CN108091826A - Non-aqueous electrolyte for secondary battery and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution - Google Patents

Non-aqueous electrolyte for secondary battery and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution Download PDF

Info

Publication number
CN108091826A
CN108091826A CN201810132906.7A CN201810132906A CN108091826A CN 108091826 A CN108091826 A CN 108091826A CN 201810132906 A CN201810132906 A CN 201810132906A CN 108091826 A CN108091826 A CN 108091826A
Authority
CN
China
Prior art keywords
carbonate
electrolytic solution
nonaqueous electrolytic
halogen atom
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810132906.7A
Other languages
Chinese (zh)
Inventor
德田浩之
藤井隆
古田土稔
竹原雅裕
大贯正道
大桥洋
大桥洋一
木下信
木下信一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mu Electrolyte Co ltd
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007111931A external-priority patent/JP2008269979A/en
Priority claimed from JP2007111961A external-priority patent/JP5374827B2/en
Priority claimed from JP2007116442A external-priority patent/JP5628469B2/en
Priority claimed from JP2007116445A external-priority patent/JP5268016B2/en
Priority claimed from JP2007116450A external-priority patent/JP5418955B2/en
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Publication of CN108091826A publication Critical patent/CN108091826A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)

Abstract

The problem of the present invention is to provide a kind of nonaqueous electrolