from LiN (CnF2n+1SO2)2In (in formula, n is 1~4 integer) and two (oxalate conjunction) lithium borates At least one.They can be used alone one kind, can also use two or more with ratio combine in any combination.
It is above-mentioned " specific by (b) that more than 10ppm is applied in combination for following (a) in non-aqueous electrolyte for secondary battery Compound ", can provide characteristics of output power and greatly improve, and High temperature storage characteristic or cycle characteristics it is excellent be used for secondary electricity The nonaqueous electrolytic solution in pond.
(a)LiN(CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) lithium borates
As (a), it is not particularly limited, LiN (CF3SO2)2Or two (oxalate conjunction) lithium borate due to can especially play The effect above and it is preferred that.
In the non-aqueous electrolyte for secondary battery of the present invention, as described above, as lithium salts, containing LiN (CnF2n+1SO2)2 (in formula, n is 1~4 integer) and/or two (oxalate conjunction) lithium borates are used as essential component, but it is also possible to be applied in combination except this Outside known lithium salts (hereinafter simply referred to as " other lithium salts ").
As other lithium salts, it is not particularly limited, for example, can enumerates following lithium salts.
Inorganic lithium salt：LiPF6、LiBF4、LiAsF6、LiSbF6Etc. inorganic fluoride salts；LiClO4、LiBrO4、LiIO4Deng Perhalide；LiAlCl4Deng butter salt etc..
Fluorine-containing organic lithium salt：LiCF3SO3Etc. perfluoroalkanesulfosalt salt；LiC(CF3SO2)3Methylated Deng perfluoroalkanesulfonyl Salt；Li[PF5(CF2CF2CF3)]、Li[PF4(CF2CF2CF3)2]、Li[PF3(CF2CF2CF3)3]、Li[PF5 (CF2CF2CF2CF3)]、Li[PF4(CF2CF2CF2CF3)2]、Li[PF3(CF2CF2CF2CF3)3] etc. fluoroalkyl fluorinated phosphate salt etc..
Other oxalates close lithium borate class：Difluoro oxalate root closes lithium borate etc..
They can be used alone one kind, can also use two or more with ratio combine in any combination.These " its In its lithium salts ", if dissolubility of the comprehensive descision in nonaqueous solvents, as secondary cell when charge-discharge characteristic, output work Rate characteristic, cycle characteristics etc., then preferred LiPF6、LiBF4, particularly preferred LiPF6。
LiN (C in nonaqueous electrolytic solutionnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) boric acid The concentration of lithium using these salt as main salt in use, usually more than 0.3mol/L, be preferably more than 0.5mol/L, more excellent Elect more than 0.7mol/L as, its upper limit be usually below 2mol/L, be preferably below 1.8mol/L, more preferably 1mol/L with Under.In addition, by LiPF6、LiBF4Etc. other lithium salts as main salt in use, LiN (CnF2n+1SO2)2(in formula, n is 1~4 Integer) and/or the concentration of two (oxalate conjunction) lithium borates be more than 0.001mol/L, be preferably more than 0.01mol/L, more preferably For more than 0.03mol/L, in addition, its upper limit is usually below 0.3mol/L, is preferably below 0.2mol/L, more preferably Below 0.1mol/L.Main salt mentioned here refers to the maximum lithium salts of concentration in nonaqueous electrolytic solution.
The total concentration of lithium salts in nonaqueous electrolytic solution, is not particularly limited, but usually more than 0.5mol/L, be preferably More than 0.6mol/L, more preferably more than 0.7mol/L.In addition, its upper limit is usually below 2mol/L, is preferably 1.8mol/L Below, it is more preferably below 1.7mol/L.If concentration is too low, the electrical conductivity of nonaqueous electrolytic solution is sometimes insufficient, the opposing party Face, if excessive concentration, due to viscosity rise, electrical conductivity is reduced sometimes, and the performance of lithium secondary battery is reduced sometimes.
Preferred example when two or more lithium salts is applied in combination is by selected from LiN (CnF2n+1SO2)2(in formula, n is 1 ~4 integer) and at least one of two (oxalate conjunction) lithium borates lithium salts and LiPF6It is applied in combination.It is special by being applied in combination It is not that can improve characteristics of output power, preservation characteristics.Now be selected from LiN (CnF2n+1SO2)2(in formula, n for 1~4 it is whole Number) and at least one of two (oxalate conjunction) lithium borates concentration of the lithium salts in nonaqueous electrolytic solution it is as follows：These lithium salts are made For main salt in use, preferably more than 0.4mol/L, more preferably more than 0.5mol/L, particularly preferably 0.6mol/L with On.Its upper limit is preferably below 1.8mol/L, more preferably below 1.5mol/L, particularly preferably below 1.2mol/L.Now LiPF6Concentration be preferably more than 0.001mol/L, more preferably more than 0.01mol/L, particularly preferably 0.1mol/L with On.In addition, its upper limit is in LiPF6Than selected from LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and two (oxalate conjunction) boron It is preferably below 1mol/L, more preferably below 0.8mol/L, special in the low scope of the concentration of at least one of sour lithium lithium salts You Xuanwei not below 0.3mol/L.
By LiPF6As main salt in use, selected from LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and two (grass Acid group is closed) concentration of at least one of lithium borate lithium salts be preferably more than 0.001mol/L, more preferably 0.01mol/L with Upper, particularly preferably more than 0.03mol/L.In addition, its upper limit be preferably below 0.3mol/L, more preferably 0.2mol/L with Under, particularly preferably below 0.1mol/L.LiPF now6Concentration be preferably more than 0.5mol/L, more preferably 0.6mol/ More than L, particularly preferably more than 0.7mol/L.In addition, its upper limit be preferably below 1.8mol/L, more preferably 1.7mol/L with Under, particularly preferably below 1.5mol/L.
In addition, if being selected from LiN (C at thisnF2n+1SO2)2(in formula, n is 1~4 integer) and two (oxalate conjunction) boric acid At least one of lithium lithium salts and LiPF6Combination in LiBF is applied in combination4, then due to suppress caused by High temperature storage The effect of deterioration and it is preferred that.Now, LiBF4Concentration be usually more than 0.001mol/L, be preferably more than 0.01mol/L, more Preferably more than 0.03mol/L, its upper limit is usually below 0.4mol/L, is preferably below 0.15mol/L, more preferably Below 0.1mol/L.
Contain LiN (CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) lithium borates and selected from upper Stating the cyclic compound shown in formula (1), the compound shown in above-mentioned formula (2), intramolecular has structure shown in formula (3) Chain compound, intramolecular have the compounds of S-F keys, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetic acid The nonaqueous electrolytic solution of at least one of compound in salt, propionate compound, due to what is manufactured using the nonaqueous electrolytic solution The cycle characteristics and High temperature storage characteristic (residual capacity and high load capacity discharge capacity particularly after High temperature storage) of battery it is flat Weighing apparatus becomes excellent, it is advantageous to.
Although the output characteristics for the rechargeable nonaqueous electrolytic battery of the nonaqueous electrolytic solution using the present invention is excellent and high The reasons why warm keeping quality or excellent cycle characteristics, is also indefinite, but is regarded as because above-mentioned specific compound has certain to electrode Effect, reduces the reaction resistance relevant with the turnover of lithium ion, so as to improve characteristics of output power.Wherein speculate, by using LiN(CnF2n+1SO2)2(in formula, n is 1~4 integer) and/or two (oxalate conjunction) lithium borates are as lithium salts, and these lithium salts exist Moderately reacted on negative pole and positive electrode surface, the lithium ion of the lithium salts is derived from the formation of other nonaqueous electrolytic solution compositions The complex protection film of the excellent stabilization of permeability, by the compelx coating, the high electrode of inhibitory activity and nonaqueous electrolytic solution Unnecessary side reaction, so that characteristics of output power is improved, while High temperature storage characteristic and cycle characteristics are improved.
<Electrolyte [6]>
In above-mentioned nonaqueous electrolytic solution, the lithium salts for preferably comprising electrolyte is fluorine-containing lithium salts, and in whole nonaqueous electrolytic solutions In the hydrogen fluoride (HF) (electrolyte [6]) containing 10ppm~300ppm.
" nonaqueous solvents ", " specific compound ", the species of " other compounds " in of the invention (electrolyte [6]) and its contain Amount, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.In (electrolyte [6]) of the invention, " fluorine-containing lithium is used as Salt ", as long as the fluorine-containing lithium salts of the known electrolyte that may be used as non-aqueous electrolytic solution used for lithium secondary batteries, is not limited especially It is fixed, it can for example use above-mentioned lithium salts.They can be used alone one kind, can also be used in any combination with ratio combine Two or more.Wherein, from the viewpoint of hydrogen fluoride (HF) is easily generated in the presence of aftermentioned alcohols, preferably LiPF6、LiBF4Deng. If in addition, dissolubility of the comprehensive descision in nonaqueous solvents, charge-discharge characteristic when being made secondary cell, power output are special Property, cycle characteristics etc., then preferred LiPF6。
In addition, not fluorine-containing lithium salts can also be used in mixed way in electrolyte in addition to fluorine-containing lithium salts, by way of example, can be with Enumerate following lithium salts.
Inorganic lithium salt：LiClO4、LiBrO4、LiIO4Deng perhalide；LiAlCl4Deng butter salt etc..
Oxalate closes borate：Two (oxalate conjunction) lithium borates etc..
The concentration of above-mentioned lithium salts in nonaqueous electrolytic solution is not particularly limited, usually more than 0.5mol/L, be preferably More than 0.6mol/L, more preferably more than 0.7mol/L.In addition, its upper limit is usually below 2mol/L, is preferably 1.8mol/L Below, it is more preferably below 1.7mol/L.If concentration is too low, the electrical conductivity of nonaqueous electrolytic solution is sometimes insufficient, the opposing party Face, if excessive concentration, due to viscosity rise, electrical conductivity is reduced sometimes, and the performance of lithium secondary battery is reduced sometimes.
The concentration of above-mentioned fluorine-containing lithium salts in nonaqueous electrolytic solution is not particularly limited, but usually more than 0.5mol/L, excellent Elect more than 0.6mol/L, more preferably more than 0.7mol/L as.In addition, its upper limit is usually below 2mol/L, is preferably Below 1.8mol/L, more preferably below 1.7mol/L.If concentration is too low, the electrical conductivity of nonaqueous electrolytic solution is sometimes insufficient Or the generation of hydrogen fluoride (HF) is sometimes insufficient, on the other hand, if excessive concentration, due to viscosity rise, electrical conductivity is sometimes Reduction or the generation of hydrogen fluoride (HF) are excessively carried out sometimes, and the performance of lithium secondary battery is likely to decrease.
Ratio of the fluorine-containing lithium salts relative to whole lithium salts in nonaqueous electrolytic solution, relative to whole lithium salts, preferably fluorine-containing lithium Salt is more than 50 mass %, particularly preferably more than 70 mass %.In addition, the lithium salts particularly preferably mixed is all fluorine-containing lithium salts. If the ratio of fluorine-containing lithium salts is too low, the generation of hydrogen fluoride is sometimes insufficient.
Lithium salts can be used alone one kind, also use two or more with ratio combine in any combination, be applied in combination 2 kinds Preferred example during above lithium salts is LiPF6And LiBF4Be applied in combination, now, LiBF4It is shared in both amount to Ratio be preferably the mass % of 0.01 mass %~20, the mass % of more preferably 0.1 mass %~5.In addition, other preferred one Is inorganic fluoride salts and perfluoroalkanesulfonyl inferior amine salt are applied in combination in individual example, now, and inorganic fluoride salts are amounted at both In shared ratio be preferably the mass % of 70 mass %~99, the mass % of more preferably 80 mass %~98.The combination of the rwo Using with the effect for suppressing the deterioration caused by High temperature storage.
LiPF is dissolved with above-mentioned nonaqueous solvents6Etc. in nonaqueous electrolytic solution obtained from fluorine-containing lithium salts, fluorine is contained mostly Change hydrogen (HF).The reason for as containing hydrogen fluoride (HF), in addition to the hydrogen fluoride of the impurity in fluorine-containing lithium salts, also deposit The hydrogen fluoride that micro moisture or alcohols and fluorine-containing lithium salts in nonaqueous solvents react and generated.In above-mentioned patent document 16, The non-water power of 9ppm in the hydrogen fluoride (HF) in nonaqueous electrolytic solution, particularly preferably below 15ppm, embodiment must strongly be removed It is most excellent result to solve the cycle characteristics of liquid.
In the case of of the invention (electrolyte [6]), as hydrogen fluoride (HF) content, usually more than 10ppm, be preferably More than 12ppm, more preferably more than 15ppm, particularly preferably more than 20ppm, and usually below 300ppm, be preferably Below 250ppm, more preferably below 200ppm, particularly preferably below 150ppm.If content is too low, power output is carried High effect is sometimes insufficient, if content exceedes the scope, has harmful effect to power output and cycle characteristics sometimes.
In order to containing hydrogen fluoride (HF), be directly added into the nonaqueous solvents of nonaqueous electrolytic solution or raw material, Huo Zheli Produced with the reaction of water or alcohols and fluorine-containing lithium salts inside nonaqueous electrolytic solution, therefore, it is possible to use adding into nonaqueous electrolytic solution Enter water or alcohols or the method that these compositions etc. are contained with appropriate concentration in advance in the nonaqueous solvents of raw material.Now, arrive Reaction terminated sometimes for the regular hour.In other words, fluorine-containing lithium salts is dissolved in the nonaqueous solvents containing water or alcohols, is prepared When adding the electrolyte of specific compound, the time is needed before the reaction of water or alcohols and fluorine-containing lithium salts terminates, but by its During for battery manufacture, it may not be necessary to wait question response to terminate.When in the present invention, as battery function, exist specific dense The hydrogen fluoride (HF) of scope is spent, can also be generated in battery.When generating hydrogen fluoride (HF) in the nonaqueous solvents of raw material, Hydrogen fluoride (HF) can also be generated in a part for the nonaqueous solvents used as raw material, by it with not containing water or alcohols Nonaqueous solvents is mixed.
When containing water or alcohols in advance in nonaqueous solvents, according to the purity of the solvent used, just contain from beginning sometimes Water or alcohols more than necessary amount.Now, nonaqueous solvents is preferably purified by methods such as adsorption treatment, distillation, crystallization precipitations, removed Remove water or alcohols and use.It can remain the water of ormal weight or the nonaqueous solvents of alcohols directly using water or alcohols is removed, also may be used Used with hydrous water or alcohols with being ormal weight in the nonaqueous solvents of purifying.
Adsorption treatment can be implemented if in the state of liquid, can be by aluminum oxide, activated carbon, silica gel, molecule Sieve dissolving or the adsorbent progress by not reacted with nonaqueous solvents in the nonaqueous solvents such as (trade name) 4A and/or molecular sieve 5A Purification process.At this time it is also possible to be the raw material of liquid at normal temperatures as purifying dimethyl carbonate respectively, and ethylene carbonate It is such to mix to form liquid with other raw materials for the raw material of solid at normal temperatures, purification process is carried out together. Contact method can enumerate the method (hereinafter referred to as continuity method) of continuously dipping nonaqueous solvents, or addition is inhaled into nonaqueous solvents Attached dose, the method for standing or stirring (hereinafter referred to as batch process).In the case of continuity method, time of contact is with liquid hourly space velocity (LHSV) (LHSV) Meter is preferably 0.1~5/ hour.In addition, Contact Temperature is preferably 10~60 DEG C.In the case of batch process, preferably with respect to non-aqueous Solvent adds 0.1~30 mass % adsorbent, handles 0.25 hour~24 hours.
In addition, crystallization precipitation processing can also be carried out for the raw material of solid under the normal temperature such as ethylene carbonate.Crystallizing precipitation can To be carried out using acetonitrile, acetone, toluene equal solvent.
The purification condition is preferably suitably adjusted according to the species or purity of the raw material used, the water of target or the content of alcohols Section.
When the nonaqueous electrolytic solution of (electrolyte [6]) of the invention is prepared without hydrogen fluoride (HF), for non-aqueous solution electrolysis Contain water or alcohols in the nonaqueous solvents of liquid.That is, after addition water or alcohols using or do not remove water or alcohols and use.It is preferred that Contain alcohols particularly unitary or di-alcohols.As alcohols, it is not particularly limited, the species of alkyl or first number of alcohol do not have yet It is particularly limited to, specifically, the monohydric alcohol such as can enumerate methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol Class；The di-alcohols such as ethylene glycol or propane diols；Ternary alcohols such as glycerine etc. is used as preferred alcohols.It is particularly preferred during as addition " water or alcohols ", methanol, ethanol, ethylene glycol, propane diols etc. can be enumerated.
In the nonaqueous solvents of the electrolyte used, using the alcohols being mixed into by reasons such as its manufacturing processes from production Consider it is industrially preferred in terms of property, cost.Particularly preferably contain methanol, second in the preferred nonaqueous solvents used Alcohol, ethylene glycol or propane diols.
In the nonaqueous solvents for the nonaqueous electrolytic solution (electrolyte [6]) of the present invention, it is desirable to which the content of water or alcohols is More than 3ppm, preferably more than 10ppm, more preferably more than 20ppm, more preferably more than 30ppm, are limited to thereon Below 150ppm, preferably below 130ppm, more preferably below 120ppm, more preferably below 100ppm.If non- The content of water or alcohols in aqueous solvent is very few, then can not fully obtain special as the high-output power of feature of present invention sometimes Property, if excessively, cycle characteristics or High temperature storage characteristic are deteriorated sometimes.
Wherein, as unary alcohol, in nonaqueous solvents be preferably more than 5ppm, more preferably more than 10ppm, further Preferably more than 15ppm, and preferably below 100ppm, more preferably below 80ppm, more preferably below 50ppm.This Outside, as di-alcohols, in nonaqueous solvents for more than 3ppm, be preferably more than 10ppm, more preferably more than 15ppm, enter one Step preferably more than 20ppm, and preferably below 100ppm, more preferably below 90ppm, more preferably below 80ppm, Particularly preferably below 70ppm.In addition, water is more than 3ppm in nonaqueous solvents, is preferably more than 5ppm, more preferably More than 10ppm, and preferably below 100ppm, more preferably below 80ppm, more preferably below 70ppm.
If above-mentioned a certain amount of hydrogen fluoride (HF) and above-mentioned specific compound coexist in nonaqueous electrolytic solution, will not be right Cycle characteristics brings harmful effect, it is possible to improve the power output of lithium secondary battery.
Will not be to following by the way that a certain amount of hydrogen fluoride (HF) and specific compound coexists in the nonaqueous electrolytic solution of the present invention Although the reasons why ring property brings harmful effect and improves power output is also indefinite, following reason is regarded as.In addition, this Invention is not limited to following effects principle.That is, above-mentioned specific compound is possible to improve effect with power output to a certain degree, But regardless of hydrogen fluoride (HF) content how.It is thought that because specific compound has certain effect to the electrode of battery, reduction The reaction resistance relevant with the turnover of lithium ion.Wherein, hydrogen fluoride (HF) is possible to play enhancing or transmits the work(of the effect Energy.For example, specific compound and hydrogen fluoride (HF) one react on electrode or hydrogen fluoride when specific compound acts on electrode (HF) function of medium is played.Additionally, it is believed that so assigning the hydrogen fluoride (HF) of function can stably exist in battery, from And be difficult to bring the harmful effects such as the reduction of cycle characteristics.
<Electrolyte [7]>
In above-mentioned nonaqueous electrolytic solution, vinylene carbonate, and the vinylene carbonate are preferably contained in the electrolytic solution Content for the mass % of 0.001 mass %~3 of electrolyte gross mass scope (electrolyte [7]).
" lithium salts ", " nonaqueous solvents ", " specific compound ", the kind of " other compounds " in (electrolyte [7]) of the invention Class and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
The nonaqueous electrolytic solution of the present invention, as described above, it is characterised in that contain vinylene carbonate.In the present invention, carbon Sour vinylene ratio shared in whole nonaqueous electrolytic solutions is usually more than 0.001 mass %, is preferably 0.01 mass % Above, more preferably more than 0.1 mass %.In addition, usually below 3 mass %, be preferably below 2.8 mass %, more preferably For below 2.5 mass %.If the concentration of vinylene carbonate is too low, the improvement for obtaining cycle characteristics is difficult to sometimes, On the other hand, if excessive concentration, the low-temperature characteristics reduction of battery is occasionally resulted in.
The content of vinylene carbonate in nonaqueous electrolytic solution is not limited especially relative to the content of above-mentioned specific compound It is fixed, by quality ratio preferably more than 0.01, more preferably more than 0.1, particularly preferably more than 0.3, in addition, its upper limit is preferred For less than 300, more preferably less than 100, particularly preferably less than 30., sometimes can not be simultaneously if deviating considerably from the scope Realize purpose as excellent cycle characteristics and low-temperature characteristics.
For by the way that vinylene carbonate is applied in combination with the above-mentioned specific compound such as difluorophosphoric acid salt, even if carbonic acid is sub- Vinyl acetate is a small amount of, although the reasons why cycle characteristics is also improved is also indefinite, thinks that its reason is：The spies such as difluorophosphoric acid salt The amount for the vinylene carbonate determined compound to inhibit discharge and recharge due to battery and consumed in positive pole, vinylene carbonate can be with Without waste in negative pole formation film；And it is mixed in one by the specific compounds such as difluorophosphoric acid salt and vinylene carbonate Rise, changed in the matter of the film of negative pole formation, form thin, low resistance and further can significantly suppress electrolyte lithium salt Decomposition high-quality film.It is thus regarded that the improvement of low-temperature characteristics can also be realized.
<Electrolyte [8]>
In above-mentioned nonaqueous electrolytic solution, preferably further contain selected from the chemical combination shown in above-mentioned formula (4) in the electrolytic solution The compound of at least one of thing, the heterocyclic compound containing nitrogen and/or sulphur, cyclic carboxylic esters, fluorine-containing cyclic carbonate, and Its content range in whole nonaqueous electrolytic solutions is the mass % (electrolyte [8]) of 0.001 mass %~5.
" lithium salts ", " nonaqueous solvents ", " specific compound ", the kind of " other compounds " in (electrolyte [8]) of the invention Class and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
In the nonaqueous electrolytic solution of (electrolyte [8]) of the invention, further containing selected from the chemical combination shown in above-mentioned formula (4) At least one of thing, the heterocyclic compound containing nitrogen and/or sulphur, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound (under Face they are referred to as sometimes " specific compound B "), and its content range in whole nonaqueous electrolytic solutions is 0.001 matter Measure the mass % of %~5.
[[compound shown in formula (4)]]
In above-mentioned formula (4), R9~R12Represent can be same to each other or different to each other by H, C, N, O, F, S and P The group that more than one element is constituted.
As the existing way of these atoms, in particular, it is preferred that be present in hydrogen atom, fluorine atom, alkyl, cycloalkyl, Alkenyl, alkynyl, haloalkyl, alkoxy, carbonyl, carbonyloxy group, Epoxide carbonyl, epoxide carbonyloxy group, sulfonyl, epoxide sulphonyl In base, sulfonyloxy, phosphoryl, phosphinyl etc..In addition, the molecular weight of compound shown in formula (4) is preferably less than 500, it In more preferably less than 300, more preferably less than 200.
As the specific example of compound shown in formula (4), vinylethylene carbonate, divinyl carbonic acid can be enumerated Ethyl, methyl vinyl esters, carbonic acid cyclic olefin copolymers, ethylvinyl, carbonic acid propyl ethylene base ester, carbonic acid divinyl base ester, carbonic acid The carbonates such as allyl methyl ester, allyl ethyl ester, allyl propyl diester, carbonic acid diallyl ester；Acetic acid Vinyl acetate, propionate, vinyl acrylate, vinyl crotonate, vinyl methacrylate, allyl acetate, propionic acid Allyl ester, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, EMA, methyl-prop The esters such as olefin(e) acid propyl ester；Divinylsulfone, methyl ethylene sulfone, ethyl vinyl sulfone, propyl ethylene base sulfone, diallyl sulfone, The sulfone classes such as allyl methyl sulfone, pi-allyl ethyl sulfone, pi-allyl propyl group sulfone；Divinyl sulfite, methyl ethylene sulfurous The sulfurous esters such as acid esters, ethyl vinyl sulfite, diallyl sulfite；Vinyl methanesulfonates, vinyl second The sulfonic acid such as sulphonic acid ester, allylic mesylate, pi-allyl esilate, methyl ethylene sulphonic acid ester, ethyl vinyl sulphonic acid ester Esters；The sulfuric esters such as divinyl sulfuric ester, methyl ethylene sulfuric ester, ethyl vinyl sulfuric ester, diallyl sulfuric ester Class etc..Wherein, particularly preferred vinylethylene carbonate, divinyl ethylene carbonate, vinyl acetate, propionate, Vinyl acrylate, divinylsulfone, vinyl methanesulfonates etc..
[[heterocyclic compound containing nitrogen and/or sulphur]]
As the heterocyclic compound containing nitrogen and/or sulphur, it is not particularly limited, for example, can enumerates 1- methyl -2- pyrroles Alkanone, 1,3- dimethyl -2-Pyrrolidone, 1,5- dimethyl -2-Pyrrolidone, 1- ethyl-2-pyrrolidones, 1- cyclohexyl - The pyrrolidinone compounds such as 2-Pyrrolidone；3- methyl -2-Oxazolidone, 3- ethyls -2-Oxazolidone, 3- cyclohexyl -2-Oxazolidine Ketone etc.(oxazolidinon-5-yl-methyl)-2-thiophene-carboxamides；The piperidines ketones such as 1- methyl -2- piperidones, 1- ethyl -2- piperidones；1,3- dimethyl -2- imidazolines The imidazolone types such as ketone, 1,3- diethyl -2- imidazolones；The sulfolane such as sulfolane, 2- methyl sulfolanes, 3- methyl sulfolanes Class；Cyclobufene sultone；The sulfurous esters such as ethylidene sulfite, propylidene sulfite；1,3- propane sultones, 1- methyl- 1,3- propane sultones, 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1,3- propene sultones, 1,4- butylene Sultones class such as sultones etc..Wherein, particularly preferred 1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 1,3- third Sultones, 1,4- butyl sultones, 1,3- propene sultones, 1,4- butylene sultones etc..
[[cyclic carboxylic esters]]
As cyclic carboxylic esters, be not particularly limited, can for example enumerate gamma-butyrolacton, gamma-valerolactone, γ-oneself in Ester, γ-heptalactone, γ-octalactone, nonyl lactone, γ-decalactone, γ-hendecane lactone, γ-dodecane lactone, α-first Base-gamma-butyrolacton, α-ethyl-gamma-butyrolacton, α-propyl group-gamma-butyrolacton, Alpha-Methyl-gamma-valerolactone, α-ethyl-γ-penta Lactone, alpha, alpha-dimethyl-gamma-butyrolacton, alpha, alpha-dimethyl-gamma-valerolactone, δ-valerolactone, δ-caprolactone, δ-octalactone, δ- Nonalactone, δ-decalactone, δ-hendecane lactone, δ-dodecane lactone etc..Wherein, particularly preferred gamma-butyrolacton, gamma-valerolactone Deng.
[[fluorine-containing cyclic carbonate]]
As fluorine-containing cyclic carbonate, be not particularly limited, can enumerate fluorine ethylene carbonate, difluoro ethylene carbonate, Trifluoro ethylene carbonate, tetrafluoro ethylene carbonate, trifluoro propylene carbonate etc..Wherein, particularly preferred fluorine ethylene carbonate etc..
Specific compound B, i.e., selected from the compound shown in formula (4), the heterocyclic compound containing nitrogen and/or sulphur, ring-type The compound of at least one of carboxylate, fluorine-containing cyclic carbonate can be used alone one kind, can also be in any combination Compound of more than two kinds is used with ratio combine.In addition, in specific compound B, even the above-mentioned compound classified respectively, It can also be used alone a kind of or with ratio combine use compound of more than two kinds in any combination.
The specific compound of these in nonaqueous electrolytic solution B relative to whole nonaqueous electrolytic solutions containing ratio in terms of total amount generally For more than 0.001 mass %, more preferably more than 0.05 mass %, more preferably more than 0.1 mass %.In addition, with total Gauge, its upper limit is usually below 5 mass %, is more preferably below 4 mass %, more preferably below 3 mass %.If Specific compound B concentration is too low, then is difficult to the improvement for obtaining cycle characteristics and preservation characteristics sometimes, on the other hand, such as Fruit excessive concentration, then occasionally result in the reduction of efficiency for charge-discharge.
Using the nonaqueous electrolytic solution of the present invention rechargeable nonaqueous electrolytic battery cryogenic discharging characteristic is excellent and high temperature dwell Although the reasons why depositing characteristic or excellent cycle characteristics is also indefinite, following reason is regarded as, but the invention is not restricted to following Action principle.I.e., thus it is speculated that its reason is as follows：By reduction decomposition on negative pole during specific compound B chargings in the early stage, negative The film of the stabilization from specific compound B is formed on the surface of pole, preservation characteristics, cycle characteristics can be improved.But the painting Film at low temperature resistance increase significantly, the problem of there is cryogenic discharging characteristic reduction.By being coexisted with specific compound A, suppression Specific compound B processed excessive response, even if also forming the excellent stable complex protection film of lithium ion permeability at low temperature, So as to improve cryogenic discharging characteristic and improve High temperature storage characteristic or cycle characteristics.
Further it is considered due to the battery that the battery element stored in 1 battery case of secondary cell has When capacity is more than 3 ampere-hours (Ah) and/or secondary cell DC resistance component be 10 milliohms (Ω) below when, direct current The contribution for hindering composition is reduced, and compared with the big battery of the contribution of DC resistance component, easily shows the nonaqueous electrolytic solution original Effect.
<Electrolyte [9]>
In above-mentioned nonaqueous electrolytic solution, overcharge preventing agent (electrolyte [9]) is preferably further contained in the electrolytic solution.
" lithium salts ", " nonaqueous solvents ", " specific compound ", the kind of " other compounds " in (electrolyte [9]) of the invention Class and its content, use condition, the preparation method of nonaqueous electrolytic solution etc. are same as described above.
The non-aqueous electrolyte for secondary battery of (electrolyte [9]) of the invention is characterised by, contains overcharge preventing agent.Make For overcharge preventing agent, it is not particularly limited, but the compound preferably shown in following (1), (2) or (3) etc..
(1) biphenyl, terphenyl, diphenyl ether or the dibenzofurans that can be replaced by alkyl and/or fluorine atom；
(2) the part hydride of terphenyl；
(3) by the benzene of tertiary alkyl, cycloalkyl, fluorine atom and/or methoxy substitution.
As the compound of (1), it is not particularly limited, the phenyl ring such as can enumerate biphenyl, alkyl biphenyl, terphenyl connects Connect compounds；The fluorine-containing phenyl ring connection compounds such as 2- fluorine biphenyl；The aromatic series ethers such as diphenyl ether；The virtues such as dibenzofurans Fragrant race's heterocycle connection compounds etc..
As the compound of (3), it is not particularly limited, such as can enumerate cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene (ring) alkyl benzene；Adjacent cyclohexyl fluorobenzene, to the fluorine atom substituted benzene such as cyclohexyl fluorobenzene；2,4 difluorobenzene methyl ether, 2,5- bis- Classes containing fluoroanisole such as fluoroanisole, 2,6- difluoroanisoles, 3,5- difluoroanisoles etc..
As preferred specific example, part hydride, the ring of biphenyl, alkyl biphenyl, terphenyl, terphenyl can be enumerated The aromatic compounds such as hexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether, dibenzofurans.These compounds are due to this hair Speed characteristics improvement increase after High temperature storage in bright, thus particularly preferably.
Overcharge preventing agent can be applied in combination two or more.When being applied in combination two or more, particularly preferably by cyclohexyl Benzene or terphenyl (or part thereof hydride) and tert-butyl benzene or tert-amyl benzene are applied in combination.
The part hydride of terphenyl mentioned here refer in the double bond of the phenyl ring of terphenyl partly addition hydrogen and Obtained hydride.The part hydride of terphenyl can be single compound or the mixing containing multiple compounds Thing.For example, it may be the mixture of the part hydride of more than 2 terphenyls with different part hydrogenation ratios, can also It is the part hydride of the equal terphenyl of part hydrogenation ratio.Furthermore, it is possible to be the different hydride in the position of the phenyl ring of hydrogenation Mixture, can also be the different mixture of position of double bond or the mixture containing constitutional isomer.
The part hydrogenation ratio of terphenyl refers to, the part hydrogenation ratio of the addition hydrogen not in the double bond of the phenyl ring of terphenyl is made It is (18 moles of the addition in 1 mole of terphenyl during addition hydrogen in whole double bonds for 0%, by the complete hydride of terphenyl During hydrogen atom) part hydrogenation ratio calculated as 100% obtained from value, be every mole of average value during mixture.Example Such as, on 1 mole of terphenyl during the hydrogen atom of 2 moles of addition, part hydrogenation ratio is 11.1% (=2/18).
During using part hydrogenation ratio defined above, the part hydrogenation of the part hydride of the terphenyl used in the present invention Rate can take the value more than 0% and less than 100%.The part hydride of terphenyl can contain terphenyl (part hydrogenation ratio 0%), the complete hydride (part hydrogenation ratio 100%) of meta-terphenyl, mole average portion hydrogenation ratio of mixture preferably takes super Cross 0% and the value less than 100%.From the aspect of dissolubility from the preservation characteristics of battery and in the electrolytic solution, the portion of terphenyl It is preferably 30~70%, more preferably 35~60% to divide hydrogenation ratio.In addition, as terphenyl or the part hydride of terphenyl, It is not particularly limited, but the particularly preferably part hydride of meta-terphenyl or meta-terphenyl.
The ratio of these overcharge preventing agents in nonaqueous electrolytic solution is usually more than 0.01 mass % respectively, is preferably More than 0.1 mass %, particularly preferably more than 0.2 mass %, its upper limit is usually below 5 mass %, be preferably 3 mass % with Under, particularly preferably below 2 mass %.If less than lower limit, then security during overcharge can not be substantially ensured that sometimes, if More than the upper limit, even if the excellent battery of preservation characteristics can not be formed by then being mixed sometimes with following specific compounds.
It is not likely to produce for existing during above-mentioned specific compound speed is special after the preservation caused by overcharge additives Although the reason for variation of property is also indefinite, following reason is speculated as.In general, although overcharge preventing agent can be The internal resistance for polymerizeing film and greatly improving battery is formed during overcharge on positive electrode surface, or is produced during by the polymerization Gas the current interruptive device inside battery can is worked, thus improve security etc. of secondary cell, but even in filling Also a part of polymerization film is generated during the High temperature storage of electricity condition battery, so that the reduction of the discharge capacity as battery or speed The reason for characteristic is deteriorated.If in wherein in the presence of the present invention specific compound specified, compound effects in positive electrode surface, By forming weak shielding, suppress the reaction of overcharge preventing agent and positive active material under common charged state.But, in electricity When pond overcharge, positive pole turn into the state of overactivity, weak the shielding destruction or the reaction of positive pole and overcharge preventing agent add Speed, more than by shielding the obstruction formed, thus carries out polymerisation, it can be ensured that the security during overcharge of purpose.
<Battery design (battery structure)>
The structure (battery structure) to the lithium secondary battery of the present invention is described in detail below.
The present invention can discharge and recharge lithium secondary battery at least by can with occlusion and release lithium ion positive pole and negative pole, on Nonaqueous electrolytic solution, micro-porous film dividing plate, current-collecting terminals and the shell of configuration between a positive electrode and a negative electrode etc. is stated to constitute.According to need Protection element can also be installed in the inside of battery and/or the outside of battery.Moreover, in this specification, sometimes by the present invention The characteristic of structure (battery structure) of lithium secondary battery be referred to as structure [1]~structure [6].
[discharge capacity] (structure [3])
In the lithium secondary battery of the present invention, if the battery element stored in 1 battery case of secondary cell is had Electric capacity (electric capacity when battery is discharged into discharge condition by fully charged state) (being referred to as sometimes " battery capacity ") be 3 It is more than ampere-hour (Ah), then due to characteristics of output power raising effect increase and it is preferred that.Therefore, positive plate is preferably designed to Discharge capacity is 3 ampere-hours (Ah)~20Ah, more preferably 4Ah~10Ah (structure [3]) under full charge.During less than 3Ah, When discharging high current, the voltage reduction increase caused by electrode reaction resistance, power efficiency is deteriorated sometimes.The opposing party Face, during more than 20Ah, although electrode reaction resistance reduces, and power efficiency improves, but electricity when being due to pulse discharge and recharge The Temperature Distribution that heat release is formed inside pond is big, the poor durability of repeated charge, and for overcharge or internal short-circuit etc. The exothermal efficiency drastically generated heat when abnormal is also deteriorated, and internal pressure rises, and gas release valve work phenomenon (valve work) does not stop, with It is possible to improve as the probability for occurring the phenomenon (rupture) that cell contents outwards drastically spray
[current collecting] (structure [2], structure [4])
Current collecting is not particularly limited, but in order to which the power output for the lithium secondary battery for more effectively realizing the present invention is special Property raising, it is necessary to formed reduction distribution part or bonding part resistance structure.The internal resistance hour, can be especially excellent Ground plays the effect using above-mentioned nonaqueous electrolytic solution.
When electrode group is aftermentioned laminated construction, preferably uses and be connected to collector plate (collection Electricity タ Block) harness of each electrode layer Structure formed by terminal.During due to one piece of electrode area increase, internal resistance increase, therefore set many preferably in electrode Individual collector plate reduces resistance.When electrode group is winding-structure described later, multiple collector plates are set respectively on positive pole and negative pole, Harness is on terminal, it is possible thereby to reduce internal resistance.
By optimizing above-mentioned current collecting, internal resistance can be reduced as much as possible.The battery used with high current In, the impedance (hereinafter simply referred to as " DC resistance component ") determined with 10kHz alternating current methods be preferably 20 milliohms (m Ω) below, more Preferably 10 milliohms (m Ω) below, more preferably 5 milliohms (m Ω) below (structure [2]).On the other hand, if D.C. resistance Composition is less than 0.1 milliohm, although then high-output power characteristic is improved, the ratio shared by current collecting material used Increase, battery capacity is reduced sometimes.
In the measure of impedance, the battery manufactured using SOLAR (ソ ー ラ ー ト ロ Application) company determines the He of device 1470 The frequency response analyzer 1255B of SOLAR companies manufacture are as device is determined, to applying 10kHz's under 5mV bias Resistance during exchange is measured, and is used as DC resistance component.
The related reaction of the turnover of above-mentioned nonaqueous electrolytic solution in the present invention for reduction to lithium in electrode active material Resistance is effective, so that it is believed that it, which turns into, can realize the main cause of excellent characteristics of output power.But, it is common straight In the big battery of leakage resistance composition, hindered by DC resistance component, reaction resistance reduction effect can not 100% reflection to output In power characteristic.The problem can be improved by using the small battery of DC resistance component, so as to give full play to the present invention Effect.
In addition, from the viewpoint of manufacture plays the effect of nonaqueous electrolytic solution and the battery with high-output power characteristic, Particularly preferably meet the condition simultaneously and the above-mentioned battery element stored in 1 battery case of secondary cell has Electric capacity (electric capacity when battery is discharged to discharge condition by fully charged state) (battery capacity) is bars more than 3 ampere-hours (Ah) Part.
The connection of above-mentioned collector plate and terminal preferably by spot welding, high-frequency welding or ultrasonic bonding any one come Engage (structure [4]).These welding methods were that resistance is small, easy welding method in the past, but were due to use for a long time, were welded Part deteriorate with the reaction such as the impurity or accessory substance in nonaqueous electrolytic solution, and DC resistance component increases.But, using containing spy When determining the above-mentioned nonaqueous electrolytic solution of compound, stable film can be formed in welding portion, in addition, nonaqueous electrolytic solution can be suppressed Side reaction in positive pole, thus even in for a long time in use, the deterioration of welding portion be not easy to carry out, direct current will not be increased Resistance components simultaneously can maintain high-output power.
[battery case 1] (structure 5)
As long as the material of the nonaqueous electrolytic solution stabilization used is not particularly limited the material of battery case.Tool Say body, can be used nickel plating steel plate, stainless steel, aluminum or aluminum alloy, the metal class such as magnesium alloy, or resin and aluminium foil stack membrane (laminated film) is used as preferred material.From the aspect of lightweight, particularly preferably using the metal or laminated film of aluminum or aluminum alloy.
When in the present invention, using above-mentioned nonaqueous electrolytic solution, particularly preferably using the metal (structure of aluminum or aluminum alloy [5]).Aluminum or aluminum alloy is the high material of light weight, mouldability, but be due to as battery case it is prolonged in use, with it is non- Impurity or accessory substance in water electrolysis liquid etc. are reacted and deteriorated, and intensity or the perforate of shell are likely to decrease if being deteriorated.Use During above-mentioned nonaqueous electrolytic solution containing specific compound, stable film can be formed in aluminium surface or aluminum alloy surface, this Outside, side reaction of the nonaqueous electrolytic solution on positive pole can be suppressed, though so use for a long time, the deterioration of shell be not easy into OK.
For the shell using above-mentioned metal class, it can enumerate gold by laser welding, resistance welding, ultrasonic bonding Category welding and the shell for forming sealing closed structure, or the outer of above-mentioned metal class formation riveted structure is used by resin-made packing ring Shell.For the shell using above-mentioned laminated film, it can enumerate by the way that by resin bed, heat fused formation seals closed structure each other Shell etc..In order to improve sealing, there can be the resin different from the resin used in laminated film between above-mentioned resin bed. When resin bed heat fused being formed into closed structure especially by current-collecting terminals, due to forming the engagement of metal and resin, because This preferably uses the resin with polar group or has imported the modified resin of polar group as being present between resin bed Resin.
[battery case 2] (structure [6])
In the present invention, in the sheathing material for forming battery case, at least a portion of the inner face side of preferred battery, which is included, to be made Load wherein with piece formed by thermoplastic resin, and by the electrode group, while the thermoplastic resin layer is sealed, it is possible thereby to Seal the battery pack (structure [6]).
In order to realize battery lightweight, the material of the battery case of structure [6] situation is light weight and non-aqueous for what is used The stable material of electrolyte, due to necessary easy and positively enclosed electrode group, therefore at least a portion of the inner face side of battery It must contain using piece formed by thermoplastic resin.
In structure [6], the electrode group is sealed by the way that thermoplastic resin layer is sealed, wherein, so-called " heat-sealing " refers to On the basis of making thermoplastic resin layer closely sealed each other, the temperature more than fusing point of the thermoplastic resin is set, by the thermoplastic resin Lipid layer is bonded to each other.Preferably use the heating part with banding, and the sealer that can be heated while pressurization.This Outside, at least a portion of the inner face side of battery uses thermoplastic resin, wherein, " at least a portion " refers to the outer peripheral portion in piece Region containing the part that can only seal the electrode group, only can use thermoplastic resin in heat seal lands.From the making of piece From the aspect of the efficiency of process, the whole piece surface of the inner face side of preferred battery is covered by thermoplastic resin layer.
In addition, in structure [6], when micro-porous film dividing plate described later has the property by heating plugging hole, from overcharging From the aspect of security when electricity etc. is abnormal, sheathing material preferably contains to use at least a portion of the inner face side of battery to be had Piece formed by the thermoplastic resin of the fusing point higher than the blocking start temperature in the hole of the micro-porous film dividing plate.That is, in overcharge When producing abnormal heating in, battery temperature rise, if it exceeds the fusing point of the thermoplastic resin of sheathing material, then have battery Outer casing rupture or generation electrolyte leak the situation so that on fire, but if micro-porous film dividing plate has by heating blocking The property in hole, then due to producing hole plug of the electrolyte from micro-porous film dividing plate before sheathing material leakage, can suppress more Many heatings, thus be unlikely to rupture, it is on fire, it is advantageous to.Wherein, so-called fusing point refers to by melting that JIS K7121 are determined Change temperature.
As the thermoplastic resin in structure [6], it is not particularly limited, preferably enumerates polyethylene, polypropylene, is modified and gathers The TPOs such as alkene, polyolefin copolymer；The polyesters such as polyethylene terephthalate；Nylon etc. is polyamide-based etc..Heat Plastic resin can use one kind, can also use two or more.
As " at least a portion of sheathing material " in the structure [6], thermoplastic resin can be used only, it is preferred that Use the composite of thermoplastic resin and heat-curing resin, elastomer, metal material, glass fibre, carbon fiber etc..Separately Outside, the packing materials such as filler can also be contained.As composite, particularly preferred thermoplastic resin layer and aluminium, iron, copper, nickel, The laminated sheet of the alloy such as the elemental metals such as titanium, molybdenum, gold or the anti-corrosion Langaloy of stainless steel, haas troy, further preferably with The laminated sheet of the aluminum metal of excellent in workability.That is, sheathing material further preferably at least includes having aluminium lamination and thermoplastic resin Laminated sheet obtained from layer laminate.These metal or alloy can be used in the form of the paper tinsel of metal etc., can also be with metal steam The form of plated film is used.
In structure [6], in the shell using above-mentioned sheathing material, it can enumerate by the way that resin bed heat fused is formed Seal shell of closed structure etc..In order to improve sealing, can exist between above-mentioned resin bed with being used in sheathing material The different resin of resin.When resin bed heat fused being formed into closed structure especially by current-collecting terminals, due to forming gold Category and the engagement of resin, therefore preferably use the resin with polar group or imported the modified resin of polar group as depositing It is the resin between resin bed.
In structure [6], the thickness of sheathing material is not particularly limited, but preferably more than 0.03mm, more preferably More than 0.04mm, more preferably more than 0.05mm.In addition, its upper limit be preferably below 0.5mm, more preferably 0.3mm with Under, more preferably below 0.2mm.If sheathing material is thinner than the scope, intensity reduce, have can when easily become Shape, broken etc..On the other hand, if exterior material is thicker than the scope, due to the quality increase of shell, sometimes up to less than battery Light-weighted purpose.
Have the advantages that light weight, the free degree of shape are high using the battery of the structure [6] of above-mentioned sheathing material, the opposing party Face, if inside battery produces gas, internal pressure rise, sheathing material is sometimes prone to deformation.In lithium secondary battery in the present invention, Specific compound in nonaqueous electrolytic solution is adsorbed on positive active material surface, thus can suppress the side reaction of positive pole, and suppress The generation of gas componant, even if therefore using above-mentioned sheathing material, disadvantages mentioned above is not also shown, above-mentioned outer shell material is only shown The above-mentioned advantage of material, it is advantageous to.
[micro-porous film dividing plate]
As long as the micro-porous film dividing plate used in the present invention is with electronically by the defined machinery of two electrode insulations Intensity, ion permeable degree is big, and has both the patience of the oxidisability for the side that pair connects with positive pole and to the resistance to of the reproducibility of negative side The dividing plate of property, is not not particularly limited.As the material of the micro-porous film dividing plate with the characteristic, resin, inorganic is used Thing, glass fibre etc..
As above-mentioned resin, it is not particularly limited, for example, can enumerates olefin polymer, fluorine-based polymer, cellulose Birds of the same feather flock together compound, polyimides, nylon etc..In particular, it is preferred that from stable to nonaqueous electrolytic solution and protect the excellent material of fluidity Selection, preferably uses porous chips or non-woven cloth using TPOs such as polyethylene, polypropylene as raw material etc..As above-mentioned inorganic Thing, is not particularly limited, oxide-based such as usable aluminum oxide, silica；Aluminium nitride or silicon nitride etc. are nitride-based； Sulfateses such as barium sulfate, calcium sulfate etc..For shape, particle shape or fibrous can be used.
As form, preferably non-woven cloth, weave cotton cloth, the film shape such as micro- porous membrane.In film shape, preferably use The film that aperture is 0.01~1 μm, thickness is 5~50 μm.In addition to above-mentioned independent film shape, it can use and use resin Composite porous layer containing above-mentioned inorganic particles is formed the form on the top layer of positive pole and/or negative pole by the adhesive of system. As such form, for example, it can enumerate on the two sides of positive pole, it is 1 that 90% particle diameter is formed using fluororesin as adhesive Porous layer obtained from aluminium oxide particles below μm.
The micro-porous film dividing plate used in the present invention, which preferably has, passes through the dividing plate for the property for heating plugging hole.If combination At least a portion of the inner face side in battery using above-mentioned micro-porous film dividing plate and as sheathing material is used with more micro- than this The thermoplastic resin of the high fusing point of the hole plug start temperature of perforated membrane dividing plate is come the sheathing material that is formed, then different in overcharge etc. Normal adstante febre, with the effect that can stop generating heat before battery case rupture or electrolyte leakage.In addition, mentioned here " by the property for heating plugging hole ", the porous layer that referring to form electrolyte can move between both positive and negative polarity contains thermoplasticity Resin, and when being heated near the fusing point of the thermoplastic resin, the porous layer is blocked, and electrolyte can not be moved between both positive and negative polarity Dynamic property.
[cell shapes]
Cell shapes are not particularly limited, bottom cartridge type shape can have been enumerated, had bottom square configuration, slim shape, piece Shape, paper-like etc..When being assembled into system or machine, storage property is improved in order to improve volumetric efficiency, be can also be in view of configuration The abnormity such as the shape of a hoof, combed shape in the storage of the perimeter systems of battery circumferential.From effectively the heat of inside battery is released It is put into from the aspect of outside, the square configuration in the face preferably with least one smoother large area.
In the battery for having bottom cartridge type shape, because the external surface area of the generating element relative to filling reduces, therefore it is excellent Form slection into effectively by during charge or discharge due to internal resistance produce Joule heat be discharged into outside design.Furthermore it is preferred that It is designed to improve the Temperature Distribution inside the filling ratio of the high material of thermal conductivity and reduction.
Have in the square configuration of bottom, preferably at most the area S in face1(the wide and high product of the appearance and size of removing portion of terminal, Unit cm2) 2 times with the thickness T (unit cm) of battery appearance ratio (2 × S1/ T) value be more than 100, more preferably 200 More than.By increasing largest face, even if being high-output power and the battery of Large Copacity, cyclicity or High temperature storage can also be improved Etc. characteristic, while exothermal efficiency when can improve abnormal heating, so as to suppress to be formed " rupture " or the danger of " on fire " State.
[electrode group]
Electrode group can be clipped between positive plate described later and negative plate formed by micro-porous film dividing plate described later Laminated construction electrode group, and clip micro-porous film dividing plate described later between positive plate described later and negative plate and be wound into spiral Any one of the winding-structure electrode group of shape.The volume of electrode group is shared in the volume of jut of battery case is not included Ratio (hereinafter simply referred to as " electrode group occupation rate ") be preferably 0.3~0.7, more preferably 0.4~0.6.Above-mentioned electrode group is accounted for When having rate less than 0.3, battery capacity diminishes, in addition, if more than 0.7, then because void space reduces, it is impossible to after substantially ensuring that Volume necessary to the current collecting stated, cell resistance is likely to increase, further, since battery formation high temperature, part expansion or There is the repeated charge performance or high temperature as battery in the vapour pressure rise of the liquid component of electrolyte, internal pressure rise The situation that the various characteristics reductions such as preservation or the gas release valve that internal pressure further is released into outside work.
In addition, when electrode group is laminated construction, summation L (unit cm) and the electricity of positive pole and negative pole preferred electrode circumference Pole-face accumulates S2(unit cm2) the ratio between 2 times (L/ (2 × S2)) for less than 1, more preferably less than 0.5, more preferably 0.3 with Under.In addition, its lower limit is preferably more than 0.02, more preferably more than 0.03, more preferably more than 0.05.Laminated construction In the case of, due to part close around electrode because caused by residual stress or cut-out impact under, the bonding of electrode film Property be possible to be deteriorated, therefore as L/ (2 × S2) exceed above range when, characteristics of output power is reduced sometimes.If in addition, L/ (2 × S2) being less than above range, then cell area is excessive, sometimes and impracticable.
In addition, when electrode group is winding-structure, preferred length of the length of the length direction of the positive pole for width Ratio be 15~200.If the ratio is less than above range, there is battery case has bottom cartridge type shape relative to floor space For it is highly excessive, balance is deteriorated and impracticable, or positive electrode active material layer is thickening and can not obtain the feelings of high-output power Condition.If in addition, the ratio is less than above range, there is battery case has bottom cartridge type shape high for floor space Spend it is small, balance be deteriorated and it is impracticable, or shared by collector ratio increase, battery capacity reduce situation.
[anode electrode area] (structure [1])
When in the present invention, using above-mentioned nonaqueous electrolytic solution, in terms of stability when high-output power and raising high temperature Consider, the preferably area of positive electrode active material layer is bigger than the external surface area of battery case.Specifically, from the raising of power output From the viewpoint of the heating release that effectively can be brought discharge and recharge by collector, the electrode area of preferably above-mentioned positive pole Surface area of the summation relative to the shell of secondary cell more than 15 times, more preferably more than 20 times (structures are calculated as with area ratio [1]).The external surface area of so-called shell, in the case of having bottom square configuration, refers to being filled with by the jut except terminal The gross area tried to achieve by the Size calculation of length and width and thickness of the shell parts of power generation element.In the case of having bottom cylindrical shape, it is Refer to except the shell parts filled with power generation element of the jut of terminal are approximately the geometrical surface of cylinder.So-called positive pole The summation of electrode area, refers to the geometry table of the positive pole plied timber layer opposed with the plied timber layer containing negative electrode active material Area, in the structure for forming positive pole plied timber layer on two sides by current collector foil, refers to calculate each face respectively The summation of area.
[protection element]
As above-mentioned protection element, can enumerate abnormal heating or when super-high-current flows through resistance increase PTC When (positive temperature coefficient, positive temperature coefficient), temperature fuse, thermistor, abnormal heating Valve (current blocking valve) of the electric current flowed through in circuit etc. is blocked due to cell internal pressure or drastically raising for internal temperature. Above-mentioned protection element preferably selects the element in the usually used middle inoperation condition of high current, is examined from the viewpoint of high-output power Consider, more preferably form the design for being also unlikely to abnormal heating or thermal runaway even if without protection element.
[assembled battery]
Using the lithium secondary battery of the present invention as power supply for practical application when, the voltage for power requirement is mostly single More than cell voltage, it is necessary to which correspondence uses increasing apparatus for connecting cells in series etc..Therefore, lithium secondary battery of the invention It is preferably made and uses its multiple Battery pack being connected in series.By forming Battery pack, the resistance of coupling part is reduced, from And the power output reduction as Battery pack can be suppressed.As Battery pack, from the aspect of supply voltage, it is preferably connected in series More than 5.
In addition, connection is multiple when Battery pack is made, due to the influence increase for the heating that discharge and recharge is brought, therefore preferably have For the cooling body being maintained at battery below certain temperature.As battery temperature, preferably 10 DEG C~40 DEG C, preferably water cooling But or by air cooling cooled down using outer gas.
[purposes]
The lithium secondary battery of the present invention and the Battery pack that multiple lithium secondary batteries of the invention are formed by connecting, due to tool There are high-output power, long-life, high security etc., therefore be preferred for being loaded on vehicle, its power at least supply vehicle In the purposes of drive system.
, can be with additionally, it is believed that above-mentioned specific compound is by adsorbing in positive active material surface or metal material surface Suppress the side reaction with electrolyte etc..Think the side reaction on positive active material surface by the suppression, less, i.e., gas produce It is not easy to cause the deformation of battery or the rise of internal pressure using the sheathing material of sheet, it is advantageous to.Furthermore, it is considered that passing through suppression The side reaction on positive active material surface processed, security when life-span of battery, power output, overcharge is improved, and this is conducive to Application in large-sized battery.In addition it is also believed that side reaction by suppressing metal material surface, in the company of collector plate and terminal In connecing, though using resistance is small, easy welding method when, because the increase of DC resistance component when being used for a long time is pressed down System, therefore be conducive to the application in large-sized battery.Furthermore, it is considered that the reaction resistance of reduction positive pole for by cell shapes or Positive pole area etc. be designed in the battery of high-output power further to improve power output be it is effective, it is advantageous to.
Embodiment
Below, enumerate embodiment and comparative example further illustrate the present invention, but as long as without departing from the present invention purport, then The present invention is not limited to the examples.
Positive pole [1] [positive active material]
The species and physical property of the positive active material used in the following examples and comparative example are as follows.
Positive pole [1] table 1
[table 1]
In positive pole [1] table 1, as the physical property of positive active material, according to the method for above-mentioned record, carry out BET and compare surface Product, average primary particle diameter (being determined with SEM), median particle diameter d50, tap density measure.
[positive active material A]
Positive active material A is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula LiMn0.33Ni0.33Co0.33O2Represent.With Mn:Ni:Co=1:1:1 molar ratio weighing as manganese raw material Mn3O4, be used as nickel former The NiO of the material and Co (OH) as cobalt raw material2, and slurry is made in addition pure water thereto, while stirring using circulating medium Stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, only bag raw material containing manganese, nickel raw material, the grain of cobalt raw material is obtained The substantially spherical granulation particle in about 5 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and is made The ratio between Li molal quantity and Mn, Ni and Co total mole number are 1.05, are mixed with high-speed mixer, obtain nickel raw material, cobalt The granulation particle and the mixed-powder of lithium raw material of raw material, manganese raw material.Under air circulation, 950 DEG C to the mixed-powder sintering 12 After hour (warming and cooling rate is 5 DEG C/min), crush, by 45 μm of sieve of mesh, obtain positive active material A.
[positive active material B]
Positive active material B is the lithium-transition metal composite oxide synthesized in the same manner as positive active material A, with composition Formula LiMn0.33Ni0.33Co0.33O2Represent, its difference is：The condition of spray drying is changed, the granulation of about 1 μm of particle diameter is made Particle, and sintering temperature is 930 DEG C.
[positive active material C]
The positive active material C sulphur that has been the surface attachment in positive active material A according to method synthesis shown below Positive active material formed by compound and antimonial.That is, 96.7 parts by weight positive active material A are stirred in flowing groove Mix, while the 1.3 parts sulfuric acid lithium (Li that spray thereto2SO4H2O the aqueous solution) is into spray form.Add in obtained mixture Plus 2.0 parts by weight antimony trioxide (Sb2O3, particle median particle diameter is 0.8 μm), it is sufficiently mixed.The mixture is transferred to aluminum oxide In container, sintered 2 hours in 680 DEG C under air atmosphere, obtain positive active material C.
[positive active material D]
Positive active material D is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.04Mn1.84Al0.12O4Represent.With Li:Mn:Al=1.04:1.84:0.12 molar ratio weighing as lithium raw material LiOH, It is used as the Mn of manganese raw material2O3With the AlOOH as aluminum feedstock, and thereto add pure water slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.5 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, manganese raw material, the grain of aluminum feedstock The substantially spherical granulation particle in about 10 μm of footpath.The granulation particle is sintered into 3 hours (programming rates at nitrogen circulation, 900 DEG C For 5 DEG C/min) after, circulated gases are transformed into air by nitrogen, then sinter at 900 DEG C 2 hours (cooling rate is 1 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material D.
[positive active material E]
Positive active material E is commercially available product (cobalt acid lithium of Japan Chemical Industry company manufacture), is to use composition formula Li1.03CoO2The lithium and cobalt oxides of expression.
Positive pole [1] embodiment 1
《The making of positive pole》
Mixed in N methyl pyrrolidone solvents 90 mass % as positive active material positive active material A, 5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and thickness is rolled into press for 80 μm, then be cut into The shape of uncoated portion with wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm, is used as positive pole.Just The density of pole active material is 2.35g/cm3, the value of (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 2.2。
《The making of negative pole》
Added in 98 parts by weight Delanium powder KS-44 (timcal (テ ィ system カ Le) company manufactures, trade name) 100 parts by weight as the sodium carboxymethylcellulose of thickener aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 matter Measure %), 2 parts by weight as the SBR styrene butadiene rubberses of adhesive aqueous liquid dispersion (SBR styrene butadiene rubberses it is dense Spend for 50 mass %), mixed with disperser, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, And dry, thickness is rolled into press for 75 μm, then be cut into width 104mm, the negative electrode active material of long 104mm sizes The shape of matter layer and width 30mm uncoated portion, is used as negative pole.
《The making of electrolyte》
Under dry argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:4 in the mixed solvent, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。 In addition, the hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL electrolyte is injected in the battery can equipped with electrode group, makes electrode Full penetration, seals and makes battery.The ratio between the electrode area summation of positive pole and the case surface product summation of battery are 20.6.
《The evaluation of battery》
(assay method of battery capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.1V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.The 0.2C discharge capacities of the 5th circulation now are held as initial stage Amount.The result of cell evaluation is shown in positive pole [1] table 2.
The assay method of power output (initial stage)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).The result of cell evaluation is shown in positive pole [1] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.1V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, carries out the discharge and recharge of 3 circulations in the environment of 25 DEG C with 0.2C current value, is discharged and held with the 0.2C of the 3rd circulation Amount is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carries out output test, as durable Power output afterwards.The result of cell evaluation is shown in positive pole [1] table 2.
Positive pole [1] embodiment 2
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [1] embodiment 1.The result of cell evaluation is shown in positive pole [1] table 2.
Positive pole [1] embodiment 3
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [1] embodiment 1.The result of cell evaluation is shown in positive pole [1] table 2.
Positive pole [1] embodiment 4
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [1] embodiment 1 is equally implemented.The result of cell evaluation is shown in positive pole [1] table 2.
Positive pole [1] comparative example 1
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [1] embodiment 1.Battery is commented The result of valency is shown in positive pole [1] table 2.
Positive pole [1] table 2
[table 2]
Positive pole [1] embodiment 5
Except using positive active material A and positive active material B with 2:Positive pole obtained from 1 mass ratio is sufficiently mixed Active material is made beyond positive pole as positive active material, is equally implemented with positive pole [1] embodiment 1.The positive pole of the mixing is lived Property material BET specific surface area be 1.8m2/ g, average primary particle diameter is 0.22 μm, median particle diameter d50For 3.2 μm, tap density For 1.5g/cm2.The result of cell evaluation is shown in positive pole [1] table 3.
Positive pole [1] embodiment 6
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [1] embodiment 5.The result of cell evaluation is shown in positive pole [1] table 3.
Positive pole [1] embodiment 7
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [1] embodiment 5.The result of cell evaluation is shown in positive pole [1] table 3.
Positive pole [1] embodiment 8
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [1] embodiment 5 is equally implemented.The result of cell evaluation is shown in positive pole [1] table 3.
Positive pole [1] comparative example 2
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [1] embodiment 5.Battery is commented The result of valency is shown in positive pole [1] table 3.
Positive pole [1] table 3
[table 3]
Positive pole [1] embodiment 9
Except using positive active material C as positive active material, it is made beyond positive pole, it is same with positive pole [1] embodiment 1 Sample is implemented.The result of cell evaluation is shown in positive pole [1] table 4.
Positive pole [1] embodiment 10
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [1] embodiment 9.The result of cell evaluation is shown in positive pole [1] table 4.
Positive pole [1] embodiment 11
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [1] embodiment 9.The result of cell evaluation is shown in positive pole [1] table 4.
Positive pole [1] embodiment 12
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [1] embodiment 9 is equally implemented.The result of cell evaluation is shown in positive pole [1] table 4.
Positive pole [1] comparative example 3
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [1] embodiment 9.Battery is commented The result of valency is shown in positive pole [1] table 4.
Positive pole [1] table 4
[table 4]
Positive pole [1] embodiment 13
Using positive active material D as positive active material, positive pole is made, thickness is rolled into press for 108 μm, And 28 positive poles and 29 negative poles are used, in addition, battery is made in the same manner as positive pole [1] embodiment 1.(positive pole one side Positive electrode active material layer thickness/positive electrode collector thickness) be 3.1, the summation of the electrode area of positive pole and the shell of battery The ratio between surface area summation is 18.1.The voltage range of solid measure is 3.0~4.2V, and the upper voltage limit of cyclic test is 4.2V, In addition, battery is evaluated in the same manner as positive pole [1] embodiment 1.The result of cell evaluation is shown in positive pole [1] table 5.
Positive pole [1] embodiment 14
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [1] embodiment 13.The result of cell evaluation is shown in positive pole [1] table 5.
Positive pole [1] embodiment 15
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [1] embodiment 13.The result of cell evaluation is shown in positive pole [1] table 5.
Positive pole [1] embodiment 16
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [1] embodiment 13 is equally implemented.The result of cell evaluation is shown in positive pole [1] table 5.
Positive pole [1] comparative example 4
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [1] embodiment 13.Battery is commented The result of valency is shown in positive pole [1] table 5.
Positive pole [1] table 5
[table 5]
Positive pole [1] embodiment 17
Using positive active material D and positive active material E with 2:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, thickness is rolled into press for 94 μm, and use 29 positive poles and 30 Negative pole, in addition, equally implements with positive pole [1] embodiment 1.(positive electrode active material layer thickness/positive pole current collections of positive pole one side The thickness of body) it is 2.6, the ratio between the summation of the electrode area of positive pole and the case surface product summation of battery are 18.7.In addition, this is mixed The BET specific surface area of the positive active material of conjunction is 0.8m2/ g, average primary particle diameter is 0.50 μm, median particle diameter d50For 8.3 μ M, tap density is 2.5g/cm3.The result of cell evaluation is shown in positive pole [1] table 6.
Positive pole [1] embodiment 18
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [1] embodiment 17.The result of cell evaluation is shown in positive pole [1] table 6.
Positive pole [1] embodiment 19
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [1] embodiment 17.The result of cell evaluation is shown in positive pole [1] table 6.
Positive pole [1] embodiment 20
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [1] embodiment 17 is equally implemented.The result of cell evaluation is shown in positive pole [1] table 6.
Positive pole [1] comparative example 5
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [1] embodiment 17.Battery is commented The result of valency is shown in positive pole [1] table 6.
Positive pole [1] table 6
[table 6]
From the result of positive pole [1] 2~positive pole of table [1] table 6, in any one positive pole, due to all containing in the electrolytic solution There is specific compound, therefore, power output, capability retention are improved, and after cyclic test, can also be abundant Keep battery capacity and power output.
Positive pole [2] [positive active material]
The species and physical property of the positive active material used in the following examples and comparative example are as follows.
Positive pole [2] table 1
[table 7]
In positive pole [2] table 1, as the physical property of positive active material, according to the method for above-mentioned record, carry out BET and compare surface Product, average primary particle diameter (being determined with SEM), median particle diameter d50, tap density measure.
[positive active material A]
Positive active material A is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.05Ni0.80Co0.15Al0.05O2Represent.With Ni:Co:Al=80:15:NiO of 5 molar ratio weighing as nickel raw material, conduct The Co (OH) of cobalt raw material2With the AlOOH as Al raw materials, and thereto add pure water slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.25 μm of median particle diameter.
Slurry is spray-dried by spray dryer, the grain of only bag nickel bearing raw material, cobalt raw material, aluminum feedstock is obtained The substantially spherical granulation particle in about 10 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and is made The ratio between Li molal quantity and Ni, Co and Al total mole number are 1.05, are mixed with high-speed mixer, obtain nickel raw material, cobalt The granulation particle and the mixed-powder of lithium raw material of raw material, aluminum feedstock.Oxygen circulation under, 740 DEG C to the mixed-powder sinter 6 hours After (warming and cooling rate is 5 DEG C/min), crushes, by 45 μm of sieve of mesh, obtain positive active material A.
[positive active material B]
Positive active material B is the lithium-transition metal composite oxide synthesized in the same manner as positive active material A, with composition Formula Li1.05Ni0.80Co0.15Al0.05O2Represent, its difference is：The condition of spray drying is changed, making for about 1 μm of particle diameter is made Grain particle, and sintering temperature is 720 DEG C.
[positive active material C]
The positive active material C sulphur that has been the surface attachment in positive active material A according to method synthesis shown below Positive active material formed by compound and antimonial.That is, 96.7 parts by weight positive active material A are stirred in flowing groove Mix, while the 1.3 parts sulfuric acid lithium (Li that spray thereto2SO4H2O the aqueous solution) is into spray form.Add in obtained mixture Plus 2.0 parts by weight antimony trioxide (Sb2O3, particle median particle diameter is 0.8 μm), it is sufficiently mixed.The mixture is transferred to aluminum oxide In container, sintered 2 hours in 680 DEG C under air atmosphere, obtain positive active material C.
[positive active material D]
Positive active material D is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.03Ni0.65Co0.20Mn0.15O2Represent.With Li:Co:Mn=65:20:15 molar ratio weighing as nickel raw material Ni (OH)2、 It is used as the Co (OH) of cobalt raw material2With the Mn as manganese raw material2O3, and add pure water thereto slurry is made, while stirring using following Ring type medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, only bag nickel bearing raw material, cobalt raw material, the grain of manganese raw material is obtained The substantially spherical granulation particle in about 12 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and is made The ratio between Li molal quantity and Ni, Co and Mn total mole number are 1.05, are mixed with high-speed mixer, obtain nickel raw material, cobalt The granulation particle and the mixed-powder of lithium raw material of raw material, manganese raw material.Under air circulation, 950 DEG C to the mixed-powder sintering 12 After hour (warming and cooling rate is 5 DEG C/min), crush, by 45 μm of sieve of mesh, obtain positive active material D.
[positive active material E]
Positive active material E is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.04Mn1.84Al0.12O4Represent.With Li:Mn:Al=1.04:1.84:0.12 molar ratio weighing as lithium raw material LiOH, It is used as the Mn of manganese raw material2O3With the AlOOH as aluminum feedstock, and thereto add pure water slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.5 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, manganese raw material, the grain of aluminum feedstock The substantially spherical granulation particle in about 10 μm of footpath.The granulation particle is sintered into 3 hours (programming rates at nitrogen circulation, 900 DEG C For 5 DEG C/min) after, circulated gases are transformed into air by nitrogen, then sinter at 900 DEG C 2 hours (cooling rate is 1 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material E.
Positive pole [2] embodiment 1
《The making of positive pole》
Mixed in N methyl pyrrolidone solvents 90 mass % as positive active material positive active material A, 5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and thickness is rolled into press for 66 μm, then be cut into The shape of uncoated portion with wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm, is used as positive pole.Just The density of pole active material is 2.35g/cm3, the value of (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 1.7。
《The making of negative pole》
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into width 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm not The shape of coated portion, is used as negative pole.
《The making of electrolyte》
Under dry argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:4 in the mixed solvent, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。 In addition, the hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making of battery》
34 positive poles and 35 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL electrolyte is injected in the battery can equipped with electrode group, makes electrode Full penetration, seals and makes battery.The ratio between the electrode area summation of positive pole and the case surface product summation of battery are 21.9.
《The evaluation of battery》
(assay method of battery capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.1V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.The 0.2C discharge capacities of the 5th circulation now are held as initial stage Amount.The result of cell evaluation is shown in positive pole [2] table 2.
The assay method of power output (initial stage)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).The result of cell evaluation is shown in positive pole [2] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.1V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, carries out the discharge and recharge of 3 circulations in the environment of 25 DEG C with 0.2C current value, is discharged and held with the 0.2C of the 3rd circulation Amount is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carries out output test, as durable Power output afterwards.The result of cell evaluation is shown in positive pole [2] table 2.
Positive pole [2] embodiment 2
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [2] embodiment 1.The result of cell evaluation is shown in positive pole [2] table 2.
Positive pole [2] embodiment 3
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [2] embodiment 1.The result of cell evaluation is shown in positive pole [2] table 2.
Positive pole [2] embodiment 4
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [2] embodiment 1 is equally implemented.The result of cell evaluation is shown in positive pole [2] table 2.
Positive pole [2] comparative example 1
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [2] embodiment 1.Battery is commented The result of valency is shown in positive pole [2] table 2.
Positive pole [2] table 2
[table 8]
Positive pole [2] embodiment 5
Except using positive active material A and positive active material B with 2:Positive pole obtained from 1 mass ratio is sufficiently mixed Active material is made beyond positive pole as positive active material, is equally implemented with positive pole [2] embodiment 1.The positive pole of the mixing is lived Property material BET specific surface area be 1.4m2/ g, average primary particle diameter is 0.2 μm, median particle diameter d50For 6.3 μm, tap density is 1.9g/cm2.The result of cell evaluation is shown in positive pole [2] table 3.
Positive pole [2] embodiment 6
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [2] embodiment 5.The result of cell evaluation is shown in positive pole [2] table 3.
Positive pole [2] embodiment 7
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [2] embodiment 5.The result of cell evaluation is shown in positive pole [2] table 3.
Positive pole [2] embodiment 8
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [2] embodiment 5 is equally implemented.The result of cell evaluation is shown in positive pole [2] table 3.
Positive pole [2] comparative example 2
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [2] embodiment 5.Battery is commented The result of valency is shown in positive pole [2] table 3.
Positive pole [2] table 3
[table 9]
Positive pole [2] embodiment 9
Except using positive active material C as positive active material, it is made beyond positive pole, it is same with positive pole [2] embodiment 1 Sample is implemented.The result of cell evaluation is shown in positive pole [2] table 4.
Positive pole [2] embodiment 10
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [2] embodiment 9.The result of cell evaluation is shown in positive pole [2] table 4.
Positive pole [2] embodiment 11
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [2] embodiment 9.The result of cell evaluation is shown in positive pole [2] table 4.
Positive pole [2] embodiment 12
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [2] embodiment 9 is equally implemented.The result of cell evaluation is shown in positive pole [2] table 4.
Positive pole [2] comparative example 3
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [2] embodiment 9.Battery is commented The result of valency is shown in positive pole [2] table 4.
Positive pole [2] table 4
[table 10]
Positive pole [2] embodiment 13
Using positive active material D as positive active material, positive pole is made, thickness is rolled into press for 68 μm, And 34 positive poles and 35 negative poles are used, in addition, battery is made in the same manner as positive pole [2] embodiment 1.(positive pole one side Positive electrode active material layer thickness/positive electrode collector thickness) be 1.8, the summation of the electrode area of positive pole and the shell of battery The ratio between surface area summation is 21.9.The voltage range of solid measure is 3.0~4.2V, and the upper voltage limit of cyclic test is 4.2V, In addition, battery is evaluated in the same manner as positive pole [2] embodiment 1.The result of cell evaluation is shown in positive pole [2] table 5.
Positive pole [2] embodiment 14
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [2] embodiment 13.The result of cell evaluation is shown in positive pole [2] table 5.
Positive pole [2] embodiment 15
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [2] embodiment 13.The result of cell evaluation is shown in positive pole [2] table 5.
Positive pole [2] embodiment 16
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [2] embodiment 13 is equally implemented.The result of cell evaluation is shown in positive pole [2] table 5.
Positive pole [2] comparative example 4
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [2] embodiment 13.Battery is commented The result of valency is shown in positive pole [2] table 5.
Positive pole [2] table 5
[table 11]
Positive pole [2] embodiment 17
Using positive active material A and positive active material E with 2:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, thickness is rolled into press for 76 μm, and use 32 positive poles and 33 Negative pole, in addition, equally implements with positive pole [2] embodiment 1.(positive electrode active material layer thickness/positive pole current collections of positive pole one side The thickness of body) it is 2.0, the ratio between the summation of the electrode area of positive pole and the case surface product summation of battery are 20.6.In addition, this is mixed The BET specific surface area of the positive active material of conjunction is 0.7m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 8.7 μm, Tap density is 2.2g/cm3.The result of cell evaluation is shown in positive pole [2] table 6.
Positive pole [2] embodiment 18
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [2] embodiment 17.The result of cell evaluation is shown in positive pole [2] table 6.
Positive pole [2] embodiment 19
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [2] embodiment 17.The result of cell evaluation is shown in positive pole [2] table 6.
Positive pole [2] embodiment 20
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [2] embodiment 17 is equally implemented.The result of cell evaluation is shown in positive pole [2] table 6.
Positive pole [2] comparative example 5
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [2] embodiment 17.Battery is commented The result of valency is shown in positive pole [2] table 6.
Positive pole [2] table 6
[table 12]
From the result of positive pole [2] 2~positive pole of table [2] table 6, in any one positive pole, due to all containing in the electrolytic solution There is specific compound, therefore, power output, capability retention are improved, and after cyclic test, can also be abundant Keep battery capacity and power output.
Positive pole [3] [positive active material]
The species and physical property of the positive active material used in the following examples and comparative example are as follows.
Positive pole [3] table 1
[table 13]
In positive pole [3] table 1, as the physical property of positive active material, according to the method for above-mentioned record, carry out BET and compare surface Product, average primary particle diameter (being determined with SEM), median particle diameter d50, tap density measure.
[positive active material A]
Positive active material A is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.05Ni0.8Co0.2O2Represent.With Ni:Co=80:20 the molar ratio weighing NiO as nickel raw material and the Co as cobalt raw material (OH)2, and slurry is made in addition pure water thereto, while stirring using circulating medium-stirring wet-type ball mill by slurry Solid constituent case of wet attrition into 0.25 μm of median particle diameter.
Slurry is spray-dried by spray dryer, about 8 μm of the particle diameter of only bag nickel bearing raw material, cobalt raw material is obtained Substantially spherical granulation particle.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and makes Li mole The ratio between number and Ni and Co total mole number is 1.05, is mixed with high-speed mixer, obtains the granulation grain of nickel raw material, cobalt raw material The mixed-powder of son and lithium raw material.Under oxygen circulation, 740 DEG C to mixed-powder sintering, (warming and cooling rate is 5 DEG C/minute within 6 hours Clock) after, crush, by 45 μm of sieve of mesh, obtain positive active material A.
[positive active material B]
Positive active material B is the lithium-transition metal composite oxide synthesized in the same manner as positive active material A, with composition Formula Li1.05Ni0.8Co0.2O2Represent, its difference is：The condition of spray drying is changed, the granulation particle of about 1 μm of particle diameter is made, And sintering temperature is 720 DEG C.
[positive active material C]
The positive active material C sulphur that has been the surface attachment in positive active material A according to method synthesis shown below Positive active material formed by compound and antimonial.That is, 96.7 parts by weight positive active material A are stirred in flowing groove Mix, while the 1.3 parts sulfuric acid lithium (Li that spray thereto2SO4H2O the aqueous solution) is into spray form.Add in obtained mixture Plus 2.0 parts by weight antimony trioxide (Sb2O3, particle median particle diameter is 0.8 μm), it is sufficiently mixed.The mixture is transferred to aluminum oxide In container, sintered 2 hours in 680 DEG C under air atmosphere, obtain positive active material C.
[positive active material D]
Positive active material D is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.04Mn1.84Al0.12O4Represent.With Li:Mn:Al=1.04:1.84:0.12 molar ratio weighing as lithium raw material LiOH, It is used as the Mn of manganese raw material2O3With the AlOOH as aluminum feedstock, and thereto add pure water slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.5 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, manganese raw material, the grain of aluminum feedstock The substantially spherical granulation particle in about 10 μm of footpath.The granulation particle is sintered into 3 hours (programming rates at nitrogen circulation, 900 DEG C For 5 DEG C/min) after, circulated gases are transformed into air by nitrogen, then sinter at 900 DEG C 2 hours (cooling rate is 1 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material D.
Positive pole [3] embodiment 1
《The making of positive pole》
Mixed in 1-METHYLPYRROLIDONE solvent 90 mass % as positive active material positive active material A, 5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and thickness is rolled into press for 65 μm, then be cut into The shape of uncoated portion with wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm, is made positive pole.Just The density of pole active material is 2.35g/cm3, the value of (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 1.7。
《The making of negative pole》
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into width 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm not The shape of coated portion, is used as negative pole.
《The making of electrolyte》
Under dry argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:4 in the mixed solvent, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。 In addition, the hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making of battery》
34 positive poles and 35 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL electrolyte is injected in the battery can equipped with electrode group, makes electrode Full penetration, seals and makes battery.The ratio between the electrode area summation of positive pole and the case surface product summation of battery are 21.9.
《The evaluation of battery》
(assay method of battery capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.1V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.The 0.2C discharge capacities of the 5th circulation now are held as initial stage Amount.The result of cell evaluation is shown in positive pole [3] table 2.
The assay method of power output (initial stage)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).The result of cell evaluation is shown in positive pole [3] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.1V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, carries out the discharge and recharge of 3 circulations in the environment of 25 DEG C with 0.2C current value, is discharged and held with the 0.2C of the 3rd circulation Amount is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carries out output test, as durable Power output afterwards.The result of cell evaluation is shown in positive pole [3] table 2.
Positive pole [3] embodiment 2
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [3] embodiment 1.The result of cell evaluation is shown in positive pole [3] table 2.
Positive pole [3] embodiment 3
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [3] embodiment 1.The result of cell evaluation is shown in positive pole [3] table 2.
Positive pole [3] embodiment 4
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [3] embodiment 1 is equally implemented.The result of cell evaluation is shown in positive pole [3] table 2.
Positive pole [3] comparative example 1
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [3] embodiment 1.Battery is commented The result of valency is shown in positive pole [3] table 2.
Positive pole [3] table 2
[table 14]
Positive pole [3] embodiment 5
Except using positive active material A and positive active material B with 2:Positive pole obtained from 1 mass ratio is sufficiently mixed Active material is made beyond positive pole as positive active material, is equally implemented with positive pole [3] embodiment 1.The positive pole of the mixing is lived Property material BET specific surface area be 1.8m2/ g, average primary particle diameter is 0.2 μm, median particle diameter d50For 4.3 μm, tap density is 1.8g/cm2.The result of cell evaluation is shown in positive pole [3] table 3.
Positive pole [3] embodiment 6
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [3] embodiment 5.The result of cell evaluation is shown in positive pole [3] table 3.
Positive pole [3] embodiment 7
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [3] embodiment 5.The result of cell evaluation is shown in positive pole [3] table 3.
Positive pole [3] embodiment 8
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [3] embodiment 5 is equally implemented.The result of cell evaluation is shown in positive pole [3] table 3.
Positive pole [3] comparative example 2
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [3] embodiment 5.Battery is commented The result of valency is shown in positive pole [3] table 3.
Positive pole [3] table 3
[table 15]
Positive pole [3] embodiment 9
Except using positive active material C as positive active material, it is made beyond positive pole, it is same with positive pole [3] embodiment 1 Sample is implemented.The result of cell evaluation is shown in positive pole [3] table 4.
Positive pole [3] embodiment 10
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [3] embodiment 9.The result of cell evaluation is shown in positive pole [3] table 4.
Positive pole [3] embodiment 11
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [3] embodiment 9.The result of cell evaluation is shown in positive pole [3] table 4.
Positive pole [3] embodiment 12
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [3] embodiment 9 is equally implemented.The result of cell evaluation is shown in positive pole [3] table 4.
Positive pole [3] comparative example 3
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [3] embodiment 9.Battery is commented The result of valency is shown in positive pole [3] table 4.
Positive pole [3] table 4
[table 16]
Positive pole [3] embodiment 13
Using positive active material A and positive active material D with 2:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, thickness is rolled into press for 74 μm, and use 32 positive poles and 33 Negative pole, in addition, equally implements with positive pole [3] embodiment 1.(positive electrode active material layer thickness/positive pole current collections of positive pole one side The thickness of body) it is 2.0, the ratio between the summation of the electrode area of positive pole and the case surface product summation of battery are 20.6.The mixing The BET specific surface area of positive active material is 1.2m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 6.7 μm, jolt ramming Density is 2.2g/cm2.The result of cell evaluation is shown in positive pole [3] table 5.
Positive pole [3] embodiment 14
Make the methanesulfonic acid trimethyl silyl ester that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, In addition, equally implement with positive pole [3] embodiment 13.The result of cell evaluation is shown in positive pole [3] table 5.
Positive pole [3] embodiment 15
Make the pheiiyldimetliyl silicon fluoride that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, except this with Outside, equally implement with positive pole [3] embodiment 13.The result of cell evaluation is shown in positive pole [3] table 5.
Positive pole [3] embodiment 16
Make the difluorophosphate that electrolyte contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, and just Pole [3] embodiment 13 is equally implemented.The result of cell evaluation is shown in positive pole [3] table 5.
Positive pole [3] comparative example 4
In addition to being free of hexamethyl cyclotrisiloxane in electrolyte, equally implement with positive pole [3] embodiment 13.Battery is commented The result of valency is shown in positive pole [3] table 5.
Positive pole [3] table 5
[table 17]
From the result of positive pole [3] 2~positive pole of table [3] table 5, in any one positive pole, due to all containing in the electrolytic solution There is specific compound, therefore, power output, capability retention are improved, and after cyclic test, can also be abundant Keep battery capacity and power output.
Positive pole [4] [positive active material]
The species and physical property of the positive active material used in the following examples and comparative example are as follows.
Positive pole [4] table 1
[table 18]
In positive pole [4] table 1, as the physical property of positive active material, according to the method for above-mentioned record, carry out BET and compare surface Product, average primary particle diameter (being determined with SEM), median particle diameter d50, tap density measure.
[positive active material A]
Positive active material A is the lithium cobalt composite oxide synthesized by method shown below, uses composition formula LiCoO2 Represent.With Li:Co=1:1 the molar ratio weighing LiOH as lithium raw material and the Co as cobalt raw material (OH)2, and add thereto Enter pure water and slurry is made, while stirring using circulating medium-stirring wet-type ball mill by the solid constituent wet type powder in slurry It is broken into 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, about 9 μm of the particle diameter of cobalt raw material Substantially spherical granulation particle.Under air circulation, 880 DEG C to the granulation particles sintering 6 hours (warming and cooling rate is 5 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material A.
[positive active material B]
Positive active material B is the lithium-transition metal composite oxide synthesized in the same manner as positive active material A, with composition Formula LiCoO2Represent, its difference is：The condition of spray drying is changed, the granulation particle of about 1 μm of particle diameter is made, and sinter Temperature is 860 DEG C.
[positive active material C]
The positive active material C sulphur that has been the surface attachment in positive active material A according to method synthesis shown below Positive active material formed by compound and antimonial.That is, 96.7 parts by weight positive active material A are stirred in flowing groove Mix, while the 1.3 parts sulfuric acid lithium (Li that spray thereto2SO4H2O the aqueous solution) is into spray form.Add in obtained mixture Plus 2.0 parts by weight antimony trioxide (Sb2O3, particle median particle diameter is 0.8 μm), it is sufficiently mixed.The mixture is transferred to aluminum oxide In container, sintered 2 hours in 680 DEG C under air atmosphere, obtain positive active material C.
[positive active material D]
Positive active material D is the lithium-transition metal composite oxide synthesized by method shown below, uses composition formula Li1.04Mn1.84Al0.12O4Represent.With Li:Mn:Al=1.04:1.84:0.12 molar ratio weighing as lithium raw material LiOH, It is used as the Mn of manganese raw material2O3With the AlOOH as aluminum feedstock, and thereto add pure water slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.5 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, manganese raw material, the grain of aluminum feedstock The substantially spherical granulation particle in about 10 μm of footpath.The granulation particle is sintered into 3 hours (programming rates at nitrogen circulation, 900 DEG C For 5 DEG C/min) after, circulated gases are transformed into air by nitrogen, then sinter at 900 DEG C 2 hours (cooling rate is 1 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material D.
Positive pole [4] embodiment 1
《The making of positive pole》
Mixed in N methyl pyrrolidone solvents 85 mass % as positive active material positive active material A, 10 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and thickness is rolled into press for 85 μm, then be cut into The shape of uncoated portion with wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm, is made positive pole.Just The density of pole active material is 2.35g/cm3, the value of (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 2.3。
《The making of negative pole》
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into width 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm not The shape of coated portion, is used as negative pole.
《The making of nonaqueous electrolytic solution》
Under dry argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) 3:3:The in the mixed solvent of 4 (volume ratios), the lithium hexafluoro phosphate fully dried with 1mol/L concentration dissolving (LiPF6).In addition, the hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making of battery》
31 positive poles and 32 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made battery.The ratio between the electrode area summation of positive pole and the case surface product summation of battery are 20.0。
《The evaluation of battery》
(assay method of battery capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.The 0.2C discharge capacities of the 5th circulation now are held as initial stage Amount.The result of cell evaluation is shown in positive pole [4] table 2.
The assay method of power output (initial stage)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).The result of cell evaluation is shown in positive pole [4] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.2V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, carries out the discharge and recharge of 3 circulations in the environment of 25 DEG C with 0.2C current value, is discharged and held with the 0.2C of the 3rd circulation Amount is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carries out output test, as durable Power output afterwards.The result of cell evaluation is shown in positive pole [4] table 2.
Positive pole [4] embodiment 2
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [4] embodiment 1.The result of cell evaluation is shown in positive pole [4] table 2.
Positive pole [4] embodiment 3
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [4] embodiment 1.The result of cell evaluation is shown in positive pole [4] table 2.
Positive pole [4] embodiment 4
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [4] embodiment 1.The result of cell evaluation is shown in positive pole [4] table 2.
Positive pole [4] comparative example 1
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [4] embodiment 1.Electricity The result that pond is evaluated is shown in positive pole [4] table 2.
Positive pole [4] table 2
[table 19]
Positive pole [4] embodiment 5
Except using positive active material B as positive active material, it is made beyond positive pole, it is same with positive pole [4] embodiment 1 Sample is implemented.The result of cell evaluation is shown in positive pole [4] table 3.
Positive pole [4] embodiment 6
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [4] embodiment 5.The result of cell evaluation is shown in positive pole [4] table 3.
Positive pole [4] embodiment 7
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [4] embodiment 5.The result of cell evaluation is shown in positive pole [4] table 3.
Positive pole [4] embodiment 8
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [4] embodiment 5.The result of cell evaluation is shown in positive pole [4] table 3.
Positive pole [4] comparative example 2
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [4] embodiment 5.Electricity The result that pond is evaluated is shown in positive pole [4] table 3.
Positive pole [4] table 3
[table 20]
Positive pole [4] embodiment 9
Using positive active material A and positive active material B with 2:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, in addition, equally implements with positive pole [4] embodiment 1.The positive pole of the mixing The BET specific surface area of active material is 1.8m2/ g, average primary particle diameter is 0.2 μm, median particle diameter d50For 4.9 μm, tap density For 1.8g/cm3.Cell evaluation result is shown in positive pole [4] table 4.
Positive pole [4] embodiment 10
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [4] embodiment 9.The result of cell evaluation is shown in positive pole [4] table 4.
Positive pole [4] embodiment 11
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [4] embodiment 9.The result of cell evaluation is shown in positive pole [4] table 4.
Positive pole [4] embodiment 12
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [4] embodiment 9.The result of cell evaluation is shown in positive pole [4] table 4.
Positive pole [4] comparative example 3
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [4] embodiment 9.Electricity The result that pond is evaluated is shown in positive pole [4] table 4.
Positive pole [4] table 4
[table 21]
Positive pole [4] embodiment 13
Except using positive active material C as positive active material, it is made beyond positive pole, it is same with positive pole [4] embodiment 1 Sample is implemented.The result of cell evaluation is shown in positive pole [4] table 5.
Positive pole [4] embodiment 14
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [4] embodiment 13.The result of cell evaluation is shown in positive pole [4] table 5.
Positive pole [4] embodiment 15
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [4] embodiment 13.The result of cell evaluation is shown in positive pole [4] table 5.
Positive pole [4] embodiment 16
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [4] embodiment 13.The result of cell evaluation is shown in positive pole [4] table 5.
Positive pole [4] comparative example 4
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [4] embodiment 13.Electricity The result that pond is evaluated is shown in positive pole [4] table 5.
Positive pole [4] table 5
[table 22]
Positive pole [4] embodiment 17
Using positive active material A and positive active material D with 2:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 92 μm of thickness is rolled into press, and negative using 30 positive poles and 31 Pole, in addition, equally implements with positive pole [4] embodiment 1.(the positive electrode active material layer thickness of positive pole one side)/(positive pole current collections The thickness of body) it is 2.6, the ratio between the electrode area summation of positive pole and the case surface product summation of battery are 19.4.In addition, the mixing Positive active material BET specific surface area be 1.1m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 7.3 μm, shake Real density is 2.2g/cm3.Cell evaluation result is shown in positive pole [4] table 6.
Positive pole [4] embodiment 18
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [4] embodiment 17.The result of cell evaluation is shown in positive pole [4] table 6.
Positive pole [4] embodiment 19
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [4] embodiment 17.The result of cell evaluation is shown in positive pole [4] table 6.
Positive pole [4] embodiment 20
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [4] embodiment 17.The result of cell evaluation is shown in positive pole [4] table 6.
Positive pole [4] comparative example 5
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [4] embodiment 17.Electricity The result that pond is evaluated is shown in positive pole [4] table 6.
Positive pole [4] table 6
[table 23]
It was found from the result of positive pole [4] 2~positive pole of table [4] table 6, in any one positive pole, due in nonaqueous electrolytic solution All contain specific compound, initial stage, power output was improved.In addition, capability retention is improved, even in cyclic test Afterwards, battery capacity and power output can also fully be kept.
Positive pole [5] [positive active material]
The species and physical property of the positive active material used in the following examples and comparative example are as follows.
Positive pole [5] table 1
[table 24]
In positive pole [5] table 1, as the physical property of positive active material, according to the method for above-mentioned record, carry out BET and compare surface Product, average primary particle diameter (being determined with SEM), median particle diameter d50, tap density measure.
[positive active material A]
Positive active material A is the lithium cobalt composite oxide synthesized by method shown below, uses composition formula LiCoO2 Represent.With Li:Co=1:1 the molar ratio weighing LiOH as lithium raw material and the Co as cobalt raw material (OH)2, and add thereto Enter pure water and slurry is made, while stirring using circulating medium-stirring wet-type ball mill by the solid constituent wet type powder in slurry It is broken into 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtains only including lithium raw material, about 9 μm of the particle diameter of cobalt raw material Substantially spherical granulation particle.Under air circulation, 880 DEG C to the granulation particles sintering 6 hours (warming and cooling rate is 5 DEG C/ Minute).It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive active material A.
[positive active material B]
Positive active material B is the lithium-transition metal composite oxide synthesized by the following method, with composition formula Li1.05Ni0.80Co0.2O2Represent.With Ni:Co=80:20 molar ratio weighing is used as the Co of cobalt raw material as the NiO of nickel raw material (OH)2, and slurry is made in addition pure water thereto, while stirring using circulating medium-stirring wet-type ball mill by slurry Solid constituent case of wet attrition into 0.25 μm of median particle diameter.
Slurry is spray-dried by spray dryer, it is about 8 to obtain only bag nickel bearing raw material, the particle diameter of cobalt raw material μm substantially spherical granulation particle.Addition median particle diameter is 3 μm of LiOH powder in obtained granulation particle so that Li's The ratio between molal quantity and Ni and Co total mole number is 1.05, mixed with high-speed mixer, obtains nickel raw material, cobalt raw material and makes The mixed-powder of grain particle and lithium raw material.In sintering at 740 DEG C, (warming and cooling rate is 5 DEG C/minute to the mixed-powder under oxygen circulation Clock) 6 hours, then crushed, by 45 μm of sieve of mesh, obtain positive active material B.
[positive active material C]
Positive active material C is the lithium-transition metal composite oxide synthesized by the following method, with composition formula Li1.05Ni0.80Co0.15Al0.05O2Represent.With Ni:Co:Al=80:15:5 molar ratio weighing as nickel raw material NiO, as The Co (OH) of cobalt raw material2And as the AlOOH of aluminum feedstock, pure water is added thereto slurry is made, while stirring using circulation Formula medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.25 μm of median particle diameter.
Slurry is spray-dried by spray dryer, the grain of only bag nickel bearing raw material, cobalt raw material, aluminum feedstock is obtained The substantially spherical granulation particle in about 10 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle so that The ratio of total mole number of the Li molal quantity relative to Ni, Co and Al is 1.05, is mixed with high-speed mixer, obtains nickel former Material, cobalt raw material, the granulation particle and the mixed-powder of lithium raw material of aluminum feedstock.The mixed-powder is under oxygen circulation in burning at 740 DEG C Knot (warming and cooling rate is 5 DEG C/min) 6 hours, is then crushed, by 45 μm of sieve of mesh, obtains positive electrode active material Matter C.
[positive active material D]
The positive active material C sulphur that has been the surface attachment in positive active material C according to method synthesis shown below Positive active material formed by compound and antimonial.That is, 96.7 parts by weight positive active material C are stirred in flowing groove Mix, while the 1.3 parts sulfuric acid lithium (Li that spray thereto2SO4H2O the aqueous solution) is into spray form.Add in obtained mixture Plus 2.0 parts by weight antimony trioxide (Sb2O3, particle median particle diameter is 0.8 μm), it is sufficiently mixed.The mixture is transferred to aluminum oxide In container, sintered 2 hours in 680 DEG C under air atmosphere, obtain positive active material D.
[positive active material E]
Positive active material E is the lithium-transition metal composite oxide synthesized by the following method, with composition formula LiMn0.33Ni0.33Co0.33O2Represent.With Mn:Ni:Co=1:1:1 molar ratio weighing as manganese raw material Mn3O4, be used as nickel former The NiO of the material and Co (OH) as cobalt raw material2, pure water is added thereto slurry is made, while stirring using circulating medium Stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, only bag raw material containing manganese, nickel raw material, the grain of cobalt raw material is obtained The substantially spherical granulation particle in about 5 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle so that The ratio between the total mole number of Li molal quantity relative to Mn, Ni and Co is 1.05, is mixed with high-speed mixer, obtains manganese former The granulation particle and the mixed-powder of lithium raw material of material, nickel raw material, cobalt raw material.The mixed-powder is under oxygen circulation in burning at 950 DEG C Knot (warming and cooling rate is 5 DEG C/min) 12 hours, is then crushed, by 45 μm of sieve of mesh, obtains positive electrode active material Matter E.
[positive active material F]
Positive active material F is the lithium-transition metal composite oxide synthesized by the following method, with composition formula Li1.04Mn1.84Al0.12O4Represent.With Li:Mn:Al=1.04:1.84:0.12 molar ratio weighing as lithium raw material LiOH, It is used as the Mn of manganese raw material2O3With the AlOOH as aluminum feedstock, pure water is added thereto slurry is made, while stirring using circulating Medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry into 0.5 μm of median particle diameter.
Slurry is spray-dried by spray dryer, obtained only comprising lithium raw material, manganese raw material and aluminum feedstock The substantially spherical granulation particle of about 10 μm of particle diameter.Obtained granulation particle (is lifted under nitrogen circulation in sintering at 900 DEG C Warm speed is 5 DEG C/min) 3 hours, then, circulated gases are transformed into air, then sintering (the cooling speed at 900 DEG C by nitrogen Spend for 1 DEG C/min) 2 hours.It is cooled to after room temperature, takes out and crush, by 45 μm of sieve of mesh, obtains positive electrode active material Matter F.
Positive pole [5] embodiment 1
《The making of positive pole》
By positive active material A and negative electrode active material B with 1:1 mass ratio is sufficiently mixed, and is lived using obtained positive pole Property material make positive pole.The BET specific surface area of the mixed positive active material is 1.2m2/ g, average primary particle diameter is 0.8 μm, median particle diameter d50For 6.5 μm, tap density is 2.1g/cm3。
The above-mentioned mixed positive active material A of 90 mass %, 5 mass % are mixed in N methyl pyrrolidone solvents The acetylene black and 5 mass % as conductive material as the Kynoar (PVdF) of adhesive, slurry is made.By what is obtained Slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and thickness is rolled into press for 70 μm, then be cut into width The shape of 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm uncoated portion, is made positive pole.Positive-active The density of material is 2.35g/cm3, the value of (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 1.8.
《The making of negative pole》
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into width 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm not The shape of coated portion, is used as negative pole.
《The making of nonaqueous electrolytic solution》
Under dry argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) 3:3:The in the mixed solvent of 4 (volume ratios), the lithium hexafluoro phosphate fully dried with 1mol/L concentration dissolving (LiPF6).In addition, the hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making of battery》
33 positive poles and 34 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made battery.The ratio between the electrode area summation of positive pole and the case surface product summation of battery are 21.3。
《The evaluation of battery》
(assay method of battery capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.The 0.2C discharge capacities of the 5th circulation now are held as initial stage Amount.The result of cell evaluation is shown in positive pole [5] table 2.
The assay method of power output (initial stage)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).The result of cell evaluation is shown in positive pole [5] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.2V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, carries out the discharge and recharge of 3 circulations in the environment of 25 DEG C with 0.2C current value, is discharged and held with the 0.2C of the 3rd circulation Amount is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carries out output test, as durable Power output afterwards.The result of cell evaluation is shown in positive pole [5] table 2.
Positive pole [5] embodiment 2
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 1.The result of cell evaluation is shown in positive pole [5] table 2.
Positive pole [5] embodiment 3
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 1.The result of cell evaluation is shown in positive pole [5] table 2.
Positive pole [5] embodiment 4
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 1.The result of cell evaluation is shown in positive pole [5] table 2.
Positive pole [5] comparative example 1
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 1.Electricity The result that pond is evaluated is shown in positive pole [5] table 2.
Positive pole [5] table 2
[table 25]
Positive pole [5] embodiment 5
Using positive active material A and positive active material E with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 78 μm of thickness is rolled into press, and negative using 32 positive poles and 33 Pole, in addition, equally implements with positive pole [5] embodiment 1.(the positive electrode active material layer thickness of positive pole one side)/(positive pole current collections The thickness of body) it is 2.1, the ratio between the electrode area summation of positive pole and the case surface product summation of battery are 20.6.The mixing is just The BET specific surface area of pole active material is 1.2m2/ g, average primary particle diameter is 0.8 μm, median particle diameter d50For 5.7 μm, vibration density Spend for 2.0g/cm3.Cell evaluation result is shown in positive pole [5] table 3.
Positive pole [5] embodiment 6
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 5.The result of cell evaluation is shown in positive pole [5] table 3.
Positive pole [5] embodiment 7
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 5.The result of cell evaluation is shown in positive pole [5] table 3.
Positive pole [5] embodiment 8
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 5.The result of cell evaluation is shown in positive pole [5] table 3.
Positive pole [5] comparative example 2
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 5.Electricity The result that pond is evaluated is shown in positive pole [5] table 3.
Positive pole [5] table 3
[table 26]
Positive pole [5] embodiment 9
Using positive active material A and positive active material F with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 91 μm of thickness is rolled into press, and negative using 30 positive poles and 31 Pole, in addition, equally implements with positive pole [5] embodiment 1.(the positive electrode active material layer thickness of positive pole one side)/(positive pole current collections The thickness of body) it is 2.5, the ratio between the electrode area summation of positive pole and the case surface product summation of battery are 19.4.The mixing is just The BET specific surface area of pole active material is 1.0m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 7.5 μm, vibration density Spend for 2.2g/cm3.Cell evaluation result is shown in positive pole [5] table 4.
Positive pole [5] embodiment 10
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 9.The result of cell evaluation is shown in positive pole [5] table 4.
Positive pole [5] embodiment 11
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 9.The result of cell evaluation is shown in positive pole [5] table 4.
Positive pole [5] embodiment 12
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 9.The result of cell evaluation is shown in positive pole [5] table 4.
Positive pole [5] comparative example 3
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 9.Electricity The result that pond is evaluated is shown in positive pole [5] table 4.
Positive pole [5] table 4
[table 27]
Positive pole [5] embodiment 13
Using positive active material C and positive active material E with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 72 μm of thickness is rolled into press, negative using 33 positive poles and 34 Pole, in addition, equally implements with positive pole [5] embodiment 1.The BET specific surface area of the mixed positive active material is 0.9m2/ g, average primary particle diameter is 0.7 μm, median particle diameter d50For 6.7 μm, tap density is 2.0g/cm3.(positive pole one side Positive electrode active material layer thickness)/(thickness of positive electrode collector) be 1.9, the electrode area summation of positive pole and the shell table of battery The ratio between area summation is 21.3.Except the voltage range in solid measure be 3.0~4.1V, cyclic test upper voltage limit be 4.1V In addition, battery is evaluated in the same manner as positive pole [5] embodiment 1.Cell evaluation result is shown in positive pole [5] table 5.
Positive pole [5] embodiment 14
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 13.The result of cell evaluation is shown in positive pole [5] table 5.
Positive pole [5] embodiment 15
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 13.The result of cell evaluation is shown in positive pole [5] table 5.
Positive pole [5] embodiment 16
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 13.The result of cell evaluation is shown in positive pole [5] table 5.
Positive pole [5] comparative example 4
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 13.Electricity The result that pond is evaluated is shown in positive pole [5] table 5.
Positive pole [5] table 5
[table 28]
Positive pole [5] embodiment 17
Using positive active material C and positive active material F with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 78 μm of thickness is rolled into press, negative using 32 positive poles and 33 Pole, in addition, equally implements with positive pole [5] embodiment 1.(the positive electrode active material layer thickness of positive pole one side)/(positive pole current collections The thickness of body) it is 2.1, the ratio between the electrode area summation of positive pole and the case surface product summation of battery are 20.6.The mixing is just The BET specific surface area of pole active material is 0.8m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 8.5 μm, vibration density Spend for 2.2g/cm3.Cell evaluation result is shown in positive pole [5] table 6.
Positive pole [5] embodiment 18
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 6.
Positive pole [5] embodiment 19
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 6.
Positive pole [5] embodiment 20
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 6.
Positive pole [5] comparative example 5
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 17.Electricity The result that pond is evaluated is shown in positive pole [5] table 6.
Positive pole [5] table 6
[table 29]
Positive pole [5] embodiment 21
Using positive active material D and positive active material E with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 72 μm of thickness is rolled into press, negative using 33 positive poles and 34 Pole, in addition, equally implements with positive pole [5] embodiment 1.The BET specific surface area of the mixed positive active material is 0.9m2/ g, average primary particle diameter is 0.7 μm, median particle diameter d50For 6.7 μm, tap density is 2.0g/cm3.(positive pole one side Positive electrode active material layer thickness)/(thickness of positive electrode collector) be 1.9, the electrode area summation of positive pole and the shell table of battery The ratio between area summation is 21.3.Except the voltage range in solid measure be 3.0~4.1V, cyclic test upper voltage limit be 4.1V In addition, battery is evaluated in the same manner as positive pole [5] embodiment 1.Cell evaluation result is shown in positive pole [5] table 7.
Positive pole [5] embodiment 22
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 7.
Positive pole [5] embodiment 23
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 7.
Positive pole [5] embodiment 24
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 7.
Positive pole [5] comparative example 6
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 17.Electricity The result that pond is evaluated is shown in positive pole [5] table 7.
Positive pole [5] table 7
[table 30]
Positive pole [5] embodiment 25
Using positive active material E and positive active material F with 1:Positive-active obtained from 1 mass ratio is sufficiently mixed Positive pole is made as positive active material in material, and 86 μm of thickness is rolled into press, negative using 31 positive poles and 32 Pole, in addition, equally implements with positive pole [5] embodiment 1.(the positive electrode active material layer thickness of positive pole one side)/(positive pole current collections The thickness of body) it is 2.4, the ratio between the electrode area summation of positive pole and the case surface product summation of battery are 20.0.This is mixed The BET specific surface area of positive active material is 1.1m2/ g, average primary particle diameter is 0.6 μm, median particle diameter d50For 6.2 μm, jolt ramming Density is 2.0g/cm3.Cell evaluation result is shown in positive pole [5] table 8.
Positive pole [5] embodiment 26
Make the methanesulfonic acid trimethyl silyl ester that nonaqueous electrolytic solution contains 0.3 mass % to replace the silica of pregnancy basic ring three Alkane, in addition, equally implements with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 8.
Positive pole [5] embodiment 27
Make the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, remove Beyond this, equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 8.
Positive pole [5] embodiment 28
Make the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % to replace hexamethyl cyclotrisiloxane, in addition, Equally implement with positive pole [5] embodiment 17.The result of cell evaluation is shown in positive pole [5] table 8.
Positive pole [5] comparative example 7
In addition to being free of hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, equally implement with positive pole [5] embodiment 17.Electricity The result that pond is evaluated is shown in positive pole [5] table 8.
Positive pole [5] table 8
[table 31]
It was found from the result of positive pole [5] 2~positive pole of table [5] table 8, in any one positive pole, due in nonaqueous electrolytic solution All contain specific compound, therefore, power output, capability retention are improved, and after cyclic test, can also Fully keep battery capacity and power output.
Negative pole [1] [making of negative electrode active material]
(making 1 of negative electrode active material)
In order to prevent being mixed into oversize grain in the commercially available natural graphite powder as particle shape carbonaceous material, use The sieve of ASTM400 mesh is sieved 5 times repeatedly.It regard the negative material so obtained as carbonaceous material (A).
(making 2 of negative electrode active material)
The petroleum-type heavy oil obtained when being pyrolyzed in non-active gas to naphtha implements 1300 DEG C of carbonization treatment, so Afterwards, carbonaceous material (B) is obtained by carrying out classification processing to sinter.In classification processing, in order to prevent being mixed into oversize grain, make Sieved repeatedly 5 times with the sieve of ASTM400 mesh.
(making 3 of negative electrode active material)
95 mass % carbonaceous material (A) and 5 mass % carbonaceous material (B) are uniformly mixed, mixture is regard as 2 kinds Crystallinity carbonaceous material mixture (C).
(making 4 of negative electrode active material)
The petroleum-type heavy oil obtained in carbonaceous material (A) during the pyrolysis of mixing naphtha, implements in non-active gas 1300 DEG C of carbonization treatment, then, carbonaceous material (D), the composite carbonaceous thing is obtained by carrying out classification processing to sinter Matter (D) is that the composite carbonaceous material with different crystalline carbonaceous materials has been coated on carbonaceous material (A) particle surface.Point During level processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.From carbon yield it was determined that Obtained negative electrode active material powder is coated relative to 95 parts by weight of graphite for the low-crystalline carbonaceous material of 5 weight.
(making 5 of negative electrode active material)
In making 4 except reducing negative electrode active material the petroleum-type heavy oil that is obtained when naphtha be pyrolyzed and mixing with Outside, carried out according to the same method of the making 4 with negative electrode active material, obtain composite carbonaceous material (E), it is by relative to 99 weights Part graphite is measured to coat for the low-crystalline carbonaceous material of 1 weight.
(making 6 of negative electrode active material)
In making 4 except increasing negative electrode active material the petroleum-type heavy oil that is obtained when naphtha be pyrolyzed and mixing with Outside, carried out according to the same method of the making 4 with negative electrode active material, obtain composite carbonaceous material (F), it is by relative to 90 weights Part graphite is measured to coat for the low-crystalline carbonaceous material of 10 weight.
(making 7 of negative electrode active material)
In making 4 except increasing negative electrode active material the petroleum-type heavy oil that is obtained when naphtha be pyrolyzed and mixing with Outside, carried out according to the same method of the making 4 with negative electrode active material, obtain composite carbonaceous material (G), it is by relative to 70 weights Part graphite is measured to coat for the low-crystalline carbonaceous material of 30 weight.
(making 8 of negative electrode active material)
In addition to implementing 3000 DEG C of graphitization processing in non-active gas in the making 4 in negative electrode active material, Carried out according to the identical method of making 4 with negative electrode active material, obtain composite carbonaceous material (I), it is by relative to 95 weight Part graphite coats for the low-crystalline carbonaceous material of 5 weight.
(making 9 of negative electrode active material)
Mixing phenol-formalin in carbonaceous material (A), the carbonization treatment of 1300 DEG C of implementation in non-active gas, Then, composite carbonaceous material powder is obtained by carrying out classification processing to sinter, the composite carbonaceous material powder is in stone The composite carbonaceous material powder with different crystalline carbonaceous materials has been coated on black particle surface.During classification processing, in order to Prevent from being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, obtain composite carbonaceous material (J).Can from carbon yield To determine, obtained negative electrode active material powder is by relative to the low-crystalline carbonaceous material bag that 95 parts by weight of graphite are 5 weight Cover.
(making 10 of negative electrode active material)
In reacting furnace at 460 DEG C by the composition insoluble in quinoline for below 0.05 mass % coal tar asphalt carry out It is heat-treated within 10 hours, will be obtained using pulverizer (the orient mill (オ リ エ Application ト ミ Le) that seishin enterprise-like corporations manufacture) Block carbonaceous material crush, reuse the atomizer turbine type of manufacture (matsubo (マ Star ボ ー) company mill) carry out it is micro- Crush, miniaturization to 17 μm of median particle diameter.In the container that the particle is fitted into metal manufacture, in the electric furnace of box-shaped, nitrogen stream In 540 DEG C be heat-treated within 2 hours under logical.With Roughpulverizer, (Jitian makes manufactured roll-type and crushed obtained cake mass Machine (ロ ー Le ジ ョ ー Network ラ ッ シ ャ ー)) crushed, then entered with atomizer (turbine type that matsubo companies manufacture is ground) Row Crushing of Ultrafine, obtained powder is loaded in container, under nitrogen atmosphere, sintered 1 hour at 1300 DEG C with electric furnace.Then, Classification processing is carried out to obtained sinter, carbonaceous material (K) is thus obtained.During classification processing, in order to prevent from being mixed into thick grain Son, is sieved 5 times repeatedly using the sieve of ASTM400 mesh.
(making 11 of negative electrode active material)
Mixing phenol-formalin in carbonaceous material (K), the carbonization treatment of 1300 DEG C of implementation in non-active gas, Then, composite carbonaceous material powder is obtained by carrying out classification processing to sinter, the composite carbonaceous material powder is in stone The composite carbonaceous material powder with different crystalline carbonaceous materials has been coated on black particle surface.During classification processing, in order to Prevent from being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, obtain composite carbonaceous material (L).Can from carbon yield To determine, obtained negative electrode active material powder is by relative to the low-crystalline carbonaceous material bag that 60 parts by weight of graphite are 40 weight Cover.
(making 12 of negative electrode active material)
The petroleum-type heavy oil obtained in carbonaceous material (K) during the pyrolysis of mixing naphtha, implements in non-active gas 1300 DEG C of carbonization treatment, then, composite carbonaceous material powder, the composite carbon is obtained by carrying out classification processing to sinter Metallic substance powder is that the composite carbonaceous material powder with different crystalline carbonaceous materials has been coated on Graphite particle surfaces. During classification processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, obtain composite carbonaceous material (M).From carbon yield it was determined that obtained negative electrode active material powder is by relative to the low knot that 95 parts by weight of graphite are 5 weight Crystalline substance carbonaceous material is coated.
(making 13 of negative electrode active material)
In reacting furnace at 460 DEG C by the composition insoluble in quinoline for below 0.05 mass % coal tar asphalt carry out It is heat-treated within 10 hours, using pulverizer (senshin enterprise-like corporations manufacture orient mill) by obtained block carbonaceous material Crush, reuse atomizer (the turbine type mill of matsubo companies manufacture) and carry out Crushing of Ultrafine, miniaturization to the μ of median particle diameter 17 m.In the container that the particle is fitted into metal manufacture, carried out in the electric furnace of box-shaped, under nitrogen circulation in 540 DEG C at 2 hours heat Reason.Obtained cake mass is crushed with Roughpulverizer (Jitian makes manufactured roll crusher), then uses atomizer (the turbine type mill of matsubo companies manufacture) carries out Crushing of Ultrafine, and obtained powder is loaded in container, under nitrogen atmosphere, used Electric furnace is sintered 1 hour at 1000 DEG C.Then, the powder after sintering is transferred in graphite crucible, with direct-electrifying stove non- In carrying out graphitization with 5 hours at 3000 DEG C in active gases atmosphere, carbonaceous material (N) is obtained.Mixed in carbonaceous material (N) The petroleum-type heavy oil that naphtha is obtained when being pyrolyzed, the carbonization treatment of 900 DEG C of implementation in non-active gas, then, by burning Knot thing carries out classification processing and obtains carbonaceous material (O), and the composite carbonaceous material (O) is that tool has been coated on Graphite particle surfaces Obtained from having a different crystalline carbonaceous materials.During classification processing, in order to prevent being mixed into oversize grain, ASTM400 mesh is used Sieve sieve repeatedly 5 times.From carbon yield it was determined that obtained negative electrode active material powder is relative to 95 parts by weight of graphite The low-crystalline carbonaceous material cladding of 5 weight.
(making 14 of negative electrode active material)
In addition to the carbonaceous material (A) in the making 4 that negative electrode active material is replaced using flake natural graphite, press Carried out according to the identical method of making 4 with negative electrode active material, obtain composite carbonaceous material (P), it is by relative to 95 parts by weight Graphite coats for the low-crystalline carbonaceous material of 5 weight.
(making 15 of negative electrode active material)
In making 14 except reducing negative electrode active material the petroleum-type heavy oil that is obtained when naphtha be pyrolyzed and mixing with Outside, carry out, then, obtained powder be transferred in graphite crucible according to the same method of the making 4 with negative electrode active material, With direct-electrifying stove in non-active gas atmosphere in carrying out graphitization with 5 hours at 3000 DEG C.Then, by entering to sinter Row classification processing obtains carbonaceous material (Q), and the composite carbonaceous material (Q) has been coated on Graphite particle surfaces with difference Obtained from crystalline carbonaceous material.During classification processing, in order to prevent being mixed into oversize grain, the sieve of ASTM400 mesh is used Sieve 5 times repeatedly.From carbon yield it was determined that obtained negative electrode active material powder is 1 weight relative to 99 parts by weight of graphite Low-crystalline carbonaceous material cladding.
(making 16 of negative electrode active material)
Except the carbonaceous in the making 4 using the native graphite that volume average particle size is 48 μm to replace negative electrode active material Beyond material (A), carried out according to the identical method of making 4 with negative electrode active material, obtain composite carbonaceous material (R), its quilt Coated relative to 95 parts by weight of graphite for the low-crystalline carbonaceous material of 5 weight.
(making 17 of negative electrode active material)
Except remaining the native graphite of 1% ash content using degree of purification is low and replacing the making 4 of negative electrode active material In carbonaceous material (A) beyond, according to negative electrode active material the identical method of making 4 carry out, obtain composite carbonaceous material (S), it is coated relative to 95 parts by weight of graphite for the low-crystalline carbonaceous material of 5 weight.
The physical property of obtained negative electrode active material is shown in negative pole [1] table 1.The assay method of physical property is same as described above.
Negative pole [1] table 1
[table 32]
Negative pole [1] [making of battery]
《The making 1 of positive pole》
The 90 mass % cobalt acid lithium (LiCoO as positive active material is mixed in 1-METHYLPYRROLIDONE solvent2)、 Slurry is made as the Kynoar (PVdF) of adhesive in the 5 mass % acetylene black and 5 mass % as conductive material. Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, 80 μm of thickness is rolled into press, then be cut into The shape of uncoated portion with wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm, is used as positive pole.This When positive active material density be 2.35g/cm3。
《The making 2 of positive pole》
In addition to 2 times of the making 1 that the quality of the active material of every coated on one side is positive pole, the making 1 with positive pole is same Carry out the making of anode electrode sample.
《The making 3 of positive pole》
Mixed in 1-METHYLPYRROLIDONE solvent 90 mass % as positive active material LiNi0.80Co0.15Al0.05O2, 5 mass % the acetylene black and 5 mass % as conductive material as adhesive polyvinylidene fluoride Alkene (PVdF), is made slurry.Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, is rolled into press 65 μm of thickness, then it is cut into the uncoated portion with width 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm The shape divided, is used as positive pole.The density of positive active material now is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm, is used as negative pole.This When negative electrode active material density be 1.35g/cm3。
《The making 2 of negative pole》
In addition to 2 times of usage amount during the quality of the active material of every coated on one side is the making 1 of negative pole, with negative pole Make 1 making for similarly carrying out negative electrode.
《The making 3 of negative pole》
The density of the active material of side is 1.70g/cm in making 1 except making negative pole3In addition, with the making 1 of negative pole Similarly carry out the making of negative electrode.
《The making 4 of negative pole》
100 parts by weight are added in 95 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 8 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into and have The shape of wide 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm uncoated portion, is used as negative pole.Now Active material density is 1.35g/cm3。
《The making 1 of electrolyte》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of electrolyte》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of electrolyte》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of electrolyte》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
《The making 1 of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).
《The making 2 of battery》
16 positive poles and 17 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 7 milliohms (m Ω).
Negative pole [1] embodiment 1
Use with《The making 1 of negative pole》The negative electrode active material of item is as two kinds of crystallinity carbonaceous material mixtures (C) The negative pole that is made,《The making 1 of positive pole》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through 《The making 1 of battery》Method in makes battery.By following《The evaluation of battery》Method and said determination described in Method is measured to the battery.
Negative pole [1] embodiment 2
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (D) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 3
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (E) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 4
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (F) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 5
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (G) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 6
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (J) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 7
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (I) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 8
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (M) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 9
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (R) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 10
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (L) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 11
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (S) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 12
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (O) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 13
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (P) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 14
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses composite carbonaceous material (Q) In addition, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 15
Use with《The making 2 of negative pole》Negative electrode active material be made as composite carbonaceous material (D) negative pole, 《The making 2 of positive pole》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through《The making of battery 2》Method in makes battery.In addition, carrying out the evaluation of battery in the same manner as negative pole [1] embodiment 1.
Negative pole [1] embodiment 16
Use with《The making 3 of negative pole》Negative electrode active material be made as composite carbonaceous material (D) negative pole, 《The making 1 of positive pole》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through《The making of battery 1》Method in makes battery.In addition, carrying out the evaluation of battery in the same manner as negative pole [1] embodiment 1.
Negative pole [1] embodiment 17
Use with《The making 4 of negative pole》Negative electrode active material be made as composite carbonaceous material (D) negative pole, 《The making 1 of positive pole》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through《The making of battery 1》Method in makes battery.In addition, carrying out the evaluation of battery in the same manner as negative pole [1] embodiment 1.
The evaluation result of negative pole [1] 1~negative pole of embodiment [1] embodiment 17 is shown in negative pole [1] table 2.
Negative pole [1] embodiment 18~34
Except the electrolyte of negative pole [1] embodiment 1~17 is replaced with《The making 2 of electrolyte》Make electrolyte with Outside, the evaluation of battery is carried out in the same way.The evaluation result of negative pole [1] 18~negative pole of embodiment [1] embodiment 34 is shown in Negative pole [1] table 3.
Negative pole [1] embodiment 35~51
Except the electrolyte of negative pole [1] embodiment 1~17 is replaced with《The making 3 of electrolyte》Make electrolyte with Outside, the evaluation of battery is carried out in the same way.The evaluation result of negative pole [1] 35~negative pole of embodiment [1] embodiment 51 is shown in Negative pole [1] table 4.
Negative pole [1] comparative example 1
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (A), Battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 2
Except the electrolyte of negative pole [1] comparative example 1 is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, equally Ground makes battery, and carries out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 3
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (B), Battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 4
Except the electrolyte of negative pole [1] comparative example 3 is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, with bearing Pole [1] comparative example 3 similarly makes battery, and carries out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 5
Except the electrolyte of negative pole [1] embodiment 1 is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, with bearing Pole [1] embodiment 1 similarly makes battery, and carries out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 6
Except the electrolyte of negative pole [1] embodiment 2 is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, equally Ground makes battery, and carries out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 7
Except negative pole [1] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (K), Battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 8
Except the electrolyte of negative pole [1] comparative example 7 is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, equally Ground makes battery, and carries out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 9~11
Except the electrolyte of negative pole [1] comparative example 1,3,7 is replaced with《The making 2 of electrolyte》Make electrolyte with Outside, the evaluation of battery is carried out in the same way.
Negative pole [1] comparative example 12~14
Except the electrolyte of negative pole [1] comparative example 1,3,7 is replaced with《The making 3 of electrolyte》Make electrolyte with Outside, the evaluation of battery is carried out in the same way.
The evaluation result of negative pole [1] 1~negative pole of comparative example [1] comparative example 14 is shown in negative pole [1] table 5.
Negative pole [1] embodiment 52
Use with《The making 1 of negative pole》Negative electrode active material be made as composite carbonaceous material (D) negative pole, 《The making 1 of positive pole》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through《The system of battery Make 1》Method in makes battery, carries out《The evaluation of battery》Cell evaluation described in.
Negative pole [1] embodiment 53
Except electrolyte is used《The making 2 of electrolyte》Beyond the electrolyte that item makes, made in the same manner as embodiment 52 Battery, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] embodiment 54
Except electrolyte is used《The making 3 of electrolyte》Beyond the electrolyte that item makes, made in the same manner as embodiment 52 Battery, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [1] comparative example 15
Except electrolyte is used《The making 4 of electrolyte》Beyond the electrolyte that item makes, made in the same manner as embodiment 52 Battery, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Embodiment 52~54 and the evaluation result of comparative example 15 are shown in negative pole [1] table 6.
Negative pole [1]《The evaluation of battery》
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.Then output test shown below is carried out.
(output test)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are wrapped The area of the triangle enclosed is used as power output (W).
(cyclic test)
In the case where being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery of hot environment, cyclic test is carried out. It is charged to 2C constant-current constant-voltage methods after charging upper limit voltage 4.2V, discharge off electricity is discharged to 2C constant current 3.0V is pressed, in this, as a charge and discharge cycles, the circulation is repeated, until 500 circulations.After terminating for cyclic test Battery, the discharge and recharges of 3 circulations are carried out in the environment of 25 DEG C, using the 0.2C discharge capacities of the 3rd circulation as after circulation Capacity.By the initial capacity determined before circulation and cyclic test terminate after after the circulation that determines capacity asked by following calculating formulas Go out to circulate conservation rate.
Circulate capacity/initial capacity after conservation rate (%)=100 × circulation
Battery after terminating to cyclic test carries out the output test that (output test) item is recorded.Now, make The power output that the power output implemented after being terminated with the power output before cyclic test and cyclic test calculates shown in following formula is protected Holdup.
Power output conservation rate (%)=100 × cyclic test terminates power output before rear power output/circulation
Impedance Rct and bilayer capacity C dl in negative pole [1] table 2 are to one of contributive parameter of power output, impedance Rct value is smaller, or double-deck capacity C dl value is bigger, then power output more has the tendency of improvement.In addition, " impedance Rct " and " double-deck capacity C dl " is by illustrating that the method described in the part of impedance is obtained.
Negative pole [1] table 2
[table 33]
In negative pole [1] table 2, electrolyte contains 0.3 mass %'s《The making 1 of electrolyte》The difluorophosphoric acid lithium salts of middle making (LiPO2F2)。
Negative pole [1] table 3
[table 34]
In negative pole [1] table 3, electrolyte contains 0.3 mass %'s《The making 2 of electrolyte》The methanesulfonic acid trimethyl of middle making Silyl ester.
Negative pole [1] table 4
[table 35]
In negative pole [1] table 4, electrolyte contains 0.3 mass %'s《The making 3 of electrolyte》The silicon of pregnancy basic ring three of middle making Oxygen alkane.
Negative pole [1] table 5
[table 36]
Negative pole [1] table 6
Table [36]
From the result of negative pole [1] table 2~6, by the way that difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl will be contained Ester, the situation of hexamethyl cyclotrisiloxane and the feelings for making the negative electrode active material carbonaceous material that to contain two or more crystallinity different Condition is combined, and the power output conservation rate after circulation can be made to obtain tremendous raising.
Negative pole [2] [making of negative electrode active material]
(making 1 of negative electrode active material)
In reacting furnace at 460 DEG C by the composition insoluble in quinoline for below 0.05 mass % coal tar asphalt carry out It is heat-treated within 10 hours, using pulverizer (seishin enterprise-like corporations manufacture orient mill) by obtained block carbonaceous material Crushed, reuse atomizer (the turbine type mill of matsubo companies manufacture) and carry out Crushing of Ultrafine, miniaturization to median particle diameter 18μm.In the container that the particle is encased in metal manufacture, in the electric furnace of box-shaped, carried out 2 hours in 540 DEG C under nitrogen circulation Heat treatment.Obtained cake mass is crushed with Roughpulverizer (Jitian makes manufactured roll crusher), then uses Crushing of Ultrafine Machine (the turbine type mill of matsubo companies manufacture) carries out Crushing of Ultrafine, and obtained powder is loaded in container, under nitrogen atmosphere, Fired 1 hour at 1000 DEG C with electric furnace.Then, classification processing is carried out to obtained sinter, thus obtains amorphous carbonaceous (A).During classification processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.
(making 2 of negative electrode active material)
In reacting furnace at 460 DEG C by the composition insoluble in quinoline for below 0.05 mass % coal tar asphalt carry out It is heat-treated within 10 hours, obtained cake mass is loaded in container, under nitrogen atmosphere, carried out with box-shaped electric furnace at 1000 DEG C It is heat-treated within 2 hours.Then, classification processing is carried out to obtained sinter, thus obtains amorphous carbonaceous (A).Use coarse crushing Machine (Jitian makes manufactured roll crusher) crushes obtained amorphous cake mass, reuses atomizer (the turbine type mill of matsubo companies manufacture) carries out Crushing of Ultrafine, obtains amorphous powder.In order to prevent being mixed into obtained powder Oversize grain, is sieved 5 times repeatedly using the sieve of ASTM400 mesh.It regard the negative electrode active material so obtained as amorphous carbonaceous Material (B).
(making 3 of negative electrode active material)
The amorphous cake mass obtained in (making 2 of negative electrode active material) is then transferred in graphite crucible, used Direct-electrifying stove, under non-active gas atmosphere, is heat-treated 5 hours, with Roughpulverizer, (Jitian makes manufactured at 2200 DEG C Roll crusher) obtained cake mass is crushed, reuse the atomizer turbine type of manufacture (matsubo companies mill) and enter Row Crushing of Ultrafine, in order to prevent being mixed into oversize grain in obtained powder, is sieved 5 times repeatedly using the sieve of ASTM400 mesh.Will so Obtained negative electrode active material is used as amorphous carbon metallic substance (C).
(making 4 of negative electrode active material)
It is then transferred to amorphous cake mass is obtained in (making 2 of negative electrode active material) in graphite crucible, using straight Electric furnace is connected, under non-active gas atmosphere, 5 hour graphitizations are carried out at 3000 DEG C, (Jitian makes institute with Roughpulverizer The roll crusher of manufacture) obtained cake mass is crushed, reuse the atomizer (turbine type of matsubo companies manufacture Mill) Crushing of Ultrafine is carried out, in order to prevent being mixed into oversize grain in obtained powder, sieved repeatedly 5 times using the sieve of ASTM400 mesh. It regard the negative electrode active material so obtained as amorphous carbon metallic substance (D).
(making 5 of negative electrode active material)
In order to prevent being mixed into oversize grain in commercially available flake natural graphite powder, the sieve using ASTM400 mesh is anti- Secondary screening 5 times.It regard the negative electrode active material so obtained as amorphous carbon metallic substance (E).
Physical property, shape are determined to the negative electrode active material obtained in the making 1~5 of negative electrode active material by the above method Deng.As a result it is shown in negative pole [2] table 1.
Negative pole [2] table 1
[table 37]
Negative pole [2] [making of battery]
《The making 1 of positive pole》
The 90 mass % cobalt acid lithium (LiCoO as positive active material is mixed in 1-METHYLPYRROLIDONE solvent2)、 Slurry is made as the Kynoar (PVdF) of adhesive in the 5 mass % acetylene black and 5 mass % as conductive material. Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, 80 μm of thickness is rolled into press, then be cut into The shape of uncoated portion with wide 100mm, the active material layer of long 100mm sizes and width 30mm, is used as positive pole.Now The density of positive active material is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the active material layer of long 104mm sizes and width 30mm, is used as negative pole.Now Negative electrode active material density is 1.35g/cm3。
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
《The making 1 of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).The electrode area summation of positive pole is relative to battery case surface area The ratio between summation is 20.6.
Negative pole [2] embodiment 1
Use with《The making 1 of negative pole》The negative pole that the negative electrode active material of item is made as amorphous carbonaceous (A),《Positive pole Making 1》In the positive pole that makes and《The making 1 of electrolyte》The electrolyte made in, passes through《The making 1 of battery》 In method make battery.By following《The evaluation of battery》Method described in carries out cell evaluation to the battery.As a result It is shown in negative pole [2] table 2.
Negative pole [2] embodiment 2
Except negative pole [2] embodiment 1《The making 1 of negative pole》Negative electrode active material using amorphous carbonaceous (B) with Outside, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative pole [2] table 2.
Negative pole [2] embodiment 3
Except negative pole [2] embodiment 1《The making 1 of negative pole》Negative electrode active material using amorphous carbonaceous (C) with Outside, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative pole [2] table 2.
Negative pole [2] embodiment 4~6
Except the nonaqueous electrolytic solution of negative pole [2] embodiment 1~2 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2] embodiment 7~9
Except the nonaqueous electrolytic solution of negative pole [2] embodiment 1~3 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 1~3
Except the nonaqueous electrolytic solution of negative pole [2] comparative example 1~3 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 4
Except negative pole [2] embodiment 1《The making 1 of negative pole》Negative electrode active material using graphite carbonaceous (D) with Outside, battery is similarly made, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 5
Except negative pole [2] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses graphite carbonaceous material (E) beyond, battery is similarly made, and carry out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 6~7
Except the nonaqueous electrolytic solution of negative pole [2] comparative example 4~5 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 8~9
Except the nonaqueous electrolytic solution of negative pole [2] comparative example 4~5 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2] comparative example 10~11
Except the nonaqueous electrolytic solution of negative pole [2] comparative example 4~5 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [2] table 2.
Negative pole [2]《The evaluation of battery》
(solid measure)
To the new battery without charge and discharge cycles, 5 circulations of progress is first under 25 DEG C, 4.1V~3.0V voltage range Phase discharge and recharge (voltage range 4.1V~3.0V).The 0.2 of the 5th circulation now is (by the current value of 1 hour electric discharge rated capacity As 1C, the rated capacity depends on the discharge capacity of 1 hour rate (one-hour-rate), similarly hereinafter) C discharge capacity conducts Initial capacity.
(experiment of short time high current density charge-discharge characteristic)
At 25 DEG C of room temperature environment, carried out 150 minutes with 0.2C constant current to having carried out the battery after solid measure Charging.Centered on voltage now, it is powered about 10 seconds to charging direction, course of discharge with 10C high load capacity electric current, even Continue the experiment of circulation in 35 seconds including being repeated comprising the intermittent time.Battery is taken out at the time of circulating for the 100000th, With 0.2C current discharge to 3V, carry out 1 by the method same with (solid measure) item and circulate, be used as capacity after circulation.And And, short time high current density charge-discharge characteristic is calculated by following formula.
[short time high current density charge-discharge characteristic]=100 × [capacity after circulation]/[initial capacity]
Negative pole [2] table 2
[table 38]
From the result of negative pole [2] table 2, by containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl ester, six Methyl cyclotrisiloxane, and (002) face determined containing wide-angle x-ray diffraction interplanar distance (d002) for more than 0.337, The amorphous carbonaceous that Lc is below 80nm and Raman R value is more than 0.2 can make short time high electricity as negative electrode active material Current density charge-discharge characteristic is able to improve tremendously.
Negative pole [3] [making of negative electrode active material]
(making 1 of negative electrode active material)
In order to prevent being mixed into oversize grain, using the sieve of ASTM400 mesh by 23 μm commercially available of volume average particle size Li1.33Ti1.66O4Sieve 5 times repeatedly, obtain lithium-titanium composite oxide (A).
(making 2 of negative electrode active material)
In order to prevent being mixed into oversize grain, using the sieve of ASTM400 mesh by 1.0 μm commercially available of volume average particle size Li1.33Ti1.66O4Sieve 5 times repeatedly, obtain lithium-titanium composite oxide (B).
(making 3 of negative electrode active material)
In order to prevent being mixed into oversize grain, using the sieve of ASTM400 mesh by 0.1 μm commercially available of volume average particle size Li1.33Ti1.66O4Sieve 5 times repeatedly, obtain lithium-titanium composite oxide (C).
(making 4 of negative electrode active material)
In order to prevent being mixed into oversize grain in commercially available flake natural graphite powder, the sieve using ASTM400 mesh is anti- Secondary screening 5 times.It regard the negative electrode active material so obtained as graphite carbonaceous (D).
Composition, structure, shape, physical property of negative electrode active material etc. are concluded and are shown in negative pole [3] table 1.
Negative pole [3] table 1
[table 39]
Negative pole [3] [making of battery]
《The making 1 of positive pole》
The 90 mass % cobalt acid lithium (LiCoO as positive active material is mixed in 1-METHYLPYRROLIDONE solvent2)、 Slurry is made as the Kynoar (PVdF) of adhesive in the 5 mass % acetylene black and 5 mass % as conductive material. Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, 80 μm of thickness is rolled into press, then be cut into The shape of uncoated portion with wide 100mm, the active material layer of long 100mm sizes and width 30mm, is used as positive pole.Now The density of the active material of positive pole is 2.35g/cm3。
《The making 1 of negative pole》
Mixed in 1-METHYLPYRROLIDONE solvent 90 mass % negative electrode active materials, 5 mass % as conductive material Acetylene black and 5 mass % as the Kynoar (PVdF) of adhesive, slurry is made.Obtained slurry is coated on thickness The one side of 10 μm of rolled copper foil, and dry, 90 μm of thickness is rolled into press, then be cut into width 104mm, length The shape of the active material layer of 104mm sizes and width 30mm uncoated portion, is used as negative pole.
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
(making 1 of battery)
Negative pole and positive pole are punching into 12.5mm φ, after being dried in vacuo at 110 DEG C, glove box is transferred to It is interior, positive pole and negative pole clipped under argon atmosphere be punching into 14mm φ polyethylene separator it is opposed, and add nonaqueous electrolytic solution The nonaqueous electrolytic solution described in item is made, 2032 type coin batteries (lithium secondary battery) are made.
Negative pole [3] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material made for lithium-titanium composite oxide (A) negative pole,《Just The making 1 of pole》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The electrolyte made in, passes through《The system of battery Make 1》Method in makes battery.The battery is carried out following《The evaluation of battery》Cell evaluation described in.As a result show In negative pole [3] table 2.
Negative pole [3] embodiment 2
Except negative pole [3] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses lithium-titanium composite oxide (B) beyond, battery is made in the same manner as negative pole [3] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [3] table 2.
Negative pole [3] embodiment 3
Except negative pole [3] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses lithium-titanium composite oxide (C) beyond, battery is made in the same manner as negative pole [3] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [3] table 2.
Negative pole [3] embodiment 4~6
Except the nonaqueous electrolytic solution of negative pole [3] embodiment 1~3 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3] embodiment 7~9
Except the nonaqueous electrolytic solution of negative pole [3] embodiment 1~3 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3] comparative example 1~3
Except the nonaqueous electrolytic solution of negative pole [3] embodiment 1~3 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3] comparative example 4
Except negative pole [3] embodiment 1《The making 1 of negative pole》Negative electrode active material using graphite carbonaceous (D) with Outside, battery is made in the same manner as negative pole [3] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [3] table 2.
Negative pole [3] comparative example 5
Except the nonaqueous electrolytic solution of negative pole [3] comparative example 4 is changed into《The making 2 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3] comparative example 6
Except the nonaqueous electrolytic solution of negative pole [3] comparative example 4 is changed into《The making 3 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3] comparative example 7
Except the nonaqueous electrolytic solution of negative pole [3] comparative example 4 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made with same method respectively, and evaluated.As a result it is shown in negative pole [3] table 2.
Negative pole [3]《The evaluation of battery》
(measure of capacity)
To the new battery without charge and discharge cycles, by 175mAh/g of lithium-titanium composite oxide, graphite carbonaceous be 350mAh/g is converted, and battery capacity is calculated by the active matter quality being present on copper foil.Also, on the basis of the battery capacity Under 25 DEG C, 2.7V~1.9V voltage range, using 0.2C (by 1 hour electric discharge rated capacity current value as 1C, the volume Constant volume depends on the discharge capacity of 1 hour rate (one-hour-rate), similarly hereinafter) 5 circulations are carried out to lithium-titanium composite oxide Discharge and recharge at initial stage.Discharge and recharge at initial stage similarly is carried out to graphite carbonaceous under 25 DEG C, 4.1V~3.0V voltage range.Will The 0.2C discharge capacities of the 5th circulation now are used as initial capacity.
(measure of output resistance)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, in the environment of -30 DEG C respectively Discharged 10 seconds with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C, determine the voltage of the 10th second.By the slope of current-voltage straight line As output resistance (Ω), the results are shown in negative pole [3] table 2.
Negative pole [3] table 2
[table 40]
In negative pole [3] table 2, " output resistance slip " is the output resistance of battery corresponding with what it is without specific compound The slip (%) of output resistance obtained from being compared.
From the result of negative pole [3] table 2, by using containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl Ester, hexamethyl cyclotrisiloxane, and containing comprising can occlusion, release lithium titanium metal oxide negative electrode active material Matter, can reduce output resistance with tremendous.
Negative pole [4] [making of negative electrode active material]
(making 1 of negative electrode active material)
Using spheroidization processing unit (nara machinery manufacturing company manufacture hybrid system), with 6500rpm pairs of rotating speed The flake natural graphite (the weight % of ash content 0.05) of about 150 μm treated of median particle diameter of high purity carry out 5 minutes it is spherical Change is handled, and is reused wind-driven type grader (OMC-100 of seishin enterprise-like corporations manufacture) and is removed 45 weight % micro mists, obtains Spheroidization native graphite (C).
(making 2 of negative electrode active material)
The powder of spheroidization native graphite (C) after above-mentioned classification is attached in graphite crucible, existed using direct-electrifying stove It is heat-treated 5 hours in 3000 DEG C under inactive atmosphere, obtains carbonaceous material (D).
(making 3 of negative electrode active material)
In addition to being 2000 DEG C by the treatment temperature set in (making 2 of negative electrode active material), similarly obtain Carbonaceous material (E).
(making 4 of negative electrode active material)
In addition to being 1600 DEG C by the treatment temperature set in (making 2 of negative electrode active material), similarly obtain Carbonaceous material (F).
(making 5 of negative electrode active material)
In addition to being 1200 DEG C by the treatment temperature set in (making 2 of negative electrode active material), similarly obtain Carbonaceous material (G).
(making 5 of negative electrode active material)
17 μm of median particle diameter, the tap density 0.5g/cm that high purity is treated3, BET specific surface area 6m2/ g scale Shape native graphite (the weight % of ash content 0.1) be directly heat-treated in the same manner as (making 2 of negative electrode active material) and without Spheroidization processing, obtains heat treatment native graphite (H).
(making 6 of negative electrode active material)
20 μm of median particle diameter, the tap density 0.75g/cm that high purity is treated3, BET specific surface area 3m2/ g day Right graphite (the weight % of ash content 0.5) be directly heat-treated in the same manner as (making 2 of negative electrode active material) and without spherical Change is handled, and obtains carbonaceous material (I).
According to above-mentioned method, the spheroidization native graphite (C) made, carbonaceous material (D), carbonaceous material (E), carbon are determined Metallic substance (F), carbonaceous material (G), heat treatment native graphite (H), the shape and physical property of carbonaceous material (I).As a result it is shown in negative pole [4] table 1.
Negative pole [4] table 1
Negative pole [4] [making of battery]
《The making 1 of positive pole》
The 90 mass % cobalt acid lithium (LiCoO as positive active material is mixed in 1-METHYLPYRROLIDONE solvent2)、 Slurry is made as the Kynoar (PVdF) of adhesive in the 5 mass % acetylene black and 5 mass % as conductive material. Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, 80 μm of thickness is rolled into press, then be cut into The shape of uncoated portion with wide 100mm, the active material layer of long 100mm sizes and width 30mm, is used as positive pole.Now The density of the active material of positive pole is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the active material layer of long 104mm sizes and width 30mm, is used as negative pole.Now The density of the active material of negative pole is 1.35g/cm3。
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
(making 1 of battery)
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).The electrode area summation of positive pole is relative to battery case surface area The ratio between summation is 20.6.
Negative pole [4] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material be made for carbonaceous material (D) negative pole,《The system of positive pole Make 1》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The nonaqueous electrolytic solution made in, passes through《The making of battery 1》Method in makes battery.By following《The evaluation of battery》Method and said determination method described in is to the electricity Pond is measured.As a result it is shown in negative pole [4] table 2.
Negative pole [4] embodiment 2
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (E), Battery is made in the same manner as negative pole [4] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [4] table 2.
Negative pole [4] embodiment 3
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (F), Battery is made in the same manner as negative pole [4] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [4] table 2.
Negative pole [4] embodiment 4
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (G), Battery is made in the same manner as negative pole [4] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [4] table 2.
Negative pole [4] embodiment 5
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (I), Battery is made in the same manner as negative pole [4] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [4] table 2.
Negative pole [4] embodiment 6~10
Except the nonaqueous electrolytic solution of negative pole [4] embodiment 1~5 is changed into respectively《The making 2 of nonaqueous electrolytic solution》Made in Beyond the nonaqueous electrolytic solution of work, battery is made with same method, and evaluated.As a result it is shown in table 2 (negative pole [4] table 2).
Negative pole [4] embodiment 11~15
Except the nonaqueous electrolytic solution of negative pole [4] embodiment 1~5 is changed into respectively《The making 3 of nonaqueous electrolytic solution》Made in Beyond the nonaqueous electrolytic solution of work, battery is made with same method, and evaluated.As a result it is shown in negative pole [4] table 2.
Negative pole [4] comparative example 1
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses spheroidization native graphite (C) beyond, battery is made in the same manner as negative pole [4] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 2
Except the nonaqueous electrolytic solution of negative pole [4] comparative example 1 is used《The making 4 of nonaqueous electrolytic solution》The non-water power made in Solve beyond liquid, make battery in the same manner as negative pole [4] comparative example 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 3
Except negative pole [4] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses heat treatment native graphite (H) beyond, battery is made in the same manner as negative pole [4] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 4
Except the nonaqueous electrolytic solution of negative pole [4] comparative example 3 is used《The making 4 of nonaqueous electrolytic solution》The non-water power made in Solve beyond liquid, make battery in the same manner as negative pole [4] comparative example 3, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 5
Except the nonaqueous electrolytic solution of negative pole [4] embodiment 5 is used《The making 4 of nonaqueous electrolytic solution》The non-water power made in Solve beyond liquid, make battery in the same manner as negative pole [4] embodiment 5, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 6
Except the nonaqueous electrolytic solution of negative pole [4] embodiment 1 is used《The making 4 of nonaqueous electrolytic solution》The non-water power made in Solve beyond liquid, make battery in the same manner as negative pole [4] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.Knot Fruit is shown in negative pole [4] table 2.
Negative pole [4] comparative example 7,8
Except the nonaqueous electrolytic solution of negative pole [4] comparative example 1,3 is changed into《The making 2 of nonaqueous electrolytic solution》What is made in is non- Beyond water electrolysis liquid, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [4] table 2.
Negative pole [4] comparative example 9,10
Except the nonaqueous electrolytic solution of negative pole [4] comparative example 1,3 is changed into《The making 3 of nonaqueous electrolytic solution》What is made in is non- Beyond water electrolysis liquid, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [4] table 2.
Negative pole [4] table 2
Negative pole [4]《The evaluation of battery》
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.
(food preservation test)
Preserved under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 0.2C Constant-current constant-voltage method charge to capacity reaches the initial capacity determined during solid measure 20%, and reach in charging Voltage limit 4.2V, is then preserved 1 week under 60 DEG C of hot environment.The battery after preservation is discharged with 0.2C under 25 DEG C of environment To 3V, further the discharge and recharge of 3 circulations is being carried out under the same conditions with (solid measure), by the 0.2C of the 3rd circulation Capacity after discharge capacity is preserved as low depth of charge.After the initial capacity and food preservation test that are determined before food preservation test terminate Capacity obtains circulation conservation rate according to following calculating formulas after the low depth of charge determined is preserved.
Capacity/initial capacity after recovery rate (%)=100 × low depth of charge is preserved after low depth of charge is preserved
From the above results, by containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl ester, pregnancy basic ring three Siloxanes, and it is that more than 0.85, surface functionalities group amount O/C values are 0~0.01 that the circularity containing negative electrode active material, which is made, Carbonaceous material negative pole, can make the low depth of charge after the food preservation test of low depth of charge preserve after recovery rate leaped The raising of property.
Negative pole [5] [making of negative material]
[making 1 of negative material]
The coal tar asphalt that quinoline non-soluble composition is below 0.05 mass % is heat-treated 10 in reacting furnace in 460 DEG C small When, obtain the block heat-treated graphite crystalline precursor with meltbility of 385 DEG C of softening point.With middle pulverizer (seishin The orient mill of enterprise-like corporation's manufacture) obtained block heat-treated graphite crystalline precursor is crushed, reuse atomizer (the turbine type mill of matsubo companies manufacture) carries out Crushing of Ultrafine, obtains the graphite crystallization precursor of the miniaturization of 17 μm of median particle diameter Powder (E).
In the graphite crystallization precursor powder (E) of above-mentioned miniaturization, with relative to miniaturization graphite crystallization precursor powder and Ratio that the gross weight of native graphite is 50 mass % mixing median particle diameter is 17 μm, draw ratio is that 1.4, tap density is 1.0g/cm3, BET specific surface area be 6.5g/cm3, circularity be 0.92 native graphite, obtain mixed-powder.
The mixed-powder of the heat-treated graphite crystalline precursor is encased in metal container, in the electric furnace of box-shaped, 2 hours heat treatment A are carried out under nitrogen circulation in 540 DEG C.In heat treatment A, the graphite crystallization precursor powder melting of miniaturization, into For the block with the native graphite equably mixture of the heat-treated graphite crystalline precursor of Composite.
With Roughpulverizer (Jitian make manufactured roll crusher) by the heat-treated graphite crystalline precursor after solidifying The block of mixture crush, then carry out Crushing of Ultrafine with atomizer (turbine type that matsubo companies manufactures grind), obtain intermediate value The powder that 18.5 μm of footpath.
Obtained powder is loaded in container, under nitrogen atmosphere, fired 1 hour at 1000 DEG C with electric furnace.After firing, Obtained powder (precursor mixture (F) before heat treatment B) is still the form of powder, does not almost find to melt, fuses.
In addition, the powder after firing is transferred in graphite crucible, using direct-electrifying stove under inactive atmosphere in 3000 DEG C of graphitizations 5 hours, in order to prevent being mixed into oversize grain, are sieved 5 times, obtain different take repeatedly using the sieve of ASTM400 mesh Tropism carbon complex (G).
[making 2 of negative material]
Using the native graphite used in [making 1 of negative material] and it is used as the softening point 88 for being capable of graphited adhesive DEG C binder pitch with 100:30 weight is than mixing, then puts into and be previously heated to 128 DEG C and have a stirring of mastication type In the kneader of the wing, mix 20 minutes.
Mixture after abundant mediate is filled into and is preheating in advance in the mould of 108 DEG C of moulding press, is placed 5 minutes, Plunger is extruded in the temperature stabilization of mixture, applies 2kfg/cm2The pressure of (0.20MPa) is molded.Keep the pressure 1 minute, then stop driving, after pressure reduction terminates, take out native graphite and graphite crystallization precursor powder it is compound after shaping Body.
Obtained formed body is encased in as in the metal Fire-resistant cabinet of heatproof container, and fills in space graphite Coke powder.With electric furnace by 48 hours from room temperature to 1000 DEG C, kept for 3 hours at 1000 DEG C, progress devolatilization, Fire.Then, formed body is placed in graphite crucible, and graphite coke powder is filled in space, using direct-electrifying stove non- Heated 4 hours in 3000 DEG C in active atmosphere, carry out graphitization.
With jaw crusher after the formed body coarse crushing of obtained graphite, will use by crushing vane speed setting for 4000 revs/min of grinding mill carries out Crushing of Ultrafine.In addition, when being classified processing, in order to prevent being mixed into oversize grain, using The sieve of ASTM400 mesh is sieved 5 times repeatedly, obtains different orientation carbon complex (H).
[making 3 of negative material]
Except the heat treatment that the use direct-electrifying stove for making [making 2 of negative material] is carried out carried out at 2200 DEG C with Outside, different orientation carbon complex (I) is obtained according to the method same with [making 2 of negative material].
[making 4 of negative material]
Except the native graphite for making [making 2 of negative material] be median particle diameter be 10 μm, draw ratio be 2.3, vibration density Spend for 0.64g/cm3, BET specific surface area be 9.5m2Beyond/g, circularity is 0.83 coke, with [making 2 of negative material] Similarly, different orientation carbon complex (J) is obtained.
[making 5 of negative material]
Except the coke that will be used in [making 4 of negative material], the carborundum of graphitization catalyst and as being capable of stone The binder pitch of 88 DEG C of the softening point of the adhesive of inkization is with 100:10:Beyond 30 mass ratio mixing, with [negative material Make 2] similarly, obtain different orientation carbon complex (K).
[making 6 of negative material]
Except the native graphite for making [making 2 of negative material] be median particle diameter be 19.8 μm, draw ratio be 3.2, jolt ramming Density is 0.47g/cm3, BET specific surface area be 5.9m2Beyond/g, circularity is 0.81 flake natural graphites, with [negative pole The making 2 of material] similarly, obtain different orientation carbon complex (L).
[making 7 of negative material]
Except the native graphite for making [making 2 of negative material] be median particle diameter be 35 μm, draw ratio be 1.4, vibration density Spend for 1.02g/cm3, BET specific surface area be 3.9m2Beyond/g, circularity is 0.90 native graphites, with [the system of negative material Make 2] similarly, obtain different orientation carbon complex (M).
[making 8 of negative material]
In addition to being 1500 revs/min by the crushing vane speed setting of [making 2 of negative material], with [negative material Making 2] similarly, obtain different orientation carbon complex (N).
[making 9 of negative material]
Except the native graphite for making [making 2 of negative material] be median particle diameter be 6 μm, draw ratio be 1.5, tap density For 0.15g/cm3Native graphite beyond, in the same manner as [making 2 of negative material], obtain different orientation carbon complex (O).
[making 10 of negative material]
The graphite crystallization precursor powder (E) obtained in [making 1 of negative material] is encased in metal container, 2 hours heat treatment A are carried out in the electric furnace of box-shaped, under nitrogen circulation in 540 DEG C.In heat treatment A, graphite crystallization precursor powder (E) melt, as bulk.
With Roughpulverizer (Jitian make manufactured roll crusher) by the heat-treated graphite crystalline precursor after solidifying Block is crushed, then carries out Crushing of Ultrafine with atomizer (turbine type that matsubo companies manufacture is ground), obtains 18.5 μm of median particle diameter Powder.
Obtained powder is put into container, under nitrogen atmosphere, fired 1 hour at 1000 DEG C with electric furnace.After firing, Obtained powder is still the form of powder, does not almost find to melt, fuses.
In addition, the powder after firing is transferred in graphite crucible, using direct-electrifying stove under inactive atmosphere in 3000 DEG C of graphitizations 5 hours, in order to prevent being mixed into oversize grain, are sieved 5 times, obtain carbonaceous repeatedly using the sieve of ASTM400 mesh Material (P).
[making 11 of negative material]
The native graphite used in [making 1 of negative material] is encased in metal container, in the electric furnace of box-shaped In, nitrogen circulation under in 540 DEG C carry out 2 hours heat treatment A.After heat treatment A, native graphite does not almost find to melt, melted Close.Obtained powder is put into container, under nitrogen atmosphere, fired 1 hour at 1000 DEG C with electric furnace.After firing, obtain Powder still be powder form, almost do not find to melt, fuse.
In addition, the powder after firing is transferred in graphite crucible, using direct-electrifying stove under inactive atmosphere in 3000 DEG C of graphitizations 5 hours, in order to prevent being mixed into oversize grain, are sieved 5 times, obtain carbonaceous repeatedly using the sieve of ASTM400 mesh Material (Q).
[making 12 of negative material]
Carbonaceous material (P) and each 50 mass % of carbonaceous material (Q) are mixed, after uniform mixing, carbonaceous material is obtained Mixture (R).
Negative pole [5] [making of battery]
《The making 1 of positive pole》
The 90 mass % cobalt acid lithium (LiCoO as positive active material is mixed in 1-METHYLPYRROLIDONE solvent2)、 Slurry is made as the Kynoar (PVdF) of adhesive in the 5 mass % acetylene black and 5 mass % as conductive material. Obtained slurry is coated on to the aluminium foil two sides of 15 μm of thickness, and dried, 80 μm of thickness is rolled into press, then be cut into The shape of uncoated portion with wide 100mm, the active material layer of long 100mm sizes and width 30mm, is used as positive pole.Now The density of the active material of positive pole is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into With width
The shape of 104mm, the active material layer of long 104mm sizes and width 30mm uncoated portion, is used as negative pole.Now Negative pole active material density be 1.35g/cm3。
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
(making 1 of battery)
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The D.C. resistance that alternating current method is determined is about 5 milliohms (m Ω).
Negative pole [5] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material be made for different orientation carbon complex (G) negative pole, 《The making 1 of positive pole》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The nonaqueous electrolytic solution made in, passes through 《The making 1 of battery》Method in makes battery.By following《The evaluation of battery》Method and above-mentioned survey described in Determine method to be measured the battery.
Negative pole [5] embodiment 2
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (H) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 3
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (I) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 4
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (J) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 5
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (K) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 6
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (L) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 7
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (M) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 8
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (N) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 9
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses different orientation carbon complex (O) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] embodiment 10~18
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 1~9 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is similarly made, and carries out cell evaluation after the same method.
Negative pole [5] embodiment 19~27
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 1~9 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is similarly made, and carries out cell evaluation after the same method.
Negative pole [5] comparative example 1
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (P), Battery is made in the same manner as negative pole [5] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 2
Except the nonaqueous electrolytic solution of negative pole [5] comparative example 1 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] comparative example 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 3
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (Q), Battery is made in the same manner as negative pole [5] embodiment 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 4
Except the nonaqueous electrolytic solution of negative pole [5] comparative example 3 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] comparative example 3, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 5
Except negative pole [5] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses carbonaceous material mixture (R) beyond, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 6
Except the nonaqueous electrolytic solution of negative pole [5] comparative example 5 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] comparative example 5, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 7
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 1 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 8
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 2 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] embodiment 2, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 9
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 4 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] embodiment 4, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 10
Except the nonaqueous electrolytic solution of negative pole [5] embodiment 5 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [5] embodiment 5, and carry out《The evaluation of battery》The cell evaluation that item is recorded.
Negative pole [5] comparative example 11~13
Except the nonaqueous electrolytic solution of negative pole [5] comparative example 1,3,5 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is similarly made, and carries out cell evaluation after the same method.
Negative pole [5] comparative example 14~16
Except the nonaqueous electrolytic solution of negative pole [5] comparative example 1,3,5 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is similarly made, and carries out cell evaluation after the same method.
Negative pole [5]《The evaluation of battery》
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.Then following shown output tests are carried out.
(low depth of charge cyclic test)
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method charges to capacity reaches the initial capacity determined during solid measure 20%, and reaches charging Upper voltage limit 4.2V, is then discharged to final discharging voltage 3.0V with 2C constant current, is followed the charge and discharge cycles as 1 Ring, and the circulation is repeated until 500 circulations.
Battery after terminating for cyclic test, the discharge and recharge of 3 circulations is carried out under 25 DEG C of environment, the 3rd is followed Capacity after the 0.2C discharge capacities of ring are circulated as low depth of charge.The initial capacity and circulation determined before cyclic test is tried Test capacity after the low depth of charge circulation determined after terminating and obtain circulation conservation rate according to following calculating formulas.
Circulate capacity/initial capacity after conservation rate (%)=100 × low depth of charge circulation
The negative electrode active material guide look used in negative pole [5] embodiment and negative pole [5] comparative example is shown in negative pole [5] table 1, electricity The result that pond is evaluated is shown in negative pole [5] table 2 and negative pole [5] table 3.From the result of negative pole [5] table 2 and negative pole [5] table 3, lead to Cross containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl ester, hexamethyl cyclotrisiloxane, and combination is used as negative electrode active The different orientation carbon complex of material, can obtain the capability retention after the cyclic test of low depth of charge (circulation conservation rate) To tremendous raising.
Negative pole [5] table 1
Negative pole [5] table 2
[table 44]
Negative pole [5] table 3
[table 45]
Negative pole [6] [making of negative electrode active material]
(making 1 of negative electrode active material)
In order to prevent being mixed into oversize grain in commercially available natural graphite powder (A), using ASTM400 mesh sieve repeatedly Sieve 5 times.It regard the negative electrode active material so obtained as carbonaceous material (B).
(making 2 of negative electrode active material)
With atomizer (turbine type that matsubo companies manufacture is ground) to commercially available natural graphite powder (C) (d002： 0.336nm、Lc：More than 100nm, Raman R value：0.11st, tap density：0.46g/cm3, real density：2.27g/cm3, volume it is average Particle diameter：28.7 μm) handled, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, prepare carbon Metallic substance (D).
(making 3 of negative electrode active material)
Using hybrid system ((strain) nara machinery makes manufactured hybrid system NHS-1 types) with treating capacity 90g, rotor Peripheral speed 60m/s, 3 minutes processing times are handled natural graphite powder (C), thus carry out spheroidization, in addition, in order to Prevent from being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.It regard the negative electrode active material so obtained as carbon Metallic substance (E).By the way that the operation is repeated, it is ensured that battery is measured necessary to making.
(making 4 of negative electrode active material)
Using hybrid system with treating capacity 90g, rotor peripheral speed 30m/s, the condition of 1 minute processing time to commercially available Natural graphite powder (F) (d002：0.336nm、Lc：More than 100nm, Raman R value：0.09th, tap density：0.57g/cm3, it is true Density：2.26g/cm3, volume average particle size：85.4 μm) spheroidization is carried out, in addition, in order to prevent from being mixed into oversize grain, using The sieve of ASTM400 mesh is sieved 5 times repeatedly.It regard the negative electrode active material so obtained as carbonaceous material (G).By being repeated The operation, it is ensured that battery is measured necessary to making.
(making 5 of negative electrode active material)
The coal tar asphalt that quinoline non-soluble composition is below 0.05 mass % is heat-treated 10 in reacting furnace in 460 DEG C small When, obtain the block carbonization treatment precursor with meltbility of 385 DEG C of softening point.By obtained block carbonization treatment precursor It is encased in metal container, in 1000 DEG C be heat-treated within 2 hours in the electric furnace of box-shaped, under nitrogen circulation.Use coarse powder (matsubo is public by unbodied piece obtained crushing, then with atomizer for broken machine (Jitian makes manufactured roll crusher) The turbine type mill of department's manufacture) Crushing of Ultrafine is carried out, obtain the amorphous powder of 18 μm of volume reference average grain diameter.In order to prevent obtaining Powder in be mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.The negative electrode active material so obtained is made For carbonaceous material (H).
(making 6 of negative electrode active material)
The carbonaceous material (H) obtained in (making 5 of negative electrode active material) is then transferred in graphite crucible, using direct Energization stove carries out 5 hours graphitizations under inactive atmosphere in 3000 DEG C, in order to prevent being mixed into oversize grain in obtained powder, Sieved repeatedly 5 times using the sieve of ASTM400 mesh.It regard the negative electrode active material obtained here as carbonaceous material (I).
(making 7 of negative electrode active material)
Using hybrid system with treating capacity 90g, rotor peripheral speed 30m/s, the condition of 1 minute processing time to (negative pole The making 6 of active material) in obtained carbonaceous material (I) carry out spheroidization, in addition, in order to prevent from being mixed into oversize grain, using The sieve of ASTM400 mesh is sieved 5 times repeatedly.It regard the negative electrode active material so obtained as carbonaceous material (J).By being repeated The operation, it is ensured that battery is measured necessary to making.
(making 8 of negative electrode active material)
By purity natural graphite powder (K) (d002 lower than natural graphite powder (A)：0.336nm、Lc：More than 100nm, Raman R value：0.10th, tap density：0.49g/cm3, real density：2.27g/cm3, volume average particle size：27.3 μm, the matter of ash content 0.5 Measure %) with (making 3 of negative electrode active material) it is same under conditions of carry out spheroidization and screening, prepare carbonaceous material (L).It is logical Cross and the operation is repeated, it is ensured that battery is measured necessary to making.
(making 9 of negative electrode active material)
In order to prevent being mixed into oversize grain in commercially available flake natural graphite powder (M), the sieve of ASTM400 mesh is used Son is sieved 5 times repeatedly.It regard the negative electrode active material so obtained as carbonaceous material (N).
According to above-mentioned method determine carbonaceous material (B), (D), (E), (G), (H), (I), (J), (L), the shape of (N) and Physical property.As a result it is shown in negative pole [6] table 1.
Negative pole [6] table 1
Negative pole [6] [making of battery]
《The making 1 of positive pole》
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.Now just The density of the active material of pole is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the active material layer of long 104mm sizes and width 30mm, is used as negative pole.Now The density of the active material of negative pole is 1.35g/cm3。
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
《The making 1 of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).Shell table of the summation of the electrode area of positive pole relative to battery The ratio between summation of area is 20.6.
Negative pole [6] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material be made for carbonaceous material (D) negative pole,《The system of positive pole Make 1》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The nonaqueous electrolytic solution made in, passes through《The making of battery 1》Method in makes battery.By following《The evaluation of battery》Method and said determination method described in is to the electricity Pond is measured.As a result it is shown in table 2 (negative pole [6] table 2).
Negative pole [6] embodiment 2
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (E) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] embodiment 3
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (G) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] embodiment 4
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (J) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] embodiment 5
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (L) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] embodiment 6~10
Except the nonaqueous electrolytic solution of negative pole [6] embodiment 1~5 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [6] table 2.
Negative pole [6] embodiment 11~15
Except the nonaqueous electrolytic solution of negative pole [6] embodiment 1~5 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 1
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (B) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] comparative example 2
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 1 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] comparative example 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 3
Except the nonaqueous electrolytic solution of negative pole [6] embodiment 2 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] embodiment 2, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 4
Except the nonaqueous electrolytic solution of negative pole [6] embodiment 1 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 5
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (H) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] comparative example 6
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 5 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] comparative example 5, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 7
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (N) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] comparative example 8
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 7 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] comparative example 7, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 9
Except negative pole [6] embodiment 1《The making 1 of negative pole》In negative electrode active material using carbonaceous material (I) with Outside, battery is made in the same manner as negative pole [6] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in Negative pole [6] table 2.
Negative pole [6] comparative example 10
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 9 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [6] comparative example 9, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 11~14
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 1,5,7,9 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Nonaqueous electrolytic solution beyond, make battery after the same method respectively, and evaluated.As a result it is shown in negative pole [6] table 2.
Negative pole [6] comparative example 15~18
Except the nonaqueous electrolytic solution of negative pole [6] comparative example 1,5,7,9 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Nonaqueous electrolytic solution beyond, make battery after the same method respectively, and evaluated.As a result it is shown in negative pole [6] table 2.
Negative pole [6]《The evaluation of battery》
(solid measure)
To the new battery without charge and discharge cycles, the initial stage of 5 circulations is carried out in 25 DEG C, 4.1V~3.0V voltage range Discharge and recharge (voltage range 4.1V~3.0V).By the 0.2C of the 5th circulation now (by the electric current of 1 hour electric discharge rated capacity Value depends on the discharge capacity of 1 hour rate (one-hour-rate) as 1C, the rated capacity, similarly hereinafter) discharge capacity conduct Initial capacity.
(output test 1)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, 3 are stood under -30 DEG C of environment small When, then discharged 10 seconds with 0.1C, 0.3C, 1.0C, 3.0C, 5.0C respectively, determine the voltage of the 10th second.By current-voltage The area for the triangle that straight line and lower voltage limit (3V) are surrounded is as low temperature power output at initial stage (W).
(output test 2)
After output test 1, implement 1 hour 4.1V low-voltage charging, then by battery transfer to 25 DEG C Under environment, after 15 minutes, discharged 10 seconds with 0.1C, 0.3C, 1.0C, 3.0C, 5.0C, determine the voltage of the 10th second.By electricity Power output (W) when the area for the triangle that stream-voltage straight line and lower voltage limit (3V) are surrounded rises as temperature.
Acclimation temperature is calculated by the result of output test 1 and output test 2 by following calculating formulas to export Power increase rate (%).
Acclimation temperature power output increase rate (%)
=[(power output (W)/low temperature power output at initial stage (W) when temperature rises) -1] × 100
Impedance Rct and bilayer capacity C dl in negative pole [6] table 2 are to one of contributive parameter of power output, impedance Rct value is smaller, or double-deck capacity C dl value is bigger, then power output more has the tendency of improvement.In addition, " impedance Rct " and " double-deck capacity C dl " is by illustrating that the method described in the part of impedance is obtained.
Negative pole [6] table 2
[table 47]
From the result of negative pole [6] table 2, by containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl ester, six Methyl cyclotrisiloxane, and contain the interplanar distance that circularity is (002) face that more than 0.85, wide-angle x-ray diffraction is determined (d002) less than 0.337 and Raman R value for 0.12~0.8 graphite carbon particle as negative electrode active material, -30 can be made DEG C low-temperature condition under the recovery that rises with temperature of power output be able to accelerate tremendously.
The making ＞ of negative pole [7] ＜ negative poles
(making 1 of negative pole)
Using Si and C mixture (plectane of Si and C area ratio substantially 100 to 9) as target material, using average Surface roughness (Ra) is 0.2 μm, tensile strength is 280N/mm2, 0.2% endurance be 220N/mm2, thickness be 18 μm of electrolysis Copper foil carries out work in 45 minutes as current collection structure base board using DC sputtering device (" HSM-52 " of the manufacture of company of Shimadzu Seisakusho Ltd.) The film forming of property substance film, obtains film cathode (1).
Now, current collection structure base board is arranged on the fixture of water cooling, is maintained at about 25 DEG C, container is vacuum-drawn against in advance 4×10-4Pa, the argon gas for the 40sccm high-purities that circulated in container, the aperture of regulation main valve turns into after 1.6Pa atmosphere, in work( Rate density 4.7W/cm2, deposition velocity (film forming speed) carry out film forming under (0.108 μm/point) within about 1.8nm/ seconds.The sputter gas Oxygen concentration be 0.0010%.In addition, the oxide-film in order to remove electrolytic copper foil surface, reverse sputtering is carried out before film is formed And carry out the etching of substrate surface.
Type electron microscope (SEM) is scanned by the section of the film of the film cathode (1) to obtaining to observe, film forming The thickness of film afterwards is 6 μm (reference picture 1 (a)).In addition, when carrying out the composition analysis of film with XPS by the following method, it is thin In film containing Elements C be 24 atom %, SiC in relative to Elements C concentration C concentration ratios Q (C) equivalent to 0.49.In addition, if Represented with atomic concentration ratio, then Si/C/O=1.00/0.33/0.04.Obtained in addition, being determined by the following method using Raman During the Raman value of film, RC=0.05, the peak that RSC=sc is not detected, RS=0.55.In addition, carrying out by the following method thin During the X-ray diffraction measure of film, clear and definite SiC peak, XIsz=0.38 are not detected.As a result it is shown in negative pole [7] table 1.
In addition, by the following method using Si in electron probe microanalyzer (EPMA) measure film in film thickness direction During mass concentration distributions, shown in such as Fig. 1 (b), Si maximum or minimum value and the difference (absolute value) of average value within 25%, The Si substantially continuously film forming from collector.In addition, when determining the distribution of the Elements C in film, shown in such as Fig. 1 (c), element C is in Si films with less than 1 μm of distribution uniform in size.
(making 2 of negative pole)
In addition to target material uses Si, the film forming active material film in the same manner as (making 1 of negative pole) makes film and born Pole (2).
Type electron microscope (SEM) is scanned by the section of the film of the film cathode (2) to obtaining to observe, film forming The thickness of film afterwards is 6 μm.In addition, when carrying out the composition analysis of film, Elements C, N being free of in film, atomic concentration ratio is used During expression, Si/O=1.00/0.02.In addition, when obtaining the Raman value of film, RC=c peak not being detected, RSC is not detected =sc peak, RS=0.30.As a result it is shown in negative pole [7] table 1.
＜ XPS determine ＞
Determined as X-ray photoelectricity optical spectroscopy, using X-ray photoelectricity optical splitter (for example, what ulvac-phi companies manufactured " ESCA "), film cathode is placed on sample platform and makes surface flat, using the K alpha rays of aluminium as x-ray source, while carrying out Ar is sputtered while carrying out depth curve measure.Must reach under the certain depth of concentration (such as 200nm) Si2p (90~ 110eV), C1s (280~300eV) and O1s (525~545eV) spectrogram.Obtained C1s summit is set as 284.5eV Carry out band electronic compensating, obtain the peak area of Si2p, C1s and O1s spectrogram, multiplied by with device sensitivity coefficient, calculate respectively Si, C and O atomic concentration.Atomic concentration ratio Si/C/O (Si atomic concentrations/C are calculated by obtained Si, O and the C atomic concentration Atomic concentration/O atom concentration), it is defined as the composition value Si/C/O of film.
＜ Ramans determine ＞
Determined as Raman, using raman spectroscopy device (such as " raman spectroscopy device " that Japanese light splitting society manufactures), by film Negative pole is arranged in cell, and measure is that the specimen surface in pond is irradiated argon laser to carry out.
In addition, Raman condition determination here is as follows.
Argon laser wavelength：514.5nm
Laser power on sample：15~40mW
Resolution ratio：10~20cm-1
Measurement range：200cm-1~1900cm-1
Smooth treatment：Simple average, 15 points of convolution
＜ X-ray diffraction measures ＞
As X-ray diffraction measure, film cathode is arranged on and determined by " RINT2000PC " manufactured using company of science Chi Zhong, the measure of 2 θ=10~70 degree scopes is carried out using out-of-plane methods.Background compensation is that 2 θ=15~20 degree are attached It is near to be nearby attached and carried out with straight line with 40~45 degree.
＜ EPMA determine ＞
The distributional analysis of the mass concentration distributions or film sections of the film thickness direction of EPMA measure is taken as, electronics is used Probe-microanalyser (" JXA-8100 " of the manufacture of JEOL companies), without resin embedding to section is made with slicer Film cathode carries out the elementary analysis from collector to film surface.When obtaining the mass concentration distributions of film thickness direction, general is used Value obtained from the summation of the element of measure is converted into 100%, obtains mass concentration distributions of the Si in film thickness direction.
Negative pole [7] table 1
[table 48]
In negative pole [7] table 1, (Si) be not equivalent to element Z.
The making ＞ of negative pole [7] ＜ positive poles
(making 1 of positive pole)
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on one face of aluminium foil of 15 μm of thickness, and is dried, and 80 μm of thickness is rolled into press.
The making ＞ of negative pole [7] ＜ nonaqueous electrolytic solutions
(making 1 of nonaqueous electrolytic solution)
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
(making 2 of nonaqueous electrolytic solution)
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
(making 3 of nonaqueous electrolytic solution)
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
(making 4 of nonaqueous electrolytic solution)
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
The making ＞ of negative pole [7] ＜ lithium secondary batteries
Film cathode and positive pole are punching into 10mm φ, after being dried in vacuo at 110 DEG C, glove box is transferred to It is interior, it is by being punching into 14mm φ polyethylene separator that positive pole and negative pole is opposed under argon atmosphere, and nonaqueous electrolytic solution is added, make Make 2032 type coin batteries (lithium secondary battery).
Negative pole [7] embodiment 1
Use the positive pole and (non-water power made in the negative pole made in (making 1 of negative pole) item, (making of positive pole) item Solve the making 1 of liquid) nonaqueous electrolytic solution that makes in item, pass through《The making of lithium secondary battery》Method in makes coin electricity Pond.The battery behavior of the secondary cell is obtained by the method described in following ＜ cell evaluations ＞.
Negative pole [7] embodiment 2
What is made except the nonaqueous electrolytic solution of negative pole [7] embodiment 1 is changed into (making 2 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] embodiment 1, and carry out using the method for the ＞ records of evaluation of ＜ batteries Cell evaluation.As a result it is shown in negative pole [7] table 2.
Negative pole [7] embodiment 3
What is made except the nonaqueous electrolytic solution of negative pole [7] embodiment 1 is changed into (making 3 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] embodiment 1, and carry out using the method for the ＞ records of evaluation of ＜ batteries Cell evaluation.As a result it is shown in negative pole [7] table 2.
Negative pole [7] comparative example 1
What is made except the nonaqueous electrolytic solution of negative pole [7] embodiment 1 is changed into (making 4 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] embodiment 1, and carry out using the method for the ＞ records of evaluation of ＜ batteries Cell evaluation.As a result it is shown in negative pole [7] table 2.
Negative pole [7] comparative example 2
In addition to changing the negative pole of negative pole [7] embodiment 1 into made in (making 2 of negative pole) item electrode, with negative pole [7] embodiment 1 similarly makes battery, and carries out cell evaluation using the method for the ＞ records of evaluation of ＜ batteries.As a result it is shown in Negative pole [7] table 2.
Negative pole [7] comparative example 3
What is made except the nonaqueous electrolytic solution of negative pole [7] comparative example 2 is changed into (making 2 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] comparative example 2, and carry out using the method for the ＞ records of evaluation of ＜ batteries Cell evaluation.As a result it is shown in negative pole [7] table 2.
Negative pole [7] comparative example 4
What is made except the nonaqueous electrolytic solution of negative pole [7] comparative example 2 is changed into (making 3 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] comparative example 2, and carry out using the method for the ＞ records of evaluation of ＜ batteries Cell evaluation.As a result it is shown in negative pole [7] table 2.
Negative pole [7] comparative example 5
What is made except the nonaqueous electrolytic solution of negative pole [7] comparative example 2 is changed into (making 4 of nonaqueous electrolytic solution) item is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [7] comparative example 2, and use《The evaluation of battery》The method that item is recorded is carried out Cell evaluation.As a result it is shown in negative pole [7] table 2.
The evaluation ＞ of negative pole [7] ＜ batteries
By the following method, commenting for discharge capacity is carried out to the coin battery made in making ＞ of ＜ lithium secondary batteries Valency, Receptive determine of charging.
《The evaluation of discharge capacity》
With 1.23mA/cm2Current density to lithium to electrode charge to 4.2V, then with 4.2V constant-potential charge to electricity Flow valuve reaches 0.123mA, in negative pole after elements doped lithium, with 1.23mA/cm2Current density lithium to electrode discharge it is straight To 2.5V, 5 circulations are repeated in the charge and discharge cycles, the average value of the electric discharge of the 3rd~5 circulation are regard as discharge capacity. In addition, in the case of discharge capacity as unit mass, active material quality can be punching into phase by being subtracted by negative pole quality Try to achieve, and calculate according to the following formula with the quality of the copper foil of area.
Discharge capacity (mAh/g)
=[average discharge capacity (mAh) of the 3rd~5 circulation]/[active material quality (g)]
Active material quality (g)=negative pole quality (g)-copper foil quality (g) of the same area
《Charging is Receptive to be determined》
In the environment of 25 DEG C, will using 0.2C (by 1 hour electric discharge rated capacity current value as 1C, the specified appearance Amount depending on 1 hour rate (one-hour-rate) discharge capacity, similarly hereinafter) capacity when being charged to 4.2V charges as 0.2C Capacity, then 2.5V is discharged into 0.2C, 4.2V is then charged to 1C, capacity now is regard as 1C charging capacitys.By obtaining Result obtain charging acceptance by following formulas.
Charge acceptance (%)=100 × [1C charging capacitys]/[0.2C charging capacitys]
Negative pole [7] table 2
[table 49]
From the result of negative pole [7] table 2, difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl first are contained in nonaqueous electrolytic solution Silane base ester or hexamethyl cyclotrisiloxane, and the negative electrode active material (C) containing multielement is used as negative electrode active material The lithium secondary battery of matter, can enable charging by property it is tremendous improve, the negative electrode active material containing multielement (C) containing at least one lithium occlusion metal (A) and/or lithium occlusion alloy (B), and containing selected from least one of C or N member Plain (element Z).
Negative pole [8] [making of negative electrode active material]
(making 1 of negative electrode active material)
Using hybrid system ((strain) nara machinery makes manufactured hybrid system NHS-1 types) with treating capacity 90g, rotor Peripheral speed 60m/s, the condition of 3 minutes processing times are to natural graphite powder (d002：0.336nm、Lc：More than 100nm, drawing Graceful R values：0.11st, tap density：0.46g/cm3, real density：2.27g/cm3, volume reference average grain diameter：35.4 μm) located Reason, thus carries out spheroidization, in addition, in order to prevent from being mixed into oversize grain, being sieved repeatedly 5 times using the sieve of ASTM400 mesh.By this The negative electrode active material that sample is obtained is used as carbonaceous material (A).By the way that the operation is repeated, it is ensured that necessary to battery makes Amount.
(making 2 of negative electrode active material)
Micro mist is removed to commercially available flake natural graphite powder with wind classification device, in order to prevent in obtained powder Oversize grain is mixed into, is sieved repeatedly 5 times using the sieve of ASTM400 mesh.It regard the negative electrode active material so obtained as Carbonaceous matter Matter (B).
(making 3 of negative electrode active material)
The coal tar asphalt that quinoline non-soluble composition is below 0.05 mass % is heat-treated 10 in reacting furnace in 460 DEG C small When, obtain the block carbonization before processing body with meltbility of 385 DEG C of softening point.Obtained block carbonization before processing body is loaded Into metal container, in 1000 DEG C be heat-treated within 2 hours in the electric furnace of box-shaped, under nitrogen circulation.Use Roughpulverizer (Jitian make manufactured roll crusher) by unbodied piece obtained crushing, then with atomizer (matsubo company systems The turbine type mill made) Crushing of Ultrafine is carried out, micro mist then is removed with wind classification device, it is thick in order to prevent from being mixed into obtained powder Big particle, is sieved 5 times repeatedly using the sieve of ASTM400 mesh, obtains the amorphous powder that volume reference particle diameter is 9 μm.Will so Obtained negative electrode active material is used as carbonaceous material (C).
(making 4 of negative electrode active material)
The petroleum-type heavy oil obtained in carbonaceous material (A) during the pyrolysis of mixing naphtha, implements in non-active gas 1300 DEG C of carbonization treatment, then, obtains carbonaceous material, the carbonaceous material is in carbon by carrying out classification processing to sinter Coated on metallic substance (A) particle surface with carbonaceous material obtained from different crystalline carbonaceous materials.During classification processing, In order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, obtain carbonaceous material (D).Can from carbon yield To determine, obtained negative electrode active material powder is come from petroleum-type heavy oil relative to 95 parts by weight of graphite for 5 weight Carbonaceous is coated.
(making 5 of negative electrode active material)
80 mass % carbonaceous materials (A) and 20 mass % carbonaceous materials (B) are mixed until uniformly, mixing Carbonaceous matter is made Matter (E).
(making 6 of negative electrode active material)
95 mass % carbonaceous materials (A) and 5 mass % carbonaceous materials (C) are mixed until uniformly, mixing Carbonaceous matter is made Matter (F).
(making 7 of negative electrode active material)
80 mass % carbonaceous materials (D) and 20 mass % carbonaceous materials (A) are mixed until uniformly, mixing Carbonaceous matter is made Matter (G).
Carbonaceous material (A), (B), (C) and the mixing made in the making 1~7 for obtaining negative electrode active material in aforementioned manners Carbonaceous material (E), (F), the physical property of (G), shape etc..As a result conclude and be shown in negative pole [8] table 1.
Negative pole [8] table 1
Negative pole [8] [making of battery]
《The making 1 of positive pole》
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.Now just The density of the active material of pole is 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the active material layer of long 104mm sizes and width 30mm, is used as negative pole.Now The density of the active material of negative pole is 1.35g/cm3。
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
《The making 1 of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).Shell table of the summation of the electrode area of positive pole relative to battery The ratio between summation of area is 20.6.
Negative pole [8] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material for mix carbonaceous material (E) make negative pole,《Positive pole Making 1》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The nonaqueous electrolytic solution made in, passes through《Battery Make 1》Method in makes battery.The battery is carried out following《The evaluation of battery》Cell evaluation described in.As a result It is shown in negative pole [8] table 2.
Negative pole [8] embodiment 2
Except negative pole [8] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses mixing carbonaceous material (F) In addition, battery is made in the same manner as negative pole [8] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result show In negative pole [8] table 2.
Negative pole [8] embodiment 3
Except negative pole [8] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses mixing carbonaceous material (G) In addition, battery is made in the same manner as negative pole [8] embodiment 1, and carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result show In negative pole [8] table 2.
Negative pole [8] embodiment 4~6
Except the nonaqueous electrolytic solution of negative pole [8] embodiment 1~3 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and carry out cell evaluation.As a result it is shown in negative pole [8] table 2.
Negative pole [8] embodiment 7~9
Except the nonaqueous electrolytic solution of negative pole [8] embodiment 1~3 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and carry out cell evaluation.As a result it is shown in negative pole [8] table 2.
Negative pole [8] comparative example 1
Except the nonaqueous electrolytic solution of negative pole [8] embodiment 1 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [8] embodiment 1, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [8] table 2.
Negative pole [8] comparative example 2
Except the nonaqueous electrolytic solution of negative pole [8] embodiment 2 is changed into《The making 4 of nonaqueous electrolytic solution》What is made in is non-aqueous Beyond electrolyte, battery is made in the same manner as negative pole [8] embodiment 2, and carry out《The evaluation of battery》The cell evaluation that item is recorded. As a result it is shown in negative pole [8] table 2.
Negative pole [8] comparative example 3
Except negative pole [8] comparative example 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (A), Battery is made in the same manner as negative pole [8] comparative example 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [8] table 2.
Negative pole [8] comparative example 4
Except negative pole [8] comparative example 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (B), Battery is made in the same manner as negative pole [8] comparative example 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [8] table 2.
Negative pole [8] comparative example 5
Except negative pole [8] comparative example 1《The making 1 of negative pole》The negative electrode active material of item is used beyond carbonaceous material (C), Battery is made in the same manner as negative pole [8] comparative example 1, and is carried out《The evaluation of battery》The cell evaluation that item is recorded.As a result it is shown in negative Pole [8] table 2.
Negative pole [8] comparative example 6~8
Except the nonaqueous electrolytic solution of negative pole [8] comparative example 3~5 is changed into《The making 1 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [8] table 2.
Negative pole [8] comparative example 9~11
Except the nonaqueous electrolytic solution of negative pole [8] comparative example 3~5 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [8] table 2.
Negative pole [8] comparative example 12~14
Except the nonaqueous electrolytic solution of negative pole [8] comparative example 3~5 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made after the same method respectively, and evaluated.As a result it is shown in negative pole [8] table 2.
Negative pole [8]《The evaluation of battery》
(solid measure)
To the new battery without charge and discharge cycles, the initial stage of 5 circulations is carried out in 25 DEG C, 4.1V~3.0V voltage range Discharge and recharge (voltage range 4.1V~3.0V).By the 0.2C of the 5th circulation now (by the electric current of 1 hour electric discharge rated capacity Value depends on the discharge capacity of 1 hour rate (one-hour-rate) as 1C, the rated capacity, similarly hereinafter) discharge capacity conduct Initial capacity.
(output test 1)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, 3 are stood under -30 DEG C of environment small When, then discharged 10 seconds with 0.1C, 0.3C, 1.0C, 3.0C, 5.0C respectively, determine the voltage of the 10th second.By current-voltage The area for the triangle that straight line and lower voltage limit (3V) are surrounded is as low temperature power output (W).
(cyclic test)
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method charges to charging upper limit voltage 4.2V, is then discharged to discharge off with 2C constant current Voltage 3.0V, using the charge and discharge cycles as 1 circulation, and is repeated the circulation until 500 circulations.For cyclic test knot Battery after beam, carries out the discharge and recharges of 3 circulations under 25 DEG C of environment, using the 0.2C discharge capacities of the 3rd circulation as following Capacity after ring.By the initial capacity determined before cyclic test and cyclic test terminate after after the circulation that determines capacity according to following Calculating formula obtains circulation conservation rate.
Circulate capacity/initial capacity after conservation rate (%)=100 × circulation
Negative pole [8] table 2
[table 51]
From the result of negative pole [8] table 2, by containing difluorophosphoric acid lithium salts, methanesulfonic acid trimethyl silyl ester, six Methyl cyclotrisiloxane, and the negative pole containing the different negative electrode active material of two or more property is used, cycle characteristics and low temperature are defeated Go out power good.
Negative pole [9] [10] [making of negative electrode active material]
(making 1 of negative electrode active material)
Using spheroidization processing unit (nara machinery makes manufactured hybrid system) with rotating speed 6500rpm to high-purity Change the flake natural graphite (d002 of about 150 μm treated of median particle diameter：0.336nm、Lc：More than 100nm, Raman R value： 0.11st, real density：2.27g/cm3, ash content：0.05 mass %) spheroidization processing in 5 minutes is carried out, reuse wind-driven type grader (OMC-100 of seishin enterprise-like corporations manufacture) removes 45 mass % micro mists, obtains carbonaceous material (A).
(making 2 of negative electrode active material)
The carbonaceous material (A) made in (making 1 of negative electrode active material) is encased in graphite crucible, using directly logical Electric furnace in 3000 DEG C be heat-treated within 5 hours under inactive atmosphere, obtains carbonaceous material (B).
(making 3 of negative electrode active material)
The oil obtained in the carbonaceous material (A) that (making 1 of negative electrode active material) makes during the pyrolysis of mixing naphtha Then class heavy oil, the carbonization treatment of 1300 DEG C of implementation in non-active gas, carbon is obtained by carrying out classification processing to sinter Metallic substance, the carbonaceous material has been coated on carbonaceous material (A) particle surface with different crystalline carbonaceous materials Obtained carbonaceous material.During classification processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh, Obtain carbonaceous material (C).From carbon yield it was determined that obtained negative electrode active material powder is relative to 95 parts by weight of graphite The carbonaceous for the coming from petroleum-type heavy oil cladding of 5 weight.
(making 4 of negative electrode active material)
The coal tar asphalt that quinoline non-soluble composition is below 0.05 mass % is heat-treated 10 in reacting furnace in 460 DEG C small When, obtain the block carbonization before processing body with meltbility of 385 DEG C of softening point.Obtained block carbonization before processing body is loaded Into metal container, in 1000 DEG C be heat-treated within 2 hours in the electric furnace of box-shaped, under nitrogen circulation.Use Roughpulverizer (Jitian make manufactured roll crusher) by unbodied piece obtained crushing, then with atomizer (matsubo company systems The turbine type mill made) Crushing of Ultrafine is carried out, obtain the amorphous powder of 17 μm of volume reference average grain diameter.In order to prevent obtained powder Oversize grain is mixed into end, is sieved repeatedly 5 times using the sieve of ASTM400 mesh.It regard the negative electrode active material so obtained as carbon Metallic substance (D).
The carbonaceous material (A) of making, carbonaceous material (B), carbonaceous material (C), carbonaceous material (D) are determined in aforementioned manners Shape and physical property.As a result it is shown in negative pole [9] [10] table 1.
Negative pole [9] [10] table 1
[table 52]
Negative pole [9] [10] [making of battery]
《The making 1 of positive pole》
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the positive electrode active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.Now Positive pole positive electrode active material layer density be 2.35g/cm3。
《The making 1 of negative pole》
100 parts by weight are added in 98 parts by weight negative electrode active materials as the aqueous of the sodium carboxymethylcellulose of thickener Dispersion liquid (concentration of sodium carboxymethylcellulose is 1 mass %), 2 parts by weight are used as the SBR styrene butadiene rubberses of adhesive Aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %), is mixed with disperser, slurry is made.Will To slurry be coated on the rolled copper foil two sides of 10 μm of thickness, and dry, 75 μm of thickness be rolled into press, then be cut into The shape of uncoated portion with wide 104mm, the negative electrode active material layer of long 104mm sizes and width 30mm, is used as negative pole.
The density of the negative electrode active material layer of negative pole now is 1.33~1.36g/cm3Scope (be shown in negative pole [9] the most right column of [10] table 2).From the foregoing, in negative electrode active material layer as adhesive SBR styrene butadiene rubberses Content relative to whole negative electrode active material layer is 1 mass %.In addition, [(thickness of negative electrode active material layer simultaneously)/ (thickness of collector)] value be 75 μm/10 μm=7.5.
《The making 1 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Difluorophosphoric acid lithium salts (LiPO containing 0.3 mass %2F2)。
《The making 2 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Methanesulfonic acid trimethyl silyl ester containing 0.3 mass %.
《The making 3 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6).In addition, also Hexamethyl cyclotrisiloxane containing 0.3 mass %.
《The making 4 of nonaqueous electrolytic solution》
Under dry argon atmosphere, in ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) Mixture (volume ratio 3:3:4) in, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6)。
《The making 1 of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms (m Ω).Shell table of the summation of the electrode area of positive pole relative to battery The ratio between summation of area is 20.6.
Negative pole [9] [10] embodiment 1
Use《The making 1 of negative pole》Negative electrode active material made for carbonaceous material (A) negative pole,《The system of positive pole Make 1》In the positive pole that makes and《The making 1 of nonaqueous electrolytic solution》The nonaqueous electrolytic solution made in, passes through《The making of battery 1》Method in makes battery.It is following《The evaluation of battery》Method described in is measured to the battery.As a result it is shown in Negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 2
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 1 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 1, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 3
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 1 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 1, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] comparative example 1
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 1 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 1, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 4
Except negative pole [9] [10] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses carbonaceous material (B) In addition, battery is made according to the same method of negative pole [9] [10] embodiment 1, and is similarly evaluated.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 5
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 4 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 4, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 6
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 4 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 4, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] comparative example 2
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 4 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 4, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 7
Except negative pole [9] [10] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses carbonaceous material (C) In addition, battery is made according to the same method of negative pole [9] [10] embodiment 1, and is similarly evaluated.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 8
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 7 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 7, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 9
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 7 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 7, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] comparative example 3
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 7 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Beyond nonaqueous electrolytic solution, battery is made according to the same method of negative pole [9] [10] embodiment 7, and similarly evaluated.Knot Fruit is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 10
Except negative pole [9] [10] embodiment 1《The making 1 of negative pole》The negative electrode active material of item uses carbonaceous material (D) In addition, battery is made according to the same method of negative pole [9] [10] embodiment 1, and is similarly evaluated.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 11
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 10 is changed into《The making 2 of nonaqueous electrolytic solution》Made in Nonaqueous electrolytic solution beyond, make battery according to the same method of negative pole [9] [10] embodiment 10, and similarly commented Valency.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] embodiment 12
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 10 is changed into《The making 3 of nonaqueous electrolytic solution》Made in Nonaqueous electrolytic solution beyond, make battery according to the same method of negative pole [9] [10] embodiment 10, and similarly commented Valency.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10] comparative example 4
Except the nonaqueous electrolytic solution of negative pole [9] [10] embodiment 10 is changed into《The making 4 of nonaqueous electrolytic solution》Made in Nonaqueous electrolytic solution beyond, make battery according to the same method of negative pole [9] [10] embodiment 10, and similarly commented Valency.As a result it is shown in negative pole [9] [10] table 2.
Negative pole [9] [10]《The evaluation of battery》
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.Then following shown output tests are carried out.
(output test)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are surrounded The area of triangle be used as power output (W).It regard the power output before cyclic test as " power output at initial stage ".
(cyclic test)
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method charges to charging upper limit voltage 4.2V, is then discharged to discharge off with 2C constant current Voltage 3.0V, using the charge and discharge cycles as 1 circulation, and is repeated the circulation until 500 circulations.For cyclic test knot Battery after beam, carries out the discharge and recharges of 3 circulations under 25 DEG C of environment, using the 0.2C discharge capacities of the 3rd circulation as following Capacity after ring.By the initial capacity determined before cyclic test and cyclic test terminate after after the circulation that determines capacity according to following Calculating formula obtains circulation conservation rate.
Circulate capacity/initial capacity after conservation rate (%)=100 × circulation
Impedance Rct and bilayer capacity C dl in negative pole [9] [10] table 2 are to one of contributive parameter of power output, resistance Anti- Rct value is smaller, or double-deck capacity C dl value is bigger, then power output more has the tendency of improvement.In addition, " impedance Rct " " double-deck capacity C dl " is by illustrating that the method described in the part of impedance is obtained.
The power output that battery after terminating for cyclic test carries out described in above-mentioned (output test) item is surveyed It is fixed, and it regard obtained value as " power output after cyclic test ".Above-mentioned negative pole [9] [10] embodiment and negative pole [9] [10] ratio Compared with the output test result of the lithium secondary battery of example, solid measure result, circulation conservation rate and above-mentioned opposed impedance The reaction resistance and the measurement result of double-deck capacity obtained in measure, which are concluded, to be shown in negative pole [9] [10] table 2.
Negative pole [9] [10] table 2
[table 53]
From the result of negative pole [9] [10] table 2, by containing difluorophosphoric acid lithium salts, methanesulfonic acid in nonaqueous electrolytic solution The specific compounds such as trimethyl silyl ester, hexamethyl cyclotrisiloxane, and by being containing tap density in negative pole More than 0.1 and use mercury, Hg porosimeter determine 0.01 μm~1 μ m micropore volume for more than 0.01mL/g bearing Pole active material, even for large-scale battery, can also realize power output and high circulation conservation rate after high circulation, from And the lithium secondary battery with both high-output power and long-life can be provided.
In addition, by containing specific compound, and the reaction for producing the opposed battery of negative pole in nonaqueous electrolytic solution Resistance is 500 below Ω, even for large-scale battery, can also realize that power output and high circulation are kept after high circulation Rate, so as to have both high-output power and the good life-span.
The making ＞ of electrolyte [1] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the two sides of the copper foil of 10 μm of thickness, and dried, press is used Thickness is rolled into for 75 μm, then is cut into being not coated with width 104mm, the active material layer of long 104mm sizes and width 30mm The shape of cloth part, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The nominal discharge capacity of the battery is about 6 ampere-hours (Ah), with 10kHz The DC resistance component that alternating current method is determined is about 5 milliohms.
[evaluation of battery]
(assay method of initial capacity)
To the new battery without charge and discharge cycles, the initial stage of 5 circulations is carried out in 25 DEG C, 4.1V~3.0V voltage range Discharge and recharge (voltage range 4.1V~3.0V).By the 0.2C of the 5th circulation now (by the electric current of 1 hour electric discharge rated capacity Value depends on the discharge capacity of 1 hour rate (one-hour-rate) as 1C, the rated capacity, similarly hereinafter) discharge capacity conduct Initial capacity.
(assay method of low temperature power output)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, under -30 DEG C of environment respectively with 0.1C, 0.3C, 1.0C, 3.0C, 5.0C discharge 10 seconds, determine the voltage of the 10th second.By current-voltage straight line and lower voltage limit The area for the triangle that (3V) is surrounded is used as power output (W).
Electrolyte [1] embodiment 1
In the case where drying argon atmosphere, to the mixture (volume ratio 15 of ethylene carbonate (EC), methyl ethyl carbonate (EMC):85) In lithium hexafluoro phosphate (LiPF is added with 1mol/L6) and dissolved, the six of 0.3 mass % amount are mixed in the mixed solution Methyl cyclotrisiloxane, prepares nonaqueous electrolytic solution.Battery is made according to the method described above using the nonaqueous electrolytic solution, and determines low temperature Power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 2
Using in electrolyte [1] embodiment 1 with EC and EMC volume ratio 20:80 nonaqueous electrolytic solutions prepared make electricity Pond, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 3
EC, dimethyl carbonate (DMC), EMC mixture are changed to using the nonaqueous solvents in electrolyte [1] embodiment 1 (volume ratio 15:40:45) nonaqueous electrolytic solution prepared makes battery, and determines low temperature power output.As a result such as electrolyte [1] shown in table 1.
Electrolyte [1] embodiment 4
Using being mixed with the hexamethyl cyclotrisiloxane that pheiiyldimetliyl silicon fluoride comes in alternative electrolyte [1] embodiment 1 And the nonaqueous electrolytic solution prepared, battery is made, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 5
Using being mixed with hexamethyl cyclotrisiloxane that HMDO comes in alternative electrolyte [1] embodiment 1 and The nonaqueous electrolytic solution of preparation, makes battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 6
Using being mixed with the pregnancy basic ring three that methanesulfonic acid trimethyl silyl ester comes in alternative electrolyte [1] embodiment 1 Siloxanes and the nonaqueous electrolytic solution prepared, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 7
Prepared using hexamethyl cyclotrisiloxane that methyl fluorosulfonate comes in alternative electrolyte [1] embodiment 1 is mixed with Nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 8
Using being mixed with hexamethyl cyclotrisiloxane that lithium nitrate comes in alternative electrolyte [1] embodiment 1 and preserve 3 days Obtained from nonaqueous electrolytic solution make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 9
Using being mixed with according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7) The silica of pregnancy basic ring three that difluorophosphate prepared by the method described in page~the 582 comes in alternative electrolyte [1] embodiment 1 Alkane and the nonaqueous electrolytic solution for preparing makes battery as nonaqueous electrolytic solution, and determine low temperature power output.As a result such as electrolyte [1] shown in table 1.
Electrolyte [1] embodiment 10
In electrolyte [1] embodiment 9, it is changed to using by the combined amount of difluorophosphate relative to nonaqueous solvents and hexafluoro The mixed solution of lithium phosphate is nonaqueous electrolytic solution obtained from 0.08 mass % amount to make battery, and determines low temperature output work Rate.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 11
Using being mixed with hexamethyl cyclotrisiloxane that lithium acetate comes in alternative electrolyte [1] embodiment 1 and preserve 3 days Obtained from nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] embodiment 12
The ＞ of making -2 of ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[making of electrolyte]
Make and the same nonaqueous electrolytic solution of electrolyte [1] embodiment 1.
[assembling of battery]
Wind positive pole and negative pole are overlapping together with the dividing plate of polyethylene so that positive pole is not directly contacted with negative pole, be made Electrode body.Expose the terminal of positive pole and negative pole to be externally mounted in battery can.
Then, riveting molding is carried out, 18650 type cylinder batteries are manufactured after injection 5mL electrolyte described later thereto.Should The nominal discharge capacity of battery is about 0.7 ampere-hour (Ah), and the D.C. resistance determined with 10kHz alternating current methods is about 35 milliohm (m Ω).In addition, the summation of the electrode area of above-mentioned positive pole is 19.4 relative to the area ratio of the surface area of the shell of the secondary cell Times.For above-mentioned battery, low temperature power output is determined in the same manner as electrolyte [1] embodiment 1.As a result such as the institute of electrolyte [1] table 1 Show.
Electrolyte [1] comparative example 1
Made using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [1] embodiment 1 and preparing Battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 2
Made using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [1] embodiment 2 and preparing Battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 3
Made using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [1] embodiment 3 and preparing Battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 4
In the case where drying argon atmosphere, to the mixture (volume ratio 4 of ethylene carbonate and methyl ethyl carbonate:6) with 1mol/L in Add lithium hexafluoro phosphate (LiPF6) and dissolved, then hexamethyl is mixed using the amount relative to the mixed solution as 0.3 mass % Cyclotrisiloxane prepares nonaqueous electrolytic solution.
Battery is made using the nonaqueous electrolytic solution, and determines low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 5
Using being mixed with the hexamethyl cyclotrisiloxane that pheiiyldimetliyl silicon fluoride comes in alternative electrolyte [1] comparative example 4 And the nonaqueous electrolytic solution prepared, battery is made, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 6
Using being mixed with hexamethyl cyclotrisiloxane that HMDO comes in alternative electrolyte [1] comparative example 4 and The nonaqueous electrolytic solution of preparation, makes battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 7
Using being mixed with the pregnancy basic ring three that methanesulfonic acid trimethyl silyl ester comes in alternative electrolyte [1] comparative example 4 Siloxanes and the nonaqueous electrolytic solution prepared, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 8
Prepared using hexamethyl cyclotrisiloxane that methyl fluorosulfonate comes in alternative electrolyte [1] comparative example 4 is mixed with Nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 9
Using being mixed with hexamethyl cyclotrisiloxane that lithium nitrate comes in alternative electrolyte [1] comparative example 4 and preserve 3 days Obtained from nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 10
Prepared using hexamethyl cyclotrisiloxane that difluorophosphate comes in alternative electrolyte [1] comparative example 4 is mixed with Nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 11
Using being mixed with hexamethyl cyclotrisiloxane that lithium acetate comes in alternative electrolyte [1] comparative example 4 and preserve 3 days Obtained from nonaqueous electrolytic solution, make battery, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 12
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [1] comparative example 4 and preparing, electricity is made Pond, and determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] comparative example 13
In electrolyte [1] embodiment 12, using the nonaqueous electrolytic solution same with electrolyte [1] comparative example 1, battery is made, And determine low temperature power output.As a result as shown in electrolyte [1] table 1.
Electrolyte [1] table 1
[table 54]
From electrolyte [1] table 1, the electrolyte of the EC containing specified quantitative and specific compound in nonaqueous electrolytic solution [1] lithium secondary battery of embodiment 1~11, not only with containing excessive EC and not containing the electrolyte [1] of specific compound and comparing Lithium secondary battery compared with example 12 is compared, even if although and not containing the electricity of specific compound in particular range with EC amounts Liquid [1] is solved although comparative example 1~3 and the lithium containing electrolyte [1] comparative example 4~11 excessive specific compound EC Secondary cell is compared, and low temperature characteristics of output power is improved.In addition, in nonaqueous electrolytic solution the EC containing specified quantitative and specific The lithium secondary battery of electrolyte [1] embodiment 12 of compound, although not containing specialization in particular range with EC amounts The lithium secondary battery of electrolyte [1] comparative example 13 of compound is compared, and low temperature characteristics of output power is improved.
In addition, the effect is not both simple superpositions, by meeting two aspect conditions, effect is remarkably reinforced.Electrolyte [1] recorded in table 1 using during nonaqueous electrolytic solution containing specific compound (being in addition same composition) relative to using The climbing of low temperature power output when not containing the nonaqueous electrolytic solution of specific compound, compares with the excessive electrolyte [1] of EC amounts Compared compared with example 4~11, in electrolyte [1] embodiment 1~12, the value is big, and effect of the invention is big.
In addition, electrolyte [1] embodiment 12 is relative to the power output climbing of electrolyte [1] comparative example 13 20.8%, although and using the different electrolyte of same material battery structure [1] embodiment 1 relative to electrolyte [1] The power output climbing of comparative example 1 is 26.4%, it is known that battery structure has big to the effect of the nonaqueous electrolytic solution of the present invention Influence.That is, the small battery of battery, D.C. resistance for high power capacity, effect of the invention is especially big.
Further, although do not recorded in table, when but being less than 1 capacity % electrolyte using EC contents, with electrolyte [1] embodiment 1 is compared, and initial capacity is somewhat reduced, and the characteristics of output power or cycle characteristics under normal temperature are deteriorated.
As described above, by using the nonaqueous electrolytic solution of the present invention, the i.e. non-water power of the secondary cell with following characteristics Liquid is solved, very big low temperature characteristics of output power can be played, the feature of the non-aqueous electrolyte for secondary battery is：It is extremely Few mixed solvent containing ethylene carbonate, ethylene carbonate holds for the ratio of nonaqueous solvents total amount for 1 capacity %~25 % is measured, the nonaqueous electrolytic solution also contains selected from least one of following substances compound, and it is in whole nonaqueous electrolytic solutions In content be more than 10ppm, the material includes：Cyclic siloxane compound, the formula (2) of formula (1) expression are represented Compound that fluorosilane compounds, formula (3) are represented, intramolecular have the compounds of S-F keys, nitrate, nitrite, single fluorine Phosphate, difluorophosphoric acid salt, acetate and propionate.
In addition, compared with the battery structure of electrolyte [1] embodiment 12, in the battery structure of electrolyte [1] embodiment 1, I.e. in the small battery of the battery of high power capacity, D.C. resistance, the effect can be significantly more played.
The ＞ of making -1 of electrolyte [2] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[assembling of battery]
Wind positive pole and negative pole are overlapping together with the dividing plate of polyethylene so that positive pole is not directly contacted with negative pole, be made Electrode body.Expose the terminal of positive pole and negative pole to be externally mounted in battery can.Then, 5mL electrolysis described later are injected thereto After liquid, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The battery element that 1 battery case of secondary cell is stored is had The nominal discharge capacity of some electric capacity, i.e. secondary cell is about 0.7 ampere-hour (Ah), the direct current determined with 10kHz alternating current methods Resistance components are about 35 milliohms (m Ω).
[evaluation of battery]
(discharge and recharge at initial stage)
To the battery of manufacture, after charging to 4.2V with 0.2C constant-current constant-voltage mise-a-la-masse method at 25 DEG C, with 0.2C constant current is discharged to 3.0V.Being carried out 5 circulations makes battery stable.The electric discharge of the 5th circulation now is held Amount is used as initial capacity.Moreover, using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity is depended on 1 hour The discharge capacity of rate (one-hour-rate).
(cyclic test)
Battery to implementing discharge and recharge at initial stage, carries out charging to 4.2V with 1C constant-current constant-voltage at 60 DEG C Afterwards, then with 1C constant current 3.0V 500 circulations of discharge and recharge are discharged to.By the 500th cyclic discharge capacity phase now Ratio for the 1st cyclic discharge capacity is used as circulation conservation rate.
(low-temperature test)
Battery to implementing discharge and recharge at initial stage, is charged at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method After 4.2V, implement 0.2C constant current electric discharge at -30 DEG C., will be just using discharge capacity now as low temperature capacity at initial stage Phase low temperature capacity is used as low temperature discharge rate at initial stage relative to the ratio of initial capacity.
In addition, being charged to the battery after cyclic test at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method After 4.2V, 3.0V is discharged to 0.2C constant current.It is carried out 3 circulation, using its 3rd circulation discharge capacity as Capacity after circulation.Then, after charging to 4.2V at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method to same battery, Implement 0.2C constant current electric discharge at -30 DEG C., will be low after circulation using discharge capacity now as low temperature capacity after circulation Warm capacity is used as low temperature discharge rate after circulation relative to the ratio of capacity after circulation.
Electrolyte [2] embodiment 1
In the case where drying argon atmosphere, to the mixed of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) Compound (volume ratio 2:4:4) lithium hexafluoro phosphate (LiPF is added with 0.9mol/L in6) and dissolved, make to contain in the mixed solution Have 0.3 mass % according to Inorganic Nuclear Chemistry Letters (1969), page 581~the of 5 (7) Difluorophosphate prepared by the method described in page 582, prepares nonaqueous electrolytic solution.18650 types are manufactured using the nonaqueous electrolytic solution Cylinder battery, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.Moreover, with centrifuge Machine reclaims electrolyte from the battery after the low temperature capacity measure after circulation, by gas-chromatography (GC) to raw in ester exchange reaction Into the amount of dimethyl carbonate (DMC) analyzed when, in an amount of from 0.5 mass % in electrolyte.
Electrolyte [2] comparative example 1
In addition to not containing difluorophosphate, 18650 type cylinder batteries are made in the same manner as electrolyte [2] embodiment 1, And determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.Moreover, with centrifugal separator after circulation Low temperature capacity determine after battery in reclaim electrolyte, by gas-chromatography (GC) to the carbonic acid two that is generated in ester exchange reaction When the amount of methyl esters (DMC) is analyzed, in an amount of from 9.7 mass % in electrolyte.
Electrolyte [2] comparative example 2
In the case where drying argon atmosphere, to the mixture (volume ratio 2 of ethylene carbonate (EC) and diethyl carbonate (DEC):8) in Lithium hexafluoro phosphate (LiPF is added with 0.9mol/L6) and dissolved, make the difluoro phosphorus containing 0.3 mass % in the mixed solution Sour lithium, prepares nonaqueous electrolytic solution.18650 type cylinder batteries are manufactured using the nonaqueous electrolytic solution, and determine circulation conservation rate and low Warm discharge rate.As a result as shown in electrolyte [2] table 1.
Electrolyte [2] embodiment 2
In addition to substituting methyl ethyl carbonate using methyl n-propyl ester, in the same manner as electrolyte [2] embodiment 1 18650 type cylinder batteries are made, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.
Electrolyte [2] comparative example 3
In addition to not containing difluorophosphate, 18650 type cylinder batteries are made in the same manner as electrolyte [2] embodiment 2, And determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.
The ＞ of making -2 of electrolyte [2] ＜ secondary cells
The making ＞ of ＜ positive poles
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
The making ＞ of ＜ negative poles
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
The assembling ＞ of ＜ batteries
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, are made Electrode is thoroughly impregnated, and is sealed and is made rectangular cell.The electricity that the battery element stored in 1 battery case of secondary cell has Hold, i.e. the nominal discharge capacity of secondary cell, about 6 ampere-hours (Ah), the DC resistance component determined with 10kHz alternating current methods About 5 milliohms (m Ω).
Electrolyte [2] embodiment 3
Rectangular cell is made using the electrolyte used in electrolyte [2] embodiment 1, and using real with electrolyte [2] Apply the identical method of example 1 and implement cyclic test, low-temperature test, and determine circulation conservation rate and low temperature discharge rate.As a result as being electrolysed Shown in liquid [2] table 1.
Electrolyte [2] comparative example 4
Rectangular cell is made using the electrolyte used in electrolyte [2] comparative example 1, implements cyclic test, low temperature examination Test, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.
Electrolyte [2] comparative example 5
Rectangular cell is made using the electrolyte used in electrolyte [2] comparative example 2, implements cyclic test, low temperature examination Test, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [2] table 1.
Electrolyte [2] table 1
[table 55]
From electrolyte [2] table 1, if (electrolyte [2] embodiment 1,2, electrolyte [2] compares to each cylinder battery (electrolyte [2] embodiment 3,5) is compared, then in nonaqueous electrolytic solution electrolyte [2] comparative example 4 for example 1~3), rectangular cell The lithium secondary battery of electrolyte [2] embodiment simultaneously containing asymmetric linear carbonate and difluorophosphoric acid salt, with not containing this The lithium secondary battery of a little electrolyte [2] comparative examples of any one is compared, and circulation conservation rate, low temperature discharge rate are all improved.
As described above, the nominal discharge capacity of the present embodiment and the cylinder battery of this comparative example is less than 3 ampere-hours (Ah), DC resistance component is more than 10 milliohms (m Ω).On the other hand, the nominal discharge of the present embodiment and the rectangular cell of this comparative example holds Measure to be more than 3 ampere-hours (Ah), DC resistance component be 10 milliohms (m Ω) below.That is, the side of the present embodiment, this comparative example Shape battery is compared with cylinder battery, and resistance is small, and electric capacity is big.Moreover, being compared with electrolyte [2] embodiment 1 relative to electrolyte [2] The low-temperature characteristics of example 1 improves degree and compared, and electrolyte [2] embodiment 3 is carried relative to the low-temperature characteristics of electrolyte [2] comparative example 4 High level is big, and in the big secondary cell of electric capacity or the small secondary cell of D.C. resistance, effect of the invention is bigger.
The ＞ of manufacture -1 of electrolyte [3] ＜ secondary cells
[manufacture of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[manufacture of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.
Then, inject the following electrolyte of 20mL [3] embodiment in the battery can equipped with electrode group and electrolyte [3] compares The nonaqueous electrolytic solution of example, is thoroughly impregnated electrode, seals and make rectangular cell.The nominal discharge capacity of the battery is about 6 peaces Hour (Ah) is trained, is about 5 milliohms (m Ω) with the DC resistance component that 10kHz alternating current methods are determined.In addition, the electrode of above-mentioned positive pole The summation of area is 20.65 times relative to the area ratio of the surface area of the shell of the secondary cell.
[evaluation of battery]
(solid measure)
To the new battery without discharge and recharge, the charge and discharge at initial stage of 5 circulations is carried out in 25 DEG C, 4.1V~3.0V voltage range Electric (voltage range 4.1V~3.0V).The 0.2C of the 5th circulation now (is made the current value of 1 hour electric discharge rated capacity For 1C, the rated capacity depends on the discharge capacity of 1 hour rate (one-hour-rate), similarly hereinafter) discharge capacity is used as initial stage Capacity.
(output test)
With 0.2C constant current charge within 150 minutes under 25 DEG C of environment, under -30 DEG C of environment respectively with 0.1C, 0.3C, 1.0C, 3.0C, 5.0C discharge 10 seconds, determine the voltage of the 10th second.Will be by current-voltage straight line and lower voltage limit (3V) The area of the triangle surrounded is used as power output (W).
Electrolyte [3] embodiment 1
In the case where drying argon atmosphere, to the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and methyl propionate (MP) (volume ratio 3:6:1) lithium hexafluoro phosphate (LiPF is added with 1mol/L in6) and dissolved, then mixed in the mixed solution The hexamethyl cyclotrisiloxane of 0.3 mass % amount, prepares nonaqueous electrolytic solution.Made in aforementioned manners using the nonaqueous electrolytic solution Battery, and determine low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 2
Using the ethyl acetate (EA) with equivalent prepared come the methyl propionate in alternative electrolyte [3] embodiment 1 it is non- Water electrolysis liquid makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 3
Using the methyl acetate (MA) with equivalent prepared come the methyl propionate in alternative electrolyte [3] embodiment 1 it is non- Water electrolysis liquid makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 4
In the case where drying argon atmosphere, to ethylene carbonate (EC), methyl ethyl carbonate (EMC), methyl propionate (MP) and acetic acid first Mixture (the volume ratio 30 of ester (MA):60:5:5) lithium hexafluoro phosphate (LiPF is added with 1mol/L in6) and dissolved, then The hexamethyl cyclotrisiloxane of 0.3 mass % amount is mixed in the mixed solution, nonaqueous electrolytic solution is prepared.Use the non-water power Solution liquid makes battery in aforementioned manners, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 5
Using in electrolyte [3] embodiment 1 by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and methyl propionate (MP) The volume ratio of mixture be changed to 3:4:3 and prepare nonaqueous electrolytic solution, battery is made according to the method described above, and determine low temperature Power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 6
In the case where drying argon atmosphere, to the mixture (volume ratio 3 of ethylene carbonate (EC) and methyl propionate (MP):7) in 1mol/L adds lithium hexafluoro phosphate (LiPF6) and dissolved, the six of 0.3 mass % amount are then mixed in the mixed solution Methyl cyclotrisiloxane, prepares nonaqueous electrolytic solution.Battery is made in aforementioned manners using the nonaqueous electrolytic solution, and it is defeated to determine low temperature Go out power.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 7
The silicon of pregnancy basic ring three come using the pheiiyldimetliyl silicon fluoride of equivalent volumes in alternative electrolyte [3] embodiment 1 Nonaqueous electrolytic solution obtained from oxygen alkane makes battery as nonaqueous electrolytic solution, and determines low temperature power output.As a result as being electrolysed Shown in liquid [3] table 1.
Electrolyte [3] embodiment 8
The silicon of pregnancy basic ring three come using the pregnancy basic ring disiloxane of equivalent volumes in alternative electrolyte [3] embodiment 1 Nonaqueous electrolytic solution obtained from oxygen alkane makes battery as nonaqueous electrolytic solution, and determines low temperature power output.As a result as being electrolysed Shown in liquid [3] table 1.
Electrolyte [3] embodiment 9
The hexamethyl come using the methanesulfonic acid trimethyl silyl ester of equivalent volumes in alternative electrolyte [3] embodiment 1 Nonaqueous electrolytic solution obtained from cyclotrisiloxane makes battery as nonaqueous electrolytic solution, and determines low temperature power output.As a result As shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 10
Using the hexamethyl cyclotrisiloxane that the methyl fluorosulfonate of equivalent volumes comes in alternative electrolyte [3] embodiment 1 Obtained nonaqueous electrolytic solution makes battery as nonaqueous electrolytic solution, and determines low temperature power output.As a result such as electrolyte [3] table Shown in 1.
Electrolyte [3] embodiment 11
The hexamethyl cyclotrisiloxane that is come using the lithium nitrate of equivalent volumes in alternative electrolyte [3] embodiment 1 is simultaneously preserved Nonaqueous electrolytic solution obtained from 3 days makes battery as nonaqueous electrolytic solution, and determines low temperature power output.As a result such as electrolyte [3] shown in table 1.
Electrolyte [3] embodiment 12
Using equivalent volumes (relative to nonaqueous solvents and lithium hexafluoro phosphate mixed solution be 0.3 mass % amount) root According to Inorganic Nuclear Chemistry Letters (1969), the side described in page 581~page 582 of 5 (7) The hexamethyl cyclotrisiloxane that comes in alternative electrolyte [3] embodiment 1 of difluorophosphate prepared by method and the non-aqueous solution electrolysis prepared Liquid makes battery, and determine low temperature power output as nonaqueous electrolytic solution.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 13
It is changed to using the combined amount of the difluorophosphate in electrolyte [3] embodiment 12 relative to nonaqueous solvents and hexafluoro The nonaqueous electrolytic solution that the mixed solution of lithium phosphate is prepared for 0.08 mass % amount, makes battery, and determine low temperature output work Rate.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] embodiment 14
The ＞ of making -2 of ＜ secondary cells
The making ＞ of ＜ positive poles
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
The making ＞ of ＜ negative poles
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[preparation of electrolyte]
Prepare and the identical nonaqueous electrolytic solution of electrolyte [3] embodiment 1.
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After electrolyte, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The nominal discharge capacity of the battery is about 0.7Ah, is used The D.C. resistance that 10kHz alternating current methods are determined is about 35 milliohms (m Ω).In addition, the summation of the electrode area of above-mentioned positive pole relative to The area ratio of the surface area of the shell of the secondary cell is 19.4 times.In above-mentioned battery, in the same manner as electrolyte [3] embodiment 1 Determine low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 1
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [3] embodiment 1 and preparing, with above-mentioned Method makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 2
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [3] embodiment 2 and preparing, with above-mentioned Method makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 3
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [3] embodiment 3 and preparing, with above-mentioned Method makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 4
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [3] embodiment 4 and preparing, with above-mentioned Method makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 5
Using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane in electrolyte [3] embodiment 5 and preparing, with above-mentioned Method makes battery, and determines low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 6
In the case where drying argon atmosphere, to the mixture (volume ratio 3 of ethylene carbonate and methyl ethyl carbonate:7) with 1mol/L in Add lithium hexafluoro phosphate (LiPF6) and dissolved, prepare nonaqueous electrolytic solution.Made in aforementioned manners using the nonaqueous electrolytic solution Battery, and determine low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 7
In the case where drying argon atmosphere, to the mixture (volume ratio 3 of ethylene carbonate and methyl ethyl carbonate:7) with 1mol/L in Add lithium hexafluoro phosphate (LiPF6) and dissolved, the pregnancy basic ring of 0.3 mass % amount is then mixed in the mixed solution Trisiloxanes, prepares nonaqueous electrolytic solution.Battery is made in aforementioned manners using the nonaqueous electrolytic solution, and determines low temperature output work Rate.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 8
The silicon of pregnancy basic ring three come using the pheiiyldimetliyl silicon fluoride of equivalent volumes in alternative electrolyte [3] comparative example 7 Nonaqueous electrolytic solution obtained from oxygen alkane makes battery, and determine low temperature power output in aforementioned manners as nonaqueous electrolytic solution.Knot Fruit is as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 9
The silicon of pregnancy basic ring three come using the pregnancy basic ring disiloxane of equivalent volumes in alternative electrolyte [3] comparative example 7 Nonaqueous electrolytic solution obtained from oxygen alkane makes battery, and determine low temperature power output in aforementioned manners as nonaqueous electrolytic solution.Knot Fruit is as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 10
The hexamethyl come using the methanesulfonic acid trimethyl silyl ester of equivalent volumes in alternative electrolyte [3] comparative example 7 Nonaqueous electrolytic solution obtained from cyclotrisiloxane makes battery, and determine low temperature output in aforementioned manners as nonaqueous electrolytic solution Power.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 11
Using the hexamethyl cyclotrisiloxane that the methyl fluorosulfonate of equivalent volumes comes in alternative electrolyte [3] comparative example 7 Obtained nonaqueous electrolytic solution makes battery, and determine low temperature power output in aforementioned manners as nonaqueous electrolytic solution.As a result such as electricity Solve shown in liquid [3] table 1.
Electrolyte [3] comparative example 12
The hexamethyl cyclotrisiloxane that is come using the lithium nitrate of equivalent volumes in alternative electrolyte [3] comparative example 7 is simultaneously preserved Nonaqueous electrolytic solution obtained from 3 days makes battery, and determine low temperature power output in aforementioned manners as nonaqueous electrolytic solution.Knot Fruit is as shown in electrolyte [3] table 1.
Electrolyte [3] comparative example 13
Using the hexamethyl cyclotrisiloxane that the difluorophosphate of equivalent volumes comes in alternative electrolyte [3] comparative example 7 Obtained nonaqueous electrolytic solution makes battery, and determine low temperature power output in aforementioned manners as nonaqueous electrolytic solution.As a result such as electricity Solve shown in liquid [3] table 1.
Electrolyte [3] comparative example 14
In electrolyte [3] embodiment 14, using the nonaqueous electrolytic solution being prepared as with electrolyte [3] comparative example 1, use State method and make battery, and determine low temperature power output.As a result as shown in electrolyte [3] table 1.
Electrolyte [3] table 1
[table 56]
From electrolyte [3] table 1, the electrolyte containing chain carboxylate and specific compound in nonaqueous electrolytic solution [3] lithium secondary battery of embodiment 1~13, not only with the secondary electricity of lithium of electrolyte [3] comparative example 6 without any of which Pond is compared, even and if with electrolyte [3] comparative example 1~5 without specific compound, do not contain the electrolyte of chain carboxylate [3] lithium secondary battery of comparative example 7~13 is compared, and low temperature characteristics of output power is also improved.In addition, the effect is not for both Simple superposition, by using both, effect is remarkably reinforced.
In addition, electrolyte [3] embodiment 14 is about relative to the power output climbing of electrolyte [3] comparative example 14 21%, and different electrolyte [3] embodiment 1 of identical material, battery structure is used for the defeated of electrolyte [3] comparative example 1 It is about 29% to go out power rise rate, it is known that battery structure has an impact to the effect size of the nonaqueous electrolytic solution of the present invention.
As described above, by using the nonaqueous electrolytic solution of the present invention, the i.e. non-water power of the secondary cell with following characteristics Liquid is solved, very big low temperature characteristics of output power can be played, the non-aqueous electrolyte for secondary battery is characterized in：Containing extremely More than one few chain carboxylates, also containing selected from least one of following substances compound, and it is in all non-water power The content solved in liquid is more than 10ppm, and the material includes：Cyclic siloxane compound, formula (2) table of formula (1) expression Compound that the fluorosilane compounds shown, formula (3) are represented, intramolecular have the compounds of S-F keys, nitrate, nitrite, Mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate.
Making -1 (manufacture of rectangular cell) ＞ of electrolyte [4] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
By 2kg Delanium powder KS-44 (timcal companies manufacture, trade name) and the mixing of 1kg petroleum-types pitch, will To pulpous state mixture in batch kiln in heating up 2 hours under inactive atmosphere until 1100 DEG C, at such a temperature Kept for 2 hours.
Crushed, particle diameter is adjusted to 18~22 μm by oscillatory type sieve, finally given with 7 mass % amorphous carbon Cover " the amorphous coated graphite class carbonaceous material " of graphite surface.By this " amorphous coated graphite class carbonaceous material " as negative Pole active material, 100 parts by weight are added into 98 parts by weight " amorphous coated graphite class carbonaceous material " as the carboxylic of thickener The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 mass %) of sodium carboxymethylcellulose pyce, 2 parts by weight as adhesive benzene The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %) of ethylene-butadiene rubber, is mixed with disperser Close, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, being rolled into thickness with press is 75 μm, then be cut into width 104mm, the active material layer of long 104mm sizes and width 30mm uncoated portion shape, It is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in discharge Battery can (the external dimensions of valve：120 × 110 × 10mm) in.Then, 20mL is injected in the battery can equipped with electrode group aftermentioned Nonaqueous electrolytic solution, be thoroughly impregnated electrode, seal and make rectangular cell.Stored in 1 battery case of secondary cell The nominal discharge capacity of the electric capacity that battery element has, the i.e. battery is about 6Ah, the direct current determined with 10kHz alternating current methods It is about 5 milliohms to hinder composition.
《The evaluation of battery》
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.
(output test)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are surrounded The area of triangle be used as power output (W).
Electrolyte [4] embodiment 1
In the case where drying argon atmosphere, to ethylene carbonate (EC：143 DEG C of flash-point), gamma-butyrolacton (GBL：101 DEG C of flash-point) and Diethyl carbonate (DEC：25 DEG C of flash-point) mixture (Capacity Ratio 2:7:1) 0.3mol/L LiPF is added in6And 0.7mol/L LiBF4, and dissolved, make vinylene carbonate containing 1 mass % in the mixed solution, 0.3 mass % hexamethyl Cyclotrisiloxane, prepares nonaqueous electrolytic solution.The flash-point of the nonaqueous electrolytic solution is 61 DEG C.Using the nonaqueous electrolytic solution in aforementioned manners Rectangular cell is made, and determines power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] embodiment 2
In addition to hexamethyl cyclotrisiloxane being substituted using pheiiyldimetliyl silicon fluoride nonaqueous electrolytic solution is made, with electricity Solution liquid [4] embodiment 1 similarly makes rectangular cell, and determines power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] embodiment 3
In addition to hexamethyl cyclotrisiloxane being substituted using methyl fluorosulfonate nonaqueous electrolytic solution is made, with electrolyte [4] embodiment 1 similarly makes rectangular cell, and determines power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] embodiment 4
Except using according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7)~ Difluorophosphate prepared by the method described in page 582 is made beyond nonaqueous electrolytic solution to substitute hexamethyl cyclotrisiloxane, Rectangular cell is made in the same manner as electrolyte [4] embodiment 1, and determines power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] comparative example 1
In addition to nonaqueous electrolytic solution is not contained hexamethyl cyclotrisiloxane, made in the same manner as electrolyte [4] embodiment 1 Make rectangular cell, and determine power output.As a result as shown in electrolyte [4] table 1.
Manufacture -2 (making of cylinder battery) ＞ of electrolyte [4] ＜ secondary cells
[manufacture of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[manufacture of negative pole]
By 2kg Delanium powder KS-44 (timcal companies manufacture, trade name) and the mixing of 1kg petroleum-types pitch, will To pulpous state mixture in batch kiln in heating up 2 hours under inactive atmosphere until 1100 DEG C, at such a temperature Kept for 2 hours.
Crushed, particle diameter is adjusted to 18~22 μm by oscillatory type sieve, finally given with 7 mass % amorphous carbon Cover " the amorphous coated graphite class carbonaceous material " of graphite surface.By this " amorphous coated graphite class carbonaceous material " as negative Pole active material, 100 parts by weight are added into 98 parts by weight " amorphous coated graphite class carbonaceous material " as the carboxylic of thickener The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 mass %) of sodium carboxymethylcellulose pyce, 2 parts by weight as adhesive benzene The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %) of ethylene-butadiene rubber, is mixed with disperser Close, slurry is made.Obtained slurry is coated on to the two sides of the copper foil as 18 μm of the thickness of negative electrode collector, and dried, is used Press is rolled into thickness for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole.Wherein, surface back side 30mm uncoated portion is all set in the longitudinal direction.
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After nonaqueous electrolytic solution, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The electricity stored in 1 battery case of secondary cell The nominal discharge capacity of the electric capacity that pond key element has, the i.e. battery is about 0.7 ampere-hour (Ah), is surveyed with 10kHz alternating current methods Fixed DC resistance component is about 35 milliohms (m Ω).
Electrolyte [4] embodiment 5
The nonaqueous electrolytic solution used using in electrolyte [4] embodiment 1 makes cylinder battery as nonaqueous electrolytic solution, and Determine power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] comparative example 2
In addition to using the nonaqueous electrolytic solution used in electrolyte [4] comparative example 1 as nonaqueous electrolytic solution, with electrolyte [4] embodiment 5 similarly makes cylinder battery, and determines power output.As a result as shown in electrolyte [4] table 1.
Electrolyte [4] table 1
[table 57]
No. Specific compound Power output (W)
Embodiment 1 Hexamethyl cyclotrisiloxane 500
Embodiment 2 Pheiiyldimetliyl silicon fluoride 510
Embodiment 3 Methyl fluorosulfonate 510
Embodiment 4 Difluorophosphate 525
Embodiment 5 Hexamethyl cyclotrisiloxane 45
Comparative example 1 ――― 390
Comparative example 2 ――― 37
From electrolyte [4] table 1, if (electrolyte [4] embodiment 1~4, electrolyte [4] compares to each rectangular cell Example 1), cylinder battery (electrolyte [4] embodiment 5, electrolyte [4] comparative example 2) be compared, then understand the present embodiment lithium two The power output of primary cell is improved.
As described above, the nominal discharge capacity of the rectangular cell of the present embodiment and this comparative example for 3 ampere-hours (Ah) with On, DC resistance component be 10 milliohms (m Ω) below.On the other hand, the present embodiment and the cylinder battery of this comparative example is specified Discharge capacity is less than 3 ampere-hours (Ah), and DC resistance component is more than 10 milliohms (m Ω).That is, the present embodiment, this comparative example Rectangular cell is compared with cylinder battery, and resistance is small, and electric capacity is big.Moreover, electrolyte [4] embodiment 1 compares relative to electrolyte [4] The power output of example 1 improves degree, and the power output than electrolyte [4] embodiment 5 relative to electrolyte [4] comparative example 2 is improved Degree is big, and in the big secondary cell of electric capacity or the small secondary cell of D.C. resistance, effect of the invention is bigger.
The making ＞ of electrolyte [5] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in discharge Battery can (the external dimensions of valve：120 × 110 × 10mm) in.Then, 20mL is injected in the battery can equipped with electrode group aftermentioned Nonaqueous electrolytic solution, be thoroughly impregnated electrode, seal and make rectangular cell.Stored in 1 battery case of secondary cell The nominal discharge capacity of the electric capacity that battery element has, the i.e. battery is about 6Ah, the direct current determined with 10kHz alternating current methods It is about 5 milliohms (m Ω) to hinder composition.
[evaluation of battery]
(solid measure)
To the battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.
(output test)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are surrounded The area of triangle be used as power output (W).
(cyclic test)
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method is charged to after charging upper limit voltage 4.2V, and discharge off electricity is discharged to 2C constant current 3.0V is pressed, using this charge and discharge cycles as 1 circulation, the circulation is repeated until 500 times.
(food preservation test)
Food preservation test is carried out under 60 DEG C of hot environment.Constant-current constant-voltage will be used in the environment of 25 DEG C in advance The battery that method charges to charging upper limit voltage 4.2V is preserved 1 month at 60 DEG C.
Output test is carried out to the battery after the battery after solid measure, the battery after cyclic test, food preservation test, Respectively as power output after power output, preservation after power output at initial stage, circulation.
Electrolyte [5] embodiment 1
In the case where drying argon atmosphere, to the mixed of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) Compound (volume ratio 2:5:3) 1mol/L LiPF is added in6With 0.01mol/L LiN (CF3SO2)2, and dissolved, make this Hexamethyl cyclotrisiloxane containing 0.3 mass % in mixed solution, prepares nonaqueous electrolytic solution.Used using the nonaqueous electrolytic solution State method make battery, and determine power output at initial stage, circulation after power output and preserve after power output.As a result such as electrolyte [5] shown in table 1.
Electrolyte [5] embodiment 2
In addition to hexamethyl cyclotrisiloxane being substituted using pheiiyldimetliyl silicon fluoride nonaqueous electrolytic solution is made, with electricity Solution liquid [5] embodiment 1 similarly makes battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 3
In addition to hexamethyl cyclotrisiloxane being substituted using methyl fluorosulfonate nonaqueous electrolytic solution is made, with electrolyte [5] embodiment 1 similarly makes battery, and power output after determining after power output at initial stage, circulation power output and preserving.Knot Fruit is as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 4
Except using according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7)~ Difluorophosphate prepared by the method described in page 582 is made beyond nonaqueous electrolytic solution to substitute hexamethyl cyclotrisiloxane, Make battery in the same manner as electrolyte [5] embodiment 1, and it is defeated after determining after power output at initial stage, circulation power output and preserving Go out power.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 5
Except substituting LiN (CF using two (oxalate conjunction) lithium borates (LiBOB)3SO2)2It is made beyond nonaqueous electrolytic solution, Make battery in the same manner as electrolyte [5] embodiment 1, and it is defeated after determining after power output at initial stage, circulation power output and preserving Go out power.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 6
Except substituting LiN (CF using two (oxalate conjunction) lithium borates (LiBOB)3SO2)2It is made beyond nonaqueous electrolytic solution, Make battery in the same manner as electrolyte [5] embodiment 4, and it is defeated after determining after power output at initial stage, circulation power output and preserving Go out power.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] comparative example 1
Except undissolved LiN (CF in nonaqueous electrolytic solution3SO2)2In addition, battery is made similarly to Example 1, and is determined Initial stage power output, circulation after power output and preserve after power output.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] comparative example 2
In addition to not containing hexamethyl cyclotrisiloxane in nonaqueous electrolytic solution, made in the same manner as electrolyte [5] embodiment 1 Make battery, and power output after determining after power output at initial stage, circulation power output and preserving.As a result such as the institute of electrolyte [5] table 1 Show.
Electrolyte [5] comparative example 3
Except not containing LiN (CF in nonaqueous electrolytic solution3SO2)2It is real with electrolyte [5] beyond hexamethyl cyclotrisiloxane Apply example 1 and similarly make battery, and power output after determining after power output at initial stage, circulation power output and preserving.As a result such as Shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 7
The ＞ of manufacture -2 of ＜ secondary cells
[manufacture of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[manufacture of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After nonaqueous electrolytic solution, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The battery that 1 battery exterior of secondary cell is stored The nominal discharge capacity of the electric capacity that key element has, i.e. secondary cell is about 0.7 ampere-hour (Ah), is determined with 10kHz alternating current methods DC resistance component be about 35 milliohms (m Ω).
The nonaqueous electrolytic solution used using in electrolyte [5] embodiment 1 manufactures cylinder battery as nonaqueous electrolytic solution, and Measure power output at initial stage, circulation after power output and preserve after power output.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 8
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] embodiment 2 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 9
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] embodiment 3 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 10
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] embodiment 4 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 11
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] embodiment 5 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] embodiment 12
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] embodiment 6 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] comparative example 4
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] comparative example 1 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] comparative example 5
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] comparative example 2 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] comparative example 6
In addition to using the nonaqueous electrolytic solution used in electrolyte [5] comparative example 3 as nonaqueous electrolytic solution, with electrolyte [5] embodiment 7 similarly makes cylinder battery, and output work after determining after power output at initial stage, circulation power output and preserving Rate.As a result as shown in electrolyte [5] table 1.
Electrolyte [5] table 1
[table 58]
From electrolyte [5] table 1, if (electrolyte [5] embodiment 1~6, electrolyte [5] compares to each rectangular cell (electrolyte [5] embodiment 7~12, electrolyte [5] comparative example 4~6) be compared then are understood non-for example 1~3), cylinder battery Contain LiN (C in water electrolysis liquid simultaneouslynF2n+1SO2)2(in formula, n be 1~4 integer) and/or two (oxalate conjunctions) lithium borates and The lithium secondary battery of electrolyte [5] embodiment of specific compound, and without electrolyte [5] comparative example any in these Lithium secondary battery is compared, and power output is improved.
As described above, the nominal discharge capacity of the rectangular cell of the present embodiment and this comparative example for 3 ampere-hours (Ah) with On, DC resistance component be 10 milliohms (m Ω) below.On the other hand, the present embodiment and the cylinder battery of this comparative example is specified Discharge capacity is less than 3 ampere-hours (Ah), and DC resistance component is more than 10 milliohms (m Ω).That is, the present embodiment, this comparative example Rectangular cell is compared with cylinder battery, and resistance is small, and electric capacity is big.Moreover, electrolyte [5] embodiment 1 compares relative to electrolyte [5] The power output of example 1 improves degree, and the power output than electrolyte [5] embodiment 7 relative to electrolyte [5] comparative example 4 is improved Degree is big.Power output particularly after cycling, which is improved in the power output raising degree after degree and preservation, has big difference It is different.It follows that in the big secondary cell of electric capacity or the small secondary cell of D.C. resistance, effect of the invention is bigger.
The preparation ＞ of electrolyte [6] ＜ nonaqueous solvents
Adsorption treatment (50 DEG C, LHSV, l/ hours) is carried out to commercially available ethylene carbonate (EC) with molecular sieve 4A.The opposing party Face, is fully carried out after rectifying with reflux ratio 1, the column plate of theoretical cam curve 30 to dimethyl carbonate and methyl ethyl carbonate respectively, with point Son sieve 4A carries out adsorption treatment (25 DEG C, LHSV, l/ hours).Then, with EC:DMC:EMC (volume ratios 3:3:4) they are mixed Close, adsorption treatment (25 DEG C, LHSV, l/ hours) is further carried out with molecular sieve 4A, prepare mixing nonaqueous solvents.Now, it is non-aqueous In solvent, water outlet or alcohols are not detected.
The making ＞ of electrolyte [6] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in exhaust Battery can (the external dimensions of valve：120 × 110 × 10mm) in.Then, 20mL is injected in the battery can equipped with electrode group non-aqueous Electrolyte, is thoroughly impregnated electrode, seals and makes rectangular cell.The nominal discharge capacity of the battery is high power capacity, about 6Ah, is about 5 milliohms with the DC resistance component that 10kHz alternating current methods are determined.
[evaluation of battery]
(solid measure)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial stage Capacity.
(output test)
In the environment of 25 DEG C, by 0.2C constant current charge within 150 minutes, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.Current-voltage straight line and lower voltage limit (3V) are surrounded The area of triangle be used as power output (W).
(cyclic test)
Cyclic test is carried out under the hot environment for being counted as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method is charged to after charging upper limit voltage 4.2V, and discharge off electricity is discharged to 2C constant current 3.0V is pressed, using this charge and discharge cycles as 1 circulation, the circulation is repeated until 500 times.Electricity after terminating for cyclic test Pond, carries out the discharge and recharge of 3 circulations under 25 DEG C of environment, using the 0.2C discharge capacities of the 3rd circulation as capacity after circulation, Capacity is used as capability retention relative to the ratio of initial capacity after this is circulated.
Electrolyte [6] embodiment 1
In the case where drying argon atmosphere, the methanol of 10ppm amounts is mixed into above-mentioned mixing nonaqueous solvents, six are added with 0.8mol/L Lithium fluophosphate (LiPF6), and dissolved.Hydrogen fluoride (HF) amount in solution after 1 day is 12ppm, when being determined again after 2 weeks For 14ppm.The hexamethyl cyclotrisiloxane of 0.3 mass % of mixing amount, is prepared non-aqueous in the mixed solution (after mixing 2 weeks) Electrolyte.Battery is made in aforementioned manners using the nonaqueous electrolytic solution, and determines power output and capability retention.As a result such as electricity Solve shown in liquid [6] table 1.
Electrolyte [6] embodiment 2
It is 20ppm except the combined amount of methanol is changed to relative to mixing nonaqueous solvents in electrolyte [6] embodiment 1 Amount beyond, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 1, make battery using the nonaqueous electrolytic solution, and survey Determine power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6Mixed solution after 1 day In hydrogen fluoride (HF) amount be 16ppm, when being determined again after 2 weeks be 19ppm.
Electrolyte [6] embodiment 3
It is 35ppm except the combined amount of methanol is changed to relative to mixing nonaqueous solvents in electrolyte [6] embodiment 1 Amount beyond, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 1, make battery using the nonaqueous electrolytic solution, and survey Determine power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6Mixed solution after 1 day In hydrogen fluoride (HF) amount be 22ppm, when being determined again after 2 weeks be 27ppm.
Electrolyte [6] embodiment 4
Except being replaced in electrolyte [6] embodiment 1 relative to the ethylene glycol (EG) of mixing nonaqueous solvents mixing 15ppm amounts Beyond methanol, nonaqueous electrolytic solution is prepared as with electrolyte [6] embodiment 1, battery is made using the nonaqueous electrolytic solution, and Determine power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6Mixing after 1 day is molten Hydrogen fluoride (HF) amount in liquid is 14ppm, is 16ppm when being determined again after 2 weeks.
Electrolyte [6] embodiment 5
Except substituting first relative to the ethylene glycol of mixing nonaqueous solvents mixing 35ppm amounts in electrolyte [6] embodiment 1 Beyond alcohol, nonaqueous electrolytic solution is prepared as with electrolyte [6] embodiment 1, battery is manufactured using the nonaqueous electrolytic solution, and determine Power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6In mixed solution after 1 day Hydrogen fluoride (HF) amount be 23ppm, when being determined again after 2 weeks be 27ppm.
Electrolyte [6] embodiment 6
Except in electrolyte [6] embodiment 1 relative to mixing nonaqueous solvents mixing 25ppm methanol and 25ppm ethylene glycol In addition, nonaqueous electrolytic solution is prepared as with electrolyte [6] embodiment 1, makes battery using the nonaqueous electrolytic solution, and determine defeated Go out power and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6In mixed solution after 1 day Hydrogen fluoride (HF) amount is 31ppm, is 36ppm when being determined again after 2 weeks.
Electrolyte [6] embodiment 7
Except the difluorophosphate of the amount in electrolyte [6] embodiment 1 relative to 0.3 mass % of mixed solution mixing (according to Inorganic Nuclear Chemistry Letters (1969), described in page 581~page 582 of 5 (7) It is prepared by method) substitute beyond hexamethyl cyclotrisiloxane, nonaqueous electrolytic solution is prepared as with electrolyte [6] embodiment 1, makes Battery is made with the nonaqueous electrolytic solution, and it is fixed to determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] embodiment 8
Except the difluorophosphate for the amount for mixing 0.3 mass % relative to mixed solution in electrolyte [6] embodiment 3 comes Substitute beyond hexamethyl cyclotrisiloxane, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 3, use the non-water power Solve liquid and make battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] embodiment 9
Except the difluorophosphate for the amount for mixing 0.3 mass % relative to mixed solution in electrolyte [6] embodiment 4 comes Substitute beyond hexamethyl cyclotrisiloxane, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 4, use the non-water power Solve liquid and make battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] embodiment 10
Except the difluorophosphate for the amount for mixing 0.3 mass % relative to mixed solution in electrolyte [6] embodiment 6 comes Substitute beyond hexamethyl cyclotrisiloxane, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 6, use the non-water power Solve liquid and make battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] embodiment 11
Except the methanesulfonic acid trimethyl of the amount in electrolyte [6] embodiment 6 relative to 0.3 mass % of mixed solution mixing Silyl ester is substituted beyond hexamethyl cyclotrisiloxane, with electrolyte [6] embodiment 6 is prepared as nonaqueous electrolytic solution, Battery is made using the nonaqueous electrolytic solution, and determines power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] embodiment 12
The ＞ of making -2 of ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[making of nonaqueous electrolytic solution]
Make and the same nonaqueous electrolytic solution of electrolyte [6] embodiment 6.
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After nonaqueous electrolytic solution, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The nominal discharge capacity of the battery is about 0.7 ampere Hour (Ah), the D.C. resistance determined with 10kHz alternating current methods is about 35 milliohms (m Ω).For above-mentioned battery, with electrolyte [6] Embodiment 6 similarly determines power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] comparative example 1
In electrolyte [6] embodiment 3, using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane and preparing, make Battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] comparative example 2
In electrolyte [6] embodiment 5, using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane and preparing, make Battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] comparative example 3
In electrolyte [6] embodiment 6, using the nonaqueous electrolytic solution for not mixing hexamethyl cyclotrisiloxane and preparing, make Battery, and determine power output and capability retention.As a result as shown in electrolyte [6] table 1.
Electrolyte [6] comparative example 4
In electrolyte [6] embodiment 1, using the nonaqueous electrolytic solution for not mixing methanol in mixing nonaqueous solvents and preparing, Battery is made, and determines power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF61 day Hydrogen fluoride (HF) amount in solution afterwards is 9ppm, is still 9ppm when being determined again after 2 weeks.
Electrolyte [6] comparative example 5
In electrolyte [6] comparative example 4, the silica of pregnancy basic ring three is substituted using 0.3 mass % of mixing difluorophosphate Alkane and the nonaqueous electrolytic solution prepared, make battery, and determine power output and capability retention.As a result such as the institute of electrolyte [6] table 1 Show.
Electrolyte [6] comparative example 6
In electrolyte [6] comparative example 4, six are substituted using 0.3 mass % of mixing methanesulfonic acid trimethyl silyl ester Methyl cyclotrisiloxane and the nonaqueous electrolytic solution prepared, make battery, and determine power output and capability retention.As a result such as electricity Solve shown in liquid [6] table 1.
Electrolyte [6] comparative example 7
It is 700ppm except the combined amount of methanol is changed to relative to mixing nonaqueous solvents in electrolyte [6] embodiment 1 Amount beyond, be prepared as nonaqueous electrolytic solution with electrolyte [6] embodiment 1, make battery using the nonaqueous electrolytic solution, and survey Determine power output and capability retention.As a result as shown in electrolyte [6] table 1.In addition, mixing LiPF6In solution after 1 day Hydrogen fluoride (HF) amount is 321ppm, is 403ppm when being determined again after 2 weeks.
Electrolyte [6] comparative example 8
In electrolyte [6] embodiment 1, methanol is not mixed using in mixing nonaqueous solvents, and do not mix pregnancy basic ring Trisiloxanes and the nonaqueous electrolytic solution prepared, make battery, and determine power output and capability retention.As a result such as electrolyte [6] shown in table 1.
Electrolyte [6] comparative example 9
In addition to not mixing hexamethyl cyclotrisiloxane in electrolyte [6] embodiment 12, with electrolyte [6] embodiment 12 are prepared as nonaqueous electrolytic solution, make battery using the nonaqueous electrolytic solution, and determine power output and capability retention.Knot Fruit is as shown in electrolyte [6] table 1.
Electrolyte [6] table 1
[table 59]
From electrolyte [6] table 1, the lithium of electrolyte [6] comparative example 1~3 containing more hydrogen fluoride (HF) is secondary Battery is inferior at characteristics of output power, the aspect of cycle characteristics two compared with the lithium secondary battery of electrolyte [6] comparative example 8, still Wherein added with specific compound electrolyte [6] embodiment 1~11 lithium secondary battery, it is special in characteristics of output power, circulation Property two aspect, find characteristic raising.Further, in terms of power output, the lithium of electrolyte [6] embodiment 1~11 is secondary Battery, although the secondary electricity of lithium with containing specific compound hydrogen fluoride (HF) poor electrolyte [6] comparative example 4~6 Pond is compared, with higher performance, by there is hydrogen fluoride, and the power output realized by specific compound that strengthened is improved The surprising result of effect.But, the lithium secondary battery of electrolyte [6] comparative example 7 containing excessive hydrogen fluoride (HF) In, obtain the result of particularly cycle characteristics difference.
In addition, electrolyte [6] embodiment 12 of the high battery structure of low capacity, D.C. resistance compares relative to electrolyte [6] Power output climbing compared with example 9 is only about 19%, on the other hand, the electrolyte of the low battery structure of high power capacity, D.C. resistance [6] embodiment 6 rises relative to the power output of electrolyte [6] comparative example 3 (all containing methanol 25ppm and ethylene glycol 25ppm) Rate is about 29%, output work of electrolyte [6] embodiment 5 relative to electrolyte [6] comparative example 2 (all containing ethylene glycol 35ppm) Rate climbing is about 26%, and electrolyte [6] embodiment 3 is defeated relative to electrolyte [6] comparative example 1 (all containing methanol 35ppm) It is about 26% to go out power rise rate, larger.It can thus be appreciated that in the low battery structure of high power capacity, D.C. resistance, effect of the invention Fruit is especially big.
As described above, by using the nonaqueous electrolytic solution of the present invention, that is, mix in nonaqueous solvents fluorine-containing lithium salts and The non-aqueous electrolyte for secondary battery of formation, cycle characteristics will not be deteriorated, it is possible to obtain big characteristics of output power, described two Primary cell nonaqueous electrolytic solution is characterized in：Hydrogen fluoride (HF) in above-mentioned nonaqueous electrolytic solution is 10ppm~300ppm, is also contained Selected from least one of following substances compound, and its content in whole nonaqueous electrolytic solutions is more than 10ppm, described Material includes：Cyclic siloxane compound, the fluorosilane compounds of formula (2) expression, the formula (3) of formula (1) expression are represented Compound, intramolecular there is the compounds of S-F keys, nitrate, nitrite, mono-fluor phosphate, difluorophosphoric acid salt, acetate And propionate.
In the present embodiment, alcohols is added by the nonaqueous solvents to purifying, effect can be played, but in nonaqueous solvents originally During containing alcohols or moisture, by the purification condition for adjusting nonaqueous solvents, it is not necessary to be intentionally added alcohols, it can obtain same Effect.In general, the purifying of nonaqueous solvents needs to spend time, industrially causes cost to improve, and in the present invention, can be with High performance nonaqueous electrolytic solution is prepared without unnecessary purifying, its value is very big.
The ＞ of making -1 of electrolyte [7] ＜ batteries
[manufacture of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[preparation of electrolyte]
In the case where drying argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:4 in the mixed solvent, the lithium hexafluoro phosphate (LiPF fully dried with 1mol/L concentration dissolving6), Prepare nonaqueous electrolytic solution (1).Further make in the nonaqueous electrolytic solution (1) containing 0.5 mass % according to Inorganic Nuclear Chemistry Letters (1969), difluoro prepared by the method described in page 581~page 582 of 5 (7) Lithium phosphate, prepares nonaqueous electrolytic solution (2).
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After nonaqueous electrolytic solution, riveting molding is carried out, 18650 type cylinder batteries are manufactured.
[evaluation of battery]
(discharge and recharge at initial stage)
To the cylindrical battery of manufacture, 4.2V is charged to 0.2C constant-current constant-voltage mise-a-la-masse method at 25 DEG C Afterwards, 3.0V is discharged to 0.2C constant current.Being carried out 5 circulations makes battery stable.By putting for the 5th circulation now Capacitance is used as initial capacity.In addition, using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 The discharge capacity of hour rate (one-hour-rate).
(cyclic test)
Battery to implementing discharge and recharge at initial stage, after charging to 4.2V at 60 DEG C with 1C constant-current constant-voltage, 3.0V is discharged to 1C constant current, such discharge and recharge is subjected to 500 circulations.By the 500th circulation electric discharge now Capacity is used as circulation conservation rate relative to the ratio of the 1st cyclic discharge capacity.
(low-temperature test)
Battery to implementing discharge and recharge at initial stage, is charged at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method After 4.2V, implement 0.2C constant current electric discharge at -30 DEG C., will be just using discharge capacity now as low temperature capacity at initial stage Phase low temperature capacity is used as low temperature discharge rate at initial stage relative to the ratio of initial capacity.
In addition, being charged to the battery after cyclic test at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method After 4.2V, 3.0V is discharged to 0.2C constant current.It is carried out 3 circulation, using its 3rd circulation discharge capacity as Capacity after circulation.Then, after charging to 4.2V at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method to same battery, Implement 0.2C constant current electric discharge at -30 DEG C., will be low after circulation using discharge capacity now as low temperature capacity after circulation Warm capacity is used as low temperature discharge rate after circulation relative to the ratio of capacity after circulation.
Electrolyte [7] embodiment 1
In nonaqueous electrolytic solution (2), using relative to whole electrolyte qualities as 1 mass % amount mixed carbonic acid vinylene (hereinafter simply referred to as " VC "), prepares nonaqueous electrolytic solution (3).Using the nonaqueous electrolytic solution (3), 18650 type batteries are made, and determine Circulate conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.In addition, with centrifugal separator from discharge and recharge at initial stage knot Electrolyte is reclaimed in battery after beam, the VC measured amount is 0.40 mass %.
Electrolyte [7] comparative example 1
Using nonaqueous electrolytic solution (1), 18650 type batteries are made in the same manner as electrolyte [7] embodiment 1, and determine circulation Conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] comparative example 2
In nonaqueous electrolytic solution (1), VC is mixed using the amount relative to total electrolyte quality as 1 mass %, non-water power is prepared Solve liquid (4).Using the nonaqueous electrolytic solution (4), 18650 type batteries are made in the same manner as electrolyte [7] embodiment 1, and measure is followed Environmentally friendly holdup and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.In addition, from initial stage, discharge and recharge terminates with centrifugal separator Electrolyte is reclaimed in battery afterwards, the VC measured amount is 0.22 mass %.
Electrolyte [7] comparative example 3
Except using nonaqueous electrolytic solution (2), and do not mix beyond VC, made in the same manner as electrolyte [7] embodiment 1 18650 type batteries, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] comparative example 4
In nonaqueous electrolytic solution (2), VC is mixed using the amount relative to total electrolyte quality as 5 mass %, non-water power is prepared Solve liquid (5).In electrolyte [7] embodiment 1, using the nonaqueous electrolytic solution (5), 18650 type batteries are made, and determine circulation and are protected Holdup and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] embodiment 2
The ＞ of making -2 of ＜ batteries
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in battery can (external dimensions：120 × 110 × 10mm) in.Then, 20mL nonaqueous electrolytic solutions (3) are injected in the battery can equipped with electrode group, Electrode is thoroughly impregnated, seals and makes rectangular cell.
To the rectangular cell so made, using implementing cyclic test with the identical method of electrolyte [7] embodiment 1, low Temperature experiment, and determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] comparative example 5
In electrolyte [7] embodiment 2, nonaqueous electrolytic solution (3) is substituted using nonaqueous electrolytic solution (1), rectangular cell is made, And determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] comparative example 6
In electrolyte [7] embodiment 2, nonaqueous electrolytic solution (3) is substituted using nonaqueous electrolytic solution (4), rectangular cell is made, And determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] comparative example 7
In electrolyte [7] embodiment 2, nonaqueous electrolytic solution (3) is substituted using nonaqueous electrolytic solution (2), rectangular cell is made, And determine circulation conservation rate and low temperature discharge rate.As a result as shown in electrolyte [7] table 1.
Electrolyte [7] table 1
[table 60]
The electrolyte containing vinylene carbonate and difluorophosphoric acid salt in electrolyte [7] table 1, nonaqueous electrolytic solution [7] lithium secondary battery of embodiment 1 is with being mutually isostructural electrolyte [7] in addition to not containing them in nonaqueous electrolytic solution The lithium secondary battery of comparative example 1 is compared, and circulation conservation rate, low temperature discharge rate are all improved.
In addition understand, even if with being mutually isostructural electrolyte [7] ratio in addition to only containing VC in nonaqueous electrolytic solution Lithium secondary battery compared with example 2 is compared, and circulation conservation rate, low temperature discharge rate are also all improved.Conservation rate is circulated because of the presence or absence of VC And significant change, and by adding difluorophosphoric acid salt thereto, the increase of its effect.Gone out by the battery detecting after discharge and recharge at initial stage There is about 2 times of difference in VC amounts, it is believed that the VC wherein remained inhibits the deterioration of battery in cyclic test.
From electrolyte [7] embodiment 1 and electrolyte [7] comparative example 3, only can not fully it be improved by difluorophosphoric acid salt Circulate conservation rate.In addition, the lithium secondary battery phase of the lithium secondary battery of electrolyte [7] embodiment 1 and electrolyte [7] comparative example 3 Than, although initial stage, low temperature discharge rate was identical, but not only circulation conservation rate has low temperature discharging efficiency after big improvement, and circulation Also it is improved.Pass through VC and the synergy of difluorophosphoric acid salt, it is suppressed that the inside battery electricity caused by cyclic test The increase of resistance.
It is also above same between electrolyte [7] embodiment 2 and electrolyte [7] comparative example 5~7.
If the lithium two of the lithium secondary battery and electrolyte [7] comparative example 4 containing more VC to electrolyte [7] embodiment 1 Primary cell is compared, then is understood in electrolyte [7] comparative example 4, although circulation conservation rate is quite excellent, but low temperature discharge is special Property significance difference, it is impossible to tolerance use at low ambient temperatures.
The value of the D.C. resistance determined using 10kHz alternating current methods is shown in table.The rectangular cell of this experiment and cylinder electricity Pond is compared, and resistance is small, electric capacity is big.Low-temperature characteristics with electrolyte [7] embodiment 1 relative to electrolyte [7] comparative example 1 improves journey Degree is compared, and it is big that electrolyte [7] embodiment 2 improves degree relative to the low-temperature characteristics of electrolyte [7] comparative example 5, it is known that is used as this The objective for implementation of the nonaqueous electrolytic solution of invention, the high secondary cell of electric capacity or the small secondary cell of D.C. resistance are especially suitable 's.
The making ＞ of electrolyte [8] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in exhaust Battery can (the external dimensions of valve：120 × 110 × 10mm) in.Then, 20mL is injected in the battery can equipped with electrode group aftermentioned Nonaqueous electrolytic solution, be thoroughly impregnated electrode, seal and make rectangular cell.
The electric capacity that the battery element stored in 1 battery case of secondary cell has, i.e. the specified of secondary cell is put Capacitance is about 6 ampere-hours (Ah), and the DC resistance component determined with 10kHz alternating current methods is about 5 milliohms (m Ω).
The evaluation ＞ of electrolyte [8] ＜ batteries
[circulation conservation rate]
[discharge and recharge at initial stage]
After charging to 4.2V with 0.2C constant-current constant-voltage mise-a-la-masse method at 25 DEG C, put with 0.2C constant current Electricity is to 3.0V.Being carried out 5 circulations makes battery stable.It regard the discharge capacity of the 5th circulation now as initial capacity.And And, it regard the current value of 1 hour electric discharge rated capacity as 1C.
(cyclic test)
Battery to implementing discharge and recharge at initial stage, 4.2V is charged at 60 DEG C with 1C constant-current constant-voltage method, Then 3.0V is discharged to 1C constant current, the discharge and recharge is subjected to 500 circulations.By the 500th circulation electric discharge now Capacity is used as circulation conservation rate relative to the ratio of the 1st cyclic discharge capacity.
[low temperature discharge rate at initial stage]
(low-temperature test)
Battery to implementing discharge and recharge at initial stage, is charged at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method After 4.2V, implement 0.2C constant current electric discharge at -30 DEG C., will be just using discharge capacity now as low temperature capacity at initial stage Phase low temperature capacity is used as low temperature discharge rate at initial stage relative to the ratio of initial capacity.
[low temperature discharge rate after circulation]
In addition, being charged to the battery after cyclic test at 25 DEG C with 0.2C constant-current constant-voltage mise-a-la-masse method 4.2V, is then discharged to 3.0V with 0.2C constant current.3 circulations are carried out to it, the discharge capacity of its 3rd circulation is made For capacity after circulation.Then, 4.2V is charged to 0.2C constant-current constant-voltage mise-a-la-masse method at 25 DEG C to same battery, Then 0.2C constant current electric discharge is implemented at -30 DEG C.Using discharge capacity now as low temperature capacity after circulation, it will circulate Low temperature capacity is used as low temperature discharge rate after circulation relative to the ratio of capacity after circulation afterwards.
Electrolyte [8] embodiment 1
In the case where drying argon atmosphere, to the mixed of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) Compound (volume ratio 2:5:3) LiPF is added with 1mol/L in6, and dissolved, make to contain 0.3 mass % six in the mixed solution Methyl cyclotrisiloxane, 1 mass % vinylethylene carbonates, prepare nonaqueous electrolytic solution.Using the nonaqueous electrolytic solution with above-mentioned Method make battery, and determine circulation conservation rate, low temperature discharge rate at initial stage and circulation after low temperature discharge rate.As a result such as electrolyte [8] shown in table 1.
Electrolyte [8] embodiment 2
In addition to hexamethyl cyclotrisiloxane being substituted using pheiiyldimetliyl silicon fluoride nonaqueous electrolytic solution is made, with electricity Solution liquid [8] embodiment 1 similarly makes battery, and determines low temperature discharge after circulation conservation rate, low temperature discharge rate at initial stage and circulation Rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 3
In addition to hexamethyl cyclotrisiloxane being substituted using methyl fluorosulfonate nonaqueous electrolytic solution is made, with electrolyte [8] embodiment 1 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 4
Except using according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7)~ Difluorophosphate prepared by the method described in page 582 is made beyond nonaqueous electrolytic solution to substitute hexamethyl cyclotrisiloxane, Make battery in the same manner as electrolyte [8] embodiment 1, and determine low temperature after circulation conservation rate, low temperature discharge rate at initial stage and circulation Discharge rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 5
It is made except using the sultone of 1,3- third to substitute vinylethylene carbonate beyond nonaqueous electrolytic solution, with electrolyte [8] embodiment 1 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 6
It is real with electrolyte [8] in addition to vinylethylene carbonate being substituted using gamma-butyrolacton nonaqueous electrolytic solution is made Apply example 1 and similarly make battery, and determine low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.As a result such as Shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 7
In addition to vinylethylene carbonate being substituted using fluorine ethylene carbonate nonaqueous electrolytic solution is made, with electrolyte [8] embodiment 1 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 8
It is made except using the sultone of 1,3- third to substitute vinylethylene carbonate beyond nonaqueous electrolytic solution, with electrolyte [8] embodiment 4 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 9
It is real with electrolyte [8] in addition to vinylethylene carbonate being substituted using gamma-butyrolacton nonaqueous electrolytic solution is made Apply example 4 and similarly make battery, and determine low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.As a result such as Shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 10
In addition to vinylethylene carbonate being substituted using fluorine ethylene carbonate nonaqueous electrolytic solution is made, with electrolyte [8] embodiment 4 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] comparative example 1
In addition to nonaqueous electrolytic solution is not contained hexamethyl cyclotrisiloxane, made in the same manner as electrolyte [8] embodiment 1 Make battery, and determine low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.As a result such as the institute of electrolyte [8] table 1 Show.
Electrolyte [8] comparative example 2
In addition to nonaqueous electrolytic solution is not contained vinylethylene carbonate, made in the same manner as electrolyte [8] embodiment 1 Make battery, and determine low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.As a result such as the institute of electrolyte [8] table 1 Show.
Electrolyte [8] comparative example 3
In addition to nonaqueous electrolytic solution is not contained hexamethyl cyclotrisiloxane and vinylethylene carbonate, with electrolyte [8] embodiment 1 similarly makes battery, and determines low temperature discharge rate after circulation conservation rate, low temperature discharge rate at initial stage and circulation.Knot Fruit is as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 11
The ＞ of making -2 of ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 20 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into width 52mm, long 830mm sizes, are used as positive pole.Wherein, surface back side all sets 50mm uncoated portion in the longitudinal direction, living Property material layer length be 780mm.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is uniformly coated on and is used as the copper foil of 18 μm of the thickness of negative electrode collector Two sides, after drying, thickness is rolled into press for 85 μm, then is cut into wide 56mm, long 850mm size, is used as negative pole. Wherein, surface back side all sets 30mm uncoated portion in the longitudinal direction.
[assembling of battery]
By positive pole and negative pole together with the dividing plate of polyethylene it is overlapping wind and cause positive pole be not directly contacted with negative pole, system Into electrode body.Expose the terminal of positive pole and negative pole to be externally accommodated in battery can.Then, injection 5mL is described later thereto After nonaqueous electrolytic solution, riveting molding is carried out, 18650 type cylinder batteries are manufactured.The electricity stored in 1 battery case of secondary cell The nominal discharge capacity of the electric capacity that pond key element has, the i.e. battery is about 0.7 ampere-hour (Ah), is surveyed with 10kHz alternating current methods Fixed DC resistance component is about 35 milliohms (m Ω).
The nonaqueous electrolytic solution used using in electrolyte [8] embodiment 1 makes cylinder battery as nonaqueous electrolytic solution, and Low temperature discharge rate after determining circulation conservation rate, low temperature discharge rate at initial stage and circulating.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] embodiment 12
In addition to using the nonaqueous electrolytic solution used in electrolyte [8] embodiment 4 as nonaqueous electrolytic solution, with electrolyte [8] embodiment 11 similarly makes cylinder battery, and determines low temperature discharge after circulation conservation rate, low temperature discharge rate at initial stage and circulation Rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] comparative example 4
In addition to using the nonaqueous electrolytic solution used in electrolyte [8] comparative example 1 as nonaqueous electrolytic solution, with electrolyte [8] embodiment 11 similarly makes cylinder battery, and determines low temperature discharge after circulation conservation rate, low temperature discharge rate at initial stage and circulation Rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] comparative example 5
In addition to using the nonaqueous electrolytic solution used in electrolyte [8] comparative example 2 as nonaqueous electrolytic solution, with electrolyte [8] embodiment 11 similarly makes cylinder battery, and determines low temperature discharge after circulation conservation rate, low temperature discharge rate at initial stage and circulation Rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] comparative example 6
In addition to using the nonaqueous electrolytic solution used in electrolyte [8] comparative example 3 as nonaqueous electrolytic solution, with electrolyte [8] embodiment 11 similarly makes cylinder battery, and determines low temperature discharge after circulation conservation rate, low temperature discharge rate at initial stage and circulation Rate.As a result as shown in electrolyte [8] table 1.
Electrolyte [8] table 1
[table 61]
From electrolyte [8] table 1, if to each rectangular cell (electrolyte [8] embodiment 1~10, electrolyte [8] ratio Compared with being used in example 1~3), cylinder battery (being used in electrolyte [8] embodiment 11,12, electrolyte [8] comparative example 4~6) carries out Compare, then contain at least one specific compound A and at least one specific compound B electrolyte in nonaqueous electrolytic solution simultaneously [8] lithium secondary battery of embodiment, compared with not containing the lithium secondary battery of these electrolyte [8] comparative examples of any one, Low temperature discharge rate is all improved after circulation conservation rate, low temperature discharge rate at initial stage and circulation.
As described above, the nominal discharge capacity of the rectangular cell of the present embodiment and this comparative example for 3 ampere-hours (Ah) with On, DC resistance component be 10 milliohms (m Ω) below.On the other hand, the present embodiment and the cylinder battery of this comparative example is specified Discharge capacity is less than 3 ampere-hours (Ah), and DC resistance component is more than 10 milliohms (m Ω).That is, the present embodiment, this comparative example Rectangular cell is compared with cylinder battery, and resistance is small, and electric capacity is big.Moreover, electrolyte [8] embodiment 1 compares relative to electrolyte [8] The power output rising degree of example 1, the power output than electrolyte [8] embodiment 11 relative to electrolyte [8] comparative example 4 rises Degree is big, and in the big secondary cell of electric capacity or the small secondary cell of D.C. resistance, effect of the invention is bigger.
The making ＞ of electrolyte [9] ＜ secondary cells
[making of positive pole]
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 80 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.
[making of negative pole]
The 100 parts by weight conducts of addition in 98 parts by weight Delanium powder KS-44 (timcal companies manufacture, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 mass %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses be 50 mass %) of the SBR styrene butadiene rubberses of adhesive, with point Dissipate device to be mixed, slurry is made.Obtained slurry is coated on to the copper foil two sides of 10 μm of thickness, and dried, press pressure is used Prolong into thickness for 75 μm, then be cut into the uncoated of width 104mm, the active material layer of long 104mm sizes and width 30mm Partial shape, is used as negative pole.
[assembling of battery]
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the positive pole and the respective uncoated portion welding of negative pole, collector plate is made, electrode group is sealed in exhaust Battery can (the external dimensions of valve：120 × 110 × 10mm) in.Then, 20mL is injected in the battery can equipped with electrode group non-aqueous Electrolyte, is thoroughly impregnated electrode, seals and makes rectangular cell.
[electric capacity and DC resistance component]
The nominal discharge capacity (electric capacity that the battery element stored in 1 battery case has) of the battery is Gao Rong Amount, about 6Ah, the DC resistance component determined with 10kHz alternating current methods is about 5 milliohms.
[evaluation of battery]
(assay method of capacity)
To the new battery without charge and discharge cycles, under 25 DEG C, 4.2V~3.0V voltage range, with 0.2C current value (using the current value of 1 hour electric discharge rated capacity as 1C, the rated capacity depends on 1 hour rate (one-hour-rate) Discharge capacity, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as appearance Amount.
(5C discharge capacities after preservation)
Food preservation test is carried out under 60 DEG C of hot environment.Constant-current constant-voltage will be used in the environment of 25 DEG C in advance The battery that method charges to charging upper limit voltage 4.2V is preserved 1 month at 60 DEG C.For the battery after preservation, in 25 DEG C of environment Lower carry out speed trial.That is, charging upper limit voltage will be charged to constant-current constant-voltage method in the environment of 25 DEG C in advance 4.2V battery is discharged with the constant current value equivalent to 5C, is used as 5C discharge capacities after preservation.
(overcharge test)
Overcharge test is carried out under 25 DEG C of environment.Charged, observed with 3C constant current by discharge condition (3V) Its movement.Wherein, " valve work " represents exhaust valve operation and discharges the phenomenon of bath composition, " rupture " expression battery case with The fierce impetus ruptures, the phenomenon of content forcible aborting.
Electrolyte [9] embodiment 1
Dry argon atmosphere under, to ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mixing Thing (volume ratio 3:3:4) lithium hexafluoro phosphate (LiPF is added with 1mol/L in6), and dissolved, mix 1 in the mixed solution The hexamethyl cyclotrisiloxane of the cyclohexyl benzene (CHB) of quality % amount and 0.3 mass % amount, prepares nonaqueous electrolytic solution.Make Make battery in aforementioned manners of the nonaqueous electrolytic solution, and determine 5C discharge capacities after preservation.As a result such as the institute of electrolyte [9] table 1 Show.
Electrolyte [9] embodiment 2
Using being mixed with the hexamethyl cyclotrisiloxane that pheiiyldimetliyl silicon fluoride comes in alternative electrolyte [9] embodiment 1 And the nonaqueous electrolytic solution prepared, battery is made, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 3
Using being mixed with the pregnancy basic ring three that methanesulfonic acid trimethyl silyl ester comes in alternative electrolyte [9] embodiment 1 Siloxanes and the nonaqueous electrolytic solution prepared, make battery, and determine 5C discharge capacities after preservation.As a result such as the institute of electrolyte [9] table 1 Show.
Electrolyte [9] embodiment 4
Using being mixed with according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7) The silica of pregnancy basic ring three that difluorophosphate prepared by the method described in page~the 582 comes in alternative electrolyte [9] embodiment 1 Alkane and the nonaqueous electrolytic solution prepared, make battery, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 5
Using being mixed with the cyclohexyl benzene that biphenyl comes in alternative electrolyte [9] embodiment 1 and the nonaqueous electrolytic solution prepared, system Make battery, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 6
Using being mixed with the hexamethyl cyclotrisiloxane that pheiiyldimetliyl silicon fluoride comes in alternative electrolyte [9] embodiment 5 And the nonaqueous electrolytic solution prepared, battery is made, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 7
Using being mixed with the pregnancy basic ring three that methanesulfonic acid trimethyl silyl ester comes in alternative electrolyte [9] embodiment 5 Siloxanes and the nonaqueous electrolytic solution prepared, make battery, and determine 5C discharge capacities after preservation.As a result such as the institute of electrolyte [9] table 1 Show.
Electrolyte [9] embodiment 8
Using being mixed with according to Inorganic Nuclear Chemistry Letters (1969), page 581 of 5 (7) The silica of pregnancy basic ring three that difluorophosphate prepared by the method described in page~the 582 comes in alternative electrolyte [9] embodiment 5 Alkane and the nonaqueous electrolytic solution prepared, make battery, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 9
Using be mixed with the cyclohexyl benzene that tert-amyl benzene comes in alternative electrolyte [9] embodiment 1 and the non-aqueous solution electrolysis prepared Liquid, makes battery, and determine 5C discharge capacities after preservation.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] embodiment 10
The use of the content for being mixed with meta-terphenyl is the " part of meta-terphenyl that 3.7 mass %, part hydrogenation ratio are 42% Cyclohexyl benzene that hydride " comes in alternative electrolyte [9] embodiment 1 and the nonaqueous electrolytic solution prepared, make battery, and determine guarantor Deposit rear 5C discharge capacities.As a result as shown in electrolyte [9] table 1.In addition, the meta-terphenyl used in electrolyte [9] embodiment Part hydride, uses using meta-terphenyl as raw material, under the coexisting of platinum, palladium or nickel class catalyst, makes it in high-temperature pressurizing bar With material obtained from hydrogen reaction under part.In addition, part hydrogenation ratio is by the meta-terphenyl tried to achieve by gas chromatographic analysis The ratio of components of the constituent of part hydride is averaged and determined.The content of meta-terphenyl is also by the gas chromatographic analysis value Try to achieve.
Electrolyte [9] comparative example 1
The nonaqueous electrolytic solution that is prepared using unmixed hexamethyl cyclotrisiloxane in electrolyte [9] embodiment 1 is made Battery, and determine 5C discharge capacities.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] comparative example 2
The nonaqueous electrolytic solution that is prepared using unmixed hexamethyl cyclotrisiloxane in electrolyte [9] embodiment 5 is made Battery, and determine 5C discharge capacities.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] comparative example 3
The nonaqueous electrolytic solution manufacture electricity prepared using unmixed hexamethyl cyclotrisiloxane in electrolyte [9] embodiment 9 Pond, is measured to 5C discharge capacities.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] comparative example 4
The nonaqueous electrolytic solution that is prepared using unmixed hexamethyl cyclotrisiloxane in electrolyte [9] embodiment 10 is made Battery, and determine 5C discharge capacities.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] comparative example 5
Using in electrolyte [9] embodiment 1 unmixed hexamethyl cyclotrisiloxane, CHB any one and prepare it is non- Water electrolysis liquid makes battery, and determines 5C discharge capacities.As a result as shown in electrolyte [9] table 1.
Electrolyte [9] table 1
[table 62]
From electrolyte [9] table 1, the electrolyte containing overcharge preventing agent and specific compound in nonaqueous electrolytic solution [9] lithium secondary battery of embodiment 1~10, can self-evidently avoid cell fracture, after being saved in overcharge test High current (5C) discharge test in also show the characteristic more excellent than the lithium secondary battery of electrolyte [9] comparative example 1~4. Lithium secondary battery of the characteristic close to electrolyte [9] comparative example 5 for not containing overcharge preventing agent, it is known that improving overcharge peace While full property, practical value is very high.
As described above, being used by using secondary cell formed by lithium salts is mixed in nonaqueous solvents with following characteristics Nonaqueous electrolytic solution, high heavy-current discharge characteristic and overcharge safety, the non-water power of the secondary cell can be met simultaneously Solving liquid is characterized in：Containing overcharge preventing agent, also containing selected from least one of following substances compound, and it is complete Content in portion's nonaqueous electrolytic solution is more than 10ppm, and the material includes：It is cyclic siloxane compound that formula (1) is represented, logical Compound, the intramolecular that fluorosilane compounds that formula (2) is represented, formula (3) are represented have the compounds of S-F keys, nitrate, Asia Nitrate, mono-fluor phosphate, difluorophosphoric acid salt, acetate and propionate.Especially for the battery stored in 1 battery case The electric capacity that key element has is more than 3 ampere-hours (Ah) to be difficult to, while meeting the battery of this 2 key elements, to have in the past High practicability.
Structure [1]~[5] embodiment 1
《The making of nonaqueous electrolytic solution》
In the case where drying argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:Lithium hexafluoro phosphate (the LiPF that 4 in the mixed solvent is fully dried with 1mol/L concentration dissolving6)。 In addition, making its hexamethyl cyclotrisiloxane for containing 0.3 mass %.
《The making of positive pole》
Positive active material is the lithium-transition metal composite oxide synthesized with following methods, with composition formula LiMn0.33Ni0.33Co0.33O2Represent.With Mn:Ni:Co=1:1:1 molar ratio weighing as manganese raw material Mn3O4, be used as nickel former The NiO of the material and Co (OH) as cobalt raw material2, pure water is added thereto, slurry is made, while stirring using circulating medium Stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry to 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, only bag raw material containing manganese, nickel raw material, the grain of cobalt raw material is obtained The substantially spherical granulation particle in about 5 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and is made The ratio between Li molal quantity and Mn, Ni and Co total mole number are 1.05, are mixed with high-speed mixer, obtain nickel raw material, cobalt The granulation particle and the mixed-powder of lithium raw material of raw material, manganese raw material.Under air circulation, 950 DEG C to the mixed-powder fire 12 After hour (warming and cooling rate is 5 DEG C/min), crush, by 45 μm of sieve of mesh, obtain positive active material.The positive pole The BET specific surface area of active material is 1.2m2/ g, average primary particle diameter is 0.8 μm, median particle diameter d50For 4.4 μm, tap density For 1.6g/cm3。
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 81 μm of thickness is rolled into press, then be cut into tool There is the shape of wide 100mm, the active material layer of long 100mm sizes and width 30mm uncoated portion, be used as positive pole.Positive-active The density of material layer is 2.35g/cm3, (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 2.2, L/ (2 ×S2) it is 0.2.
《The making of negative pole》
In order to prevent being mixed into oversize grain in the commercially available natural graphite powder as particulate carbonaceous material, use The sieve of ASTM400 mesh is sieved 5 times repeatedly.It regard the negative material so obtained as carbonaceous material (A).
The petroleum-type heavy oil obtained in carbonaceous material (A) during the pyrolysis of mixing naphtha, implements in non-active gas 1300 DEG C of carbonization treatment, then, obtains composite carbonaceous material by carrying out classification processing to sinter, is used as negative electrode active material Matter, the composite carbonaceous material has been coated on carbonaceous material (A) particle surface with different crystalline carbonaceous materials Composite carbonaceous material.During classification processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.From Carbon yield is it was determined that obtained negative electrode active material powder is by relative to the low-crystalline carbon that 95 parts by weight of graphite are 5 weight Metallic substance is coated.The physical property of negative electrode active material is as shown in structure [1]~[5] table 1.
Structure [1]~[5] table 1
[table 63]
100 parts by weight are added in the above-mentioned negative electrode active material of 98 parts by weight as the sodium carboxymethylcellulose of thickener Aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 mass %), 2 parts by weight as adhesive styrene-butadiene rubber The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %) of glue, is mixed with disperser, slurry is made. Obtained slurry is coated on to the two sides of the rolled copper foil of 10 μm of thickness, and dried, thickness is rolled into press for 75 μm, then The shape of the uncoated portion with width 104mm, the active material layer of long 104mm sizes and width 30mm is cut into, as negative Pole.The density of negative electrode active material now is 1.35g/cm3, L/ (2 × S2) it is 0.19.
《The making of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By harness between the positive pole and the respective uncoated portion of negative pole, it is spot welded, collector plate is made, by electrode Group is sealed in the battery can (external dimensions of aluminum：120 × 110 × 10mm) in.As battery can, have just using in cover The current-collecting terminals of pole and negative pole, pressure relief valve, the battery can of the inlet of nonaqueous electrolytic solution.Collector plate and current-collecting terminals pass through Point welding connection.Then, 20mL nonaqueous electrolytic solutions are injected in the battery can equipped with electrode group, electrode is thoroughly impregnated, sealed Inlet, makes battery.The summation of the electrode area of positive pole relative to the case surface of battery accumulate the ratio between summation for 20.5,2 × S1/ T is 264, and electrode group occupation rate is 0.54.
《The evaluation of battery》
(assay method of battery capacity)
It is (small by 1 with current value 0.2C under 25 DEG C, 4.1V~3.0V voltage range to the new battery without discharge and recharge The current value of Shi Fang electricity rated capacities is as 1C, and the electric discharge that the rated capacity depends on 1 hour rate (one-hour-rate) is held Amount, similarly hereinafter) carry out 5 discharge and recharges at initial stage circulated.It regard the 0.2C discharge capacities of the 5th circulation now as initial capacity. The result of cell evaluation is as shown in structure [1]~[5] table 2.
The assay method of power output (initial stage)
By 0.2C constant current charge within 150 minutes under 25 DEG C of environment, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.The triangle that will be surrounded by current-voltage straight line and lower voltage limit (3V) The area of shape is used as power output (W).The result of cell evaluation is as shown in structure [1]~[5] table 2.
The assay method of series resistance (initial stage)
By 0.2C constant current charge within 150 minutes under 25 DEG C of environment, apply 10kHz exchange, determine resistance It is anti-, it is used as D.C. resistance.The result of cell evaluation is as shown in structure [1]~[5] table 2.
(cyclic test (assay method of resistance to battery capacity long afterwards and resistance to power output long afterwards))
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method is charged to after charging upper limit voltage 4.1V, and discharge off electricity is discharged to 2C constant current 3.0V is pressed, using this charge and discharge cycles as 1 circulation, the circulation is repeated until 500 circulations.After terminating for cyclic test Battery, under 25 DEG C of environment with current value 0.2C carry out 3 cycle charge-discharges, by its 3rd circulation 0.2C discharge capacities It is used as resistance to battery capacity long afterwards.In addition, the battery after terminating for cyclic test, carry out output test, as it is resistance to long afterwards Power output, is measured to series resistance, is used as resistance to series resistance long afterwards.The result of cell evaluation such as structure [1]~[5] table Shown in 2.
(overcharge test)
Overcharge test is carried out under 25 DEG C of environment.Charged, observed with 3C constant current by discharge condition (3V) Its movement.Wherein, " valve work " represents exhaust valve operation and discharges the phenomenon of bath composition, " rupture " expression battery case with The fierce impetus ruptures, the phenomenon of content forcible aborting.The result of cell evaluation is as shown in structure [1]~[5] table 2.
Structure [1]~[5] embodiment 2
The methanesulfonic acid trimethyl silyl ester containing 0.3 mass % in nonaqueous electrolytic solution is set to come alternative structure [1]~[5] Hexamethyl cyclotrisiloxane in embodiment 1, in addition, battery is made in the same manner as structure [1]~[5] embodiment 1, and together Carry out cell evaluation sample.As a result as shown in structure [1]~[5] table 2.
Structure [1]~[5] embodiment 3
The pheiiyldimetliyl silicon fluoride containing 0.3 mass % in nonaqueous electrolytic solution is set to carry out alternative structure [1]~[5] embodiment Hexamethyl cyclotrisiloxane in 1, in addition, makes battery, and similarly enter in the same manner as structure [1]~[5] embodiment 1 Row cell evaluation.As a result as shown in structure [1]~[5] table 2.
Structure [1]~[5] embodiment 4
The difluorophosphate containing 0.3 mass % in nonaqueous electrolytic solution is set to come in alternative structure [1]~[5] embodiment 1 Hexamethyl cyclotrisiloxane, in addition, makes battery, and similarly carry out electricity in the same manner as structure [1]~[5] embodiment 1 Evaluate in pond.As a result as shown in structure [1]~[5] table 2.
Structure [1]~[5] comparative example 1
Make not containing hexamethyl cyclotrisiloxane in the nonaqueous electrolytic solution in structure [1]~[5] embodiment 1, in addition, Battery is made in the same manner as structure [1]~[5] embodiment 1, and similarly carries out cell evaluation.As a result such as structure [1]~[5] table Shown in 2.
Structure [1]~[5] table 2
[table 64]
Structure [1]~[5] embodiment 5
《The making of positive pole》
Using with structure [1]~identical positive active material of [5] embodiment 1, it is same with structure [1]~[5] embodiment 1 Ground prepares slurry.On the two sides that obtained slurry is coated on to the aluminium foil of 15 μm of thickness, and it is dried, is rolled into press 81 μm of thickness, then wide 100mm, the positive electrode active material layer of long 3200mm sizes are cut into, and with every in the longitudinal direction Being spaced 20mm has the width 6mm shape of uncoated portion, is used as positive pole.The density of positive electrode active material layer is 2.35g/cm3, (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 2.2.The length of the width of positive pole is relative to length The ratio for spending the length in direction is 32.
《The making of negative pole》
Using with structure [1]~identical negative electrode active material of [5] embodiment 1, it is same with structure [1]~[5] embodiment 1 Ground prepares slurry.On the two sides that obtained slurry is coated on to the rolled copper foil of 10 μm of thickness, and it is dried, uses press pressure Prolong into 75 μm of thickness, then be cut into wide 104mm, the active material layer of long 3300mm sizes, and with every in the longitudinal direction Being spaced 20mm has the width 6mm shape of uncoated portion, is used as negative pole.The density of negative electrode active material now is 1.35g/ cm3。
《The making of battery》
The micro-porous film dividing plate (25 μm of thickness) of porous polyethylene piece is clipped between each electrode and causes positive pole and negative pole It is not directly contacted with, makes uncoated portion for opposite side that positive pole and negative pole is overlapping and be wound into circle in addition, electrode is made Body.The positive pole and negative pole are spot welded respectively on the central shaft that harness is wound, collector plate is made, electrode group is made, will The battery pack is arranged on the battery can (external dimensions of aluminum：36 φ × 120mm) in and cause negative pole collector plate be bottom.Negative pole collection Electric piece is spot welded in tank bottom, forms the structure that battery can is negative pole current-collecting terminals.Prepare the current-collecting terminals with positive pole, pressure The battery cover of power relief valve, positive pole current collections piece and positive pole current collections terminal are connected by spot welding.Then, to equipped with electrode 20mL nonaqueous electrolytic solutions are injected in the battery can of group, electrode is thoroughly impregnated, by riveting molding sealed cell cover, circle are made Cylinder battery.It is 41.0, electrode group occupation rate that the summation of the electrode area of positive pole accumulates the ratio between summation relative to the case surface of battery For 0.58.
《The evaluation of battery》
In addition to using above-mentioned cylinder battery, cell evaluation is carried out in the same manner as structure [1]~[5] embodiment 1.Battery The structure of evaluation is as shown in structure [1]~[5] table 3.
Structure [1]~[5] embodiment 6
Except the methanesulfonic acid trimethyl first for making nonaqueous electrolytic solution contain 0.3 mass % in structure [1]~[5] embodiment 5 Silane base ester is substituted beyond hexamethyl cyclotrisiloxane, in the same manner as structure [1]~[5] embodiment 5 makes battery, and equally Ground carries out cell evaluation.As a result as shown in structure [1]~[5] table 3.
Structure [1]~[5] embodiment 7
Except the pheiiyldimetliyl fluorine silicon for making nonaqueous electrolytic solution contain 0.3 mass % in structure [1]~[5] embodiment 5 Alkane is substituted beyond hexamethyl cyclotrisiloxane, makes battery in the same manner as structure [1]~[5] embodiment 5, and similarly carry out Cell evaluation.As a result as shown in structure [1]~[5] table 3.
Structure [1]~[5] embodiment 8
Replaced except making the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % in structure [1]~[5] embodiment 5 Beyond hexamethyl cyclotrisiloxane, battery is made in the same manner as structure [1]~[5] embodiment 5, and similarly carries out battery and is commented Valency.As a result as shown in structure [1]~[5] table 3.
Structure [1]~[5] comparative example 2
In addition to nonaqueous electrolytic solution is not contained hexamethyl cyclotrisiloxane in structure [1]~[5] embodiment 5, with Structure [1]~[5] embodiment 5 similarly makes battery, and similarly carries out cell evaluation.As a result such as structure [1]~[5] table 3 It is shown.
Structure [1]~[5] table 3
[table 65]
In the result of structure [1]~[5] table 2 and structure [1]~[5] table 3, any one battery, by non- Contain specific compound in water electrolysis liquid, power output, capability retention, security are all improved, even in cyclic test Afterwards, the increase of DC resistance component is also small, and battery capacity and power output are adequately maintained.
Structure [6] embodiment 1
《The making of nonaqueous electrolytic solution》
In the case where drying argon atmosphere, in the ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate of purifying (EMC) volume ratio 3:3:Lithium hexafluoro phosphate (the LiPF that 4 in the mixed solvent is fully dried with 1mol/L concentration dissolving6)。 And the hexamethyl cyclotrisiloxane for making it contain 0.3 mass %.
《The making of positive pole》
Positive active material is the lithium-transition metal composite oxide synthesized using following methods, with composition formula LiMn0.33Ni0.33Co0.33O2Represent.With Mn:Ni:Co=1:1:1 molar ratio weighing as manganese raw material Mn3O4, be used as nickel former The NiO of the material and Co (OH) as cobalt raw material2, pure water is added thereto slurry is made, stir while using circulating Medium-stirring wet-type ball mill is by the solid constituent case of wet attrition in slurry to 0.2 μm of median particle diameter.
Slurry is spray-dried by spray dryer, only bag raw material containing manganese, nickel raw material, the grain of cobalt raw material is obtained The substantially spherical granulation particle in about 5 μm of footpath.The LiOH powder of 3 μm of median particle diameter is added in obtained granulation particle, and is made The ratio between Li molal quantity and Mn, Ni and Co total mole number are 1.05, are mixed with high-speed mixer, obtain nickel raw material, cobalt The granulation particle and the mixed-powder of lithium raw material of raw material, manganese raw material.Under air circulation, 950 DEG C to the mixed-powder fire 12 After hour (warming and cooling rate is 5 DEG C/min), crush, by 45 μm of sieve of mesh, obtain positive active material.The positive pole The BET specific surface area of active material is 1.2m2/ g, average primary particle diameter is 0.8 μm, median particle diameter d50For 4.4 μm, tap density For 1.6g/cm3。
90 mass % are mixed in 1-METHYLPYRROLIDONE solvent as the cobalt acid lithium (LiCoO of positive active material2)、5 Slurry is made as the Kynoar (PVdF) of adhesive in the quality % acetylene black and 5 mass % as conductive material.Will Obtained slurry is coated on the aluminium foil two sides of 15 μm of thickness, and dries, and 81 μm of thickness is rolled into press, then be cut into width 100mm, long 100mm sizes positive electrode active material layer, and the shape of the uncoated portion with width 30mm, are used as positive pole.Just The density of pole active material layer is 2.35g/cm3, (thickness of positive electrode active material layer simultaneously)/(thickness of collector) is 2.2, L/ (2 × S2) it is 0.2.
《The making of negative pole》
In order to prevent being mixed into oversize grain in the commercially available natural graphite powder as particulate carbonaceous material, use The sieve of ASTM400 mesh is sieved 5 times repeatedly.It regard the negative material so obtained as carbonaceous material (A).
The petroleum-type heavy oil obtained in carbonaceous material (A) during the pyrolysis of mixing naphtha, implements in non-active gas 1300 DEG C of carbonization treatment, then, obtains composite carbonaceous material by carrying out classification processing to sinter, is used as negative electrode active material Matter, the composite carbonaceous material has been coated on carbonaceous material (A) particle surface with different crystalline carbonaceous materials Composite carbonaceous material.During classification processing, in order to prevent being mixed into oversize grain, sieved repeatedly 5 times using the sieve of ASTM400 mesh.From Carbon yield is it was determined that obtained negative electrode active material powder is by relative to the low-crystalline carbon that 95 parts by weight of graphite are 5 weight Metallic substance is coated.The physical property of negative electrode active material is as shown in structure [6] table 1.
Structure [6] table 1
[table 66]
100 parts by weight are added in the above-mentioned negative electrode active material of 98 parts by weight as the sodium carboxymethylcellulose of thickener Aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 mass %), 2 parts by weight as adhesive styrene-butadiene rubber The aqueous liquid dispersion (concentration of SBR styrene butadiene rubberses is 50 mass %) of glue, is mixed with disperser, slurry is made. Obtained slurry is coated on to the two sides of the rolled copper foil of 10 μm of thickness, and dried, thickness is rolled into press for 75 μm, then Wide 104mm, the active material layer of long 104mm sizes, and the shape of the uncoated portion with width 30mm are cut into, as negative Pole.The density of negative electrode active material now is 1.35g/cm3, L/ (2 × S2) it is 0.19.
《The making of battery》
32 positive poles and 33 negative poles are alternately arranged, porous polyethylene piece dividing plate is sandwiched between each electrode, and (thickness is 25 μ M), lamination is carried out.Now, make positive active material face relative with negative electrode active material face, and negative electrode active material will not be exposed Outside matter face.By the respective uncoated portion of the positive pole and negative pole harness each other, pass through together with the sheet metal as current-collecting terminals Spot welding connection, makes collector plate, electrode group is made.More than, porous polyethylene piece plugging hole more than 135 DEG C.It is used as battery Sheathing material, piece (amounts to thickness obtained from having polypropylene screen, thickness 0.04mm aluminium foil and nylon membrane using lamination successively 0.1mm), make polypropylene screen be located at inner face side to be shaped to rectangular-shaped cup, be used as shell.The fusing point of the polypropylene screen is 165 ℃.Above-mentioned electrode group is enclosed in shell and makes current-collecting terminals from the unsealing part of cup upper end to exposing outside, injection 20mL is non- Water electrolysis liquid, is thoroughly impregnated electrode.Cup upper end is sealed under reduced pressure and it is sealed, battery is made.Battery is substantially To be square, the electrode area summation of the positive pole of battery is accumulated (the sheathing material surface area for being free of heat seal lands) relative to case surface The ratio between summation is 22.6, (2 × S1/ T) it is 411.
《The evaluation of battery》
(assay method of battery capacity)
, (will with current value 0.2C under 25 DEG C, 4.1V~3.0V voltage range to the new battery without charge and discharge cycles The current value of 1 hour electric discharge rated capacity depends on putting for 1 hour rate (one-hour-rate) as 1C, the rated capacity Capacitance, similarly hereinafter) carry out 5 circulation discharge and recharges at initial stage.It regard the 5th circulation 0.2C discharge capacity now as " battery capacity " (Ah).The result of cell evaluation is as shown in structure [6] table 3.
(assay method of DC resistance component)
By 0.2C constant current charge within 150 minutes under 25 DEG C of environment, apply 10kHz exchange, determine resistance It is anti-, it is used as " DC resistance component " (m Ω).The result of cell evaluation is as shown in structure [6] table 3.
The assay method of power output (initial stage)
By 0.2C constant current charge within 150 minutes under 25 DEG C of environment, respectively with 0.1C, 0.3C, 1.0C, 3.0C, 10.0C discharge 10 seconds, determine the voltage of the 10th second.The triangle that will be surrounded by current-voltage straight line and lower voltage limit (3V) The area of shape is used as " power output at initial stage " (W).The result of cell evaluation is as shown in structure [6] table 3.
(cyclic test)
(resistance to battery capacity long afterwards, resistance to DC resistance component long afterwards, the assay method of resistance to power output long afterwards)
Cyclic test is carried out under the hot environment for being considered as 60 DEG C of actual use ceiling temperature of lithium secondary battery.With 2C constant-current constant-voltage method is charged to after charging upper limit voltage 4.1V, and discharge off electricity is discharged to 2C constant current 3.0V is pressed, using the charge and discharge cycles as 1 circulation, the circulation is repeated until 500 circulations.After terminating for cyclic test Battery, under 25 DEG C of environment with current value 0.2C carry out 3 cycle charge-discharges, by its 3rd circulation 0.2C discharge capacities It is used as " resistance to battery capacity long afterwards ".In addition, the battery after terminating for cyclic test, determines DC resistance component, as " durable DC resistance component afterwards ", carries out output test, is used as " resistance to power output long afterwards ".The result of cell evaluation such as structure [6] Shown in table 3.
(overcharge test)
Overcharge test is carried out under 25 DEG C of environment.Charged, observed with 3C constant current by discharge condition (3V) Its movement.Wherein, " valve work " represents exhaust valve operation and discharges the phenomenon of nonaqueous electrolytic solution composition, and " rupture " represents that battery holds Device is with fierce impetus rupture, the phenomenon of content forcible aborting.The result of cell evaluation is as shown in structure [6] table 3.
(assay method of volume change)
Battery volume to discharge condition (3V) under 25 DEG C of environment is measured.Volume passes through in graduated vessels Ethanol is added, battery is sunk in ethanol to determine.By the volume after cyclic test relative to the volume before cyclic test Ratio is used as " volume change ".Evaluation result is as shown in structure [6] table 3.
Structure [6] embodiment 2
Except making the methanesulfonic acid trimethyl silyl that nonaqueous electrolytic solution contains 0.3 mass % in structure [6] embodiment 1 Ester is substituted beyond hexamethyl cyclotrisiloxane, battery is made similarly to Example 1, and similarly carry out cell evaluation.Knot Fruit is as shown in structure [6] table 3.
Structure [6] embodiment 3
Replaced except making the pheiiyldimetliyl silicon fluoride that nonaqueous electrolytic solution contains 0.3 mass % in structure [6] embodiment 1 Beyond hexamethyl cyclotrisiloxane, battery is made in the same manner as structure [6] embodiment 1, and similarly carry out cell evaluation.Knot Fruit is as shown in structure [6] table 3.
Structure [6] embodiment 4
Pregnancy is substituted except making the difluorophosphate that nonaqueous electrolytic solution contains 0.3 mass % in structure [6] embodiment 1 Beyond basic ring trisiloxanes, battery is made in the same manner as structure [6] embodiment 1, and similarly carry out cell evaluation.As a result as tied Shown in structure [6] table 3.
Structure [6] comparative example 1
In addition to nonaqueous electrolytic solution is not contained hexamethyl cyclotrisiloxane in structure [6] embodiment 1, with structure [6] embodiment 1 similarly makes battery, and similarly carries out cell evaluation.As a result as shown in structure [6] table 3.
Structure [6] table 2
[table 67]
No. Specific compound in nonaqueous electrolytic solution
Embodiment 1 Hexamethyl cyclotrisiloxane
Embodiment 2 Methanesulfonic acid trimethyl silyl ester
Embodiment 3 Pheiiyldimetliyl silicon fluoride
Embodiment 4 Difluorophosphate
Comparative example 1 Nothing
Structure [6] table 3
[table 68]
From the result of structure [6] table 3, by containing specific compound in nonaqueous electrolytic solution, initial stage output work Rate, capability retention, security are improved, and battery capacity and power output also can be fully kept after cyclic test, The change of battery volume is also small.
Industrial applicibility
Purposes to the lithium secondary battery of the present invention is not particularly limited, and can be used in known various uses.It is used as tool The example of body, can enumerate notebook personal computer, an input type PC, mobile personal computer, e-book player (Electronic book player), portable phone, portable facsimile printer, portable copier, portable printer, head Wear receiver, video camera, LCD TV, convenient dust catcher, portable CD, mini formula disc player, wireless set, electricity Sub- notebook, calculator, storage card, portable tape recorder, radio, back-up source, motor, automobile, motorcycle, band Bicycle, bicycle, ligthing paraphernalia, toy, game machine, clock and watch, electric tool, stroboscope, camera of motor etc..This hair Bright lithium secondary battery, because with Large Copacity, excellent life-span and high-output power, gas is produced less, even overcharge When security it is also high, can suitably extensive use so in particularly the field of Large Copacity is required.
Although used above of the invention and specific mode is illustrated, come for those skilled in the art Say, it is obvious not depart from the intent and scope of the present invention and can carry out various changes.Moreover, the application is based on following Japanese patent application, its whole is quoted by quoting.
Japanese Patent Application 2005-331255 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-331362 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-331391 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-331477 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-331513 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-339794 (the applyings date：On November 25th, 2005)
Japanese Patent Application 2006-019863 (the applyings date：On January 27th, 2006)
Japanese Patent Application 2006-005622 (the applyings date：On January 13rd, 2005)
Japanese Patent Application 2005-367747 (the applyings date：On December 21st, 2005)
Japanese Patent Application 2005-377366 (the applyings date：On December 28th, 2005)
Japanese Patent Application 2005-349052 (the applyings date：On December 2nd, 2005)
Japanese Patent Application 2005-359061 (the applyings date：On December 13rd, 2005)
Japanese Patent Application 2006-019879 (the applyings date：On January 27th, 2006)
Japanese Patent Application 2006-013664 (the applyings date：On January 23rd, 2005)
Japanese Patent Application 2005-314043 (the applyings date：On October 28th, 2005)
Japanese Patent Application 2005-331585 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-305368 (the applyings date：On October 20th, 2005)
Japanese Patent Application 2005-344732 (the applyings date：On November 29th, 2005)
Japanese Patent Application 2005-343629 (the applyings date：On November 29th, 2005)
Japanese Patent Application 2005-332173 (the applyings date：On November 16th, 2005)
Japanese Patent Application 2005-305300 (the applyings date：On October 20th, 2005)
Japanese Patent Application 2005-353005 (the applyings date：On December 7th, 2005)
Japanese Patent Application 2005-314260 (the applyings date：On October 28th, 2005)
Japanese Patent Application 2005-369824 (the applyings date：On December 22nd, 2005)
Japanese Patent Application 2005-370024 (the applyings date：On December 22nd, 2005)
Brief description of the drawings
[Fig. 1] (a) is the cross-sectional scans type of the film cathode (1) used in the embodiment 1~3 and comparative example 1 of negative pole [7] Electron microscope (SEM) photo.(b) be show negative pole [7] film cathode (1) by electron probe microanalyzer (EPMA) photo of the elements Si obtained in the mass concentration distributions of film thickness direction.(c) it is that the film cathode to negative pole [7] is shown (1) photo of the Elements C obtained by electron probe microanalyzer (EPMA) in the mass concentration distributions of film thickness direction.

Claims (10)

1. a kind of non-aqueous electrolyte for secondary battery, the electrolyte is at least containing non-water power formed by nonaqueous solvents and lithium salts Liquid is solved, wherein, the nonaqueous electrolytic solution contains selected from least one of nitrate and difluorophosphoric acid salt compound, and it is complete Content in portion's nonaqueous electrolytic solution is more than 10ppm；
Also, the nonaqueous electrolytic solution is to meet any bar in following electrolyte [2]~[4] and electrolyte [8]~[9] The electrolyte of part：
Electrolyte [2]：The nonaqueous solvents for constituting electrolyte contains at least one asymmetric linear carbonate, and the asymmetric chain Shape carbonic ester content ratio shared in whole nonaqueous solvents is the volume % of 5 volume %~90；
Electrolyte [3]：The nonaqueous solvents for constituting electrolyte contains at least one chain carboxylate；
Electrolyte [4]：The nonaqueous solvents for constituting electrolyte contains the solvent that flash-point is more than 70 DEG C, and its content is whole non-aqueous More than the 60 capacity % of agent；
Electrolyte [8]：Also contain the compound represented selected from formula (4), the heterocyclic compound containing nitrogen and/or sulphur in the electrolytic solution At least one of thing, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound, its content in whole nonaqueous electrolytic solutions is The mass % of 0.001 mass %~5 scope,
In formula (4), R9~R12It can be the same or different, represent by selected from least one of H, C, N, O, F, S and P member The group that element is constituted；
Electrolyte [9]：In the electrolytic solution, overcharge preventing agent is also contained.
2. the non-aqueous electrolyte for secondary battery described in claim 1, wherein, the nonaqueous electrolytic solution contain 0.01 mass %~ 5 mass % are selected from least one of nitrate and difluorophosphoric acid salt compound.
3. the non-aqueous electrolyte for secondary battery described in claim 1 or claim 2, wherein, constitute the electrolyte [2] Asymmetric linear carbonate is to be selected from methyl ethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, methyl just At least one of butyl ester and carbonic acid ethyl n-butyl.
4. a kind of non-aqueous electrolyte for secondary battery, it is to contain in nonaqueous solvents formed by lithium salts, wherein,
The nonaqueous electrolytic solution contains difluorophosphoric acid salt, and the content of difluorophosphoric acid salt is more than 10ppm in electrolyte；
The nonaqueous solvents is at least mixed solvent containing ethylene carbonate, and ethylene carbonate is relative to nonaqueous solvents total amount Ratio be the capacity % of 1 capacity %~25；
Also optionally contain in the nonaqueous electrolytic solution and be selected from LiN (CF3SO2)2, two (oxalate conjunction) lithium borates, in the sulphurs of 1,3- third One or more of ester, fluorine ethylene carbonate, cyclohexyl benzene compound, and the content of vinylene carbonate is 0.01~3 matter % is measured, 1,3- third sultone, the content of fluorine ethylene carbonate are respectively 0.001~5 mass %.
5. a kind of lithium secondary battery, the lithium secondary battery is comprised at least：Positive pole and negative pole are clipped into micro-porous film dividing plate and constituted Electrode group and in nonaqueous solvents contain nonaqueous electrolytic solution formed by lithium salts, and by they be mounted in battery case in, Wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, the active material layer contain can occlusion and Release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of nitrate and difluorophosphoric acid salt compound, and it is all non-aqueous Content in electrolyte is more than 10ppm；
Also, the nonaqueous electrolytic solution is to meet any bar in following electrolyte [2]~[4] and electrolyte [8]~[9] The electrolyte of part：
Electrolyte [2]：The nonaqueous solvents for constituting electrolyte contains at least one asymmetric linear carbonate, and the asymmetric chain Shape carbonic ester content ratio shared in whole nonaqueous solvents is the volume % of 5 volume %~90；
Electrolyte [3]：The nonaqueous solvents for constituting electrolyte contains at least one chain carboxylate；
Electrolyte [4]：The nonaqueous solvents for constituting electrolyte contains the solvent that flash-point is more than 70 DEG C, and its content is whole non-aqueous More than the 60 capacity % of agent；
Electrolyte [8]：Also contain the compound represented selected from formula (4), the heterocyclic compound containing nitrogen and/or sulphur in the electrolytic solution At least one of thing, cyclic carboxylic esters, fluorine-containing cyclic carbonate compound, its content in whole nonaqueous electrolytic solutions is The mass % of 0.001 mass %~5 scope,
In formula (4), R9~R12It can be the same or different, represent by selected from least one of H, C, N, O, F, S and P member The group that element is constituted；
Electrolyte [9]：In the electrolytic solution, overcharge preventing agent is also contained.
6. the lithium secondary battery described in claim 5, wherein, the nonaqueous electrolytic solution contains the mass % choosings of 0.01 mass %~5 From at least one of nitrate and difluorophosphoric acid salt compound.
7. the lithium secondary battery described in claim 5 or claim 6, wherein, constitute the asymmetric chain of the electrolyte [2] Carbonic ester is to be selected from methyl ethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, methyl n-butyl and carbon At least one of sour ethyl n-butyl.
8. a kind of lithium secondary battery, the lithium secondary battery is comprised at least：Micro-porous film dividing plate is clipped between positive pole and negative pole and structure Into electrode group and in nonaqueous solvents contain nonaqueous electrolytic solution formed by lithium salts, and by they be mounted in battery case In, wherein,
The positive pole and the negative pole form active material layer on the current collector respectively, the active material layer contain can occlusion and Release the active material of lithium ion；
The nonaqueous electrolytic solution contains selected from least one of nitrate and difluorophosphoric acid salt compound, and it is in whole non-aqueous solution electrolysis Content in liquid is more than 10ppm；
Also, the negative pole is any one negative pole being selected from following negative poles [1]~negative pole [10]：
Negative pole [1]：Contain the different carbonaceous material of two or more crystallinity as the negative pole of negative electrode active material；
Negative pole [2]：Contain amorphous carbonaceous as the negative pole of negative electrode active material, the amorphous carbonaceous passes through wide-angle x-ray The interplanar distance (d002) in (002) face that diffraction approach is determined is more than 0.337nm, and crystallite size (Lc) is below 80nm, using argon Ion laser Raman spectroscopy determine with 1360cm-1Peak intensity relative to 1580cm-1The definition of the ratio between peak intensity Raman R values are more than 0.2；
Negative pole [3]：Contain metal oxide as the negative pole of negative electrode active material, the metal oxide contain can occlusion and Release the titanium of lithium；
Negative pole [4]：Contain carbonaceous material as the negative pole of negative electrode active material, the circularity of the carbonaceous material for 0.85 with On, surface functional group amount O/C values are 0~0.01；
Negative pole [5]：Contain different orientation carbon complex as the negative pole of negative electrode active material, the different orientation carbon complex contains There is the different carbonaceous material of two or more orientation；
Negative pole [6]：Contain graphite carbon particle as the negative pole of negative electrode active material, the circularity of the graphite carbon particle is More than 0.85, the interplanar distance (d002) in (002) face determined by wide-angle x-ray diffraction is less than 0.337nm, using argon ion Laser Raman spectrometry determine with 1360cm-1Peak intensity relative to 1580cm-1The definition of the ratio between peak intensity Raman R value For 0.12~0.8；
Negative pole [7]：Contain following negative electrode active material C comprising multielement as the negative pole of negative electrode active material, the bag Negative electrode active material C containing multielement contain selected from Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd and At least one of Sb lithium occlusion metal A and/or lithium occlusion alloy B, and containing element Z, the element Z is C and/or N；
Negative pole [8]：Contain the different negative electrode active material of more than two kinds of property as the negative pole of negative electrode active material；
Negative pole [9]：It is 0.1g/cm containing tap density3More than, and using mercury, Hg porosimeter measure equivalent to diameter The micropore volume of the particle of 0.01 μm~1 μm of scope is the negative pole of more than 0.01mL/g negative electrode active material；
Negative pole [10]：Be charged to the negative pole nominal capacity 60% when, by negative pole opposed battery produce reaction resistance be 500 below Ω negative pole.
9. the lithium secondary battery described in claim 8, wherein, nonaqueous electrolytic solution contains in nitrate and difluorophosphoric acid salt At least one compound, its content is the mass % of 0.01 mass %~5.
10. the lithium secondary battery described in claim 8 or claim 9, wherein, the negative pole [1] contains composite carbonaceous material As negative electrode active material, the composite carbonaceous material contains the different carbonaceous material of two or more crystallinity.
CN201710119547.7A 2005-10-20 2006-10-19 Lithium secondary battery and the nonaqueous electrolytic solution wherein used Pending CN107069091A (en)

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JP2005-305300 2005-10-20
JP2005305368 2005-10-20
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JP2005-314043 2005-10-28
JP2005314260 2005-10-28
JP2005314043 2005-10-28
JP2005-314260 2005-10-28
JP2005-331255 2005-11-16
JP2005331513 2005-11-16
JP2005-331391 2005-11-16
JP2005332173 2005-11-16
JP2005331585 2005-11-16
JP2005-331585 2005-11-16
JP2005-331513 2005-11-16
JP2005331391 2005-11-16
JP2005-331477 2005-11-16
JP2005331255 2005-11-16
JP2005-331362 2005-11-16
JP2005331477 2005-11-16
JP2005-332173 2005-11-16
JP2005331362 2005-11-16
JP2005-339794 2005-11-25
JP2005339794 2005-11-25
JP2005343629 2005-11-29
JP2005-343629 2005-11-29
JP2005-344732 2005-11-29
JP2005344732 2005-11-29
JP2005349052 2005-12-02
JP2005-349052 2005-12-02
JP2005-353005 2005-12-07
JP2005353005 2005-12-07
JP2005-359061 2005-12-13
JP2005359061 2005-12-13
JP2005367747 2005-12-21
JP2005-367747 2005-12-21
JP2005-370024 2005-12-22
JP2005370024 2005-12-22
JP2005-369824 2005-12-22
JP2005369824 2005-12-22
JP2005-377366 2005-12-28
JP2005377366 2005-12-28
JP2006-005622 2006-01-13
JP2006005622 2006-01-13
JP2006013664 2006-01-23
JP2006-013664 2006-01-23
JP2006-019863 2006-01-27
JP2006-019879 2006-01-27
JP2006019863 2006-01-27
JP2006019879 2006-01-27
CN2006800390896A CN101292389B (en) 2005-10-20 2006-10-19 Lithium secondary cell and nonaqueous electrolytic solution for use therein

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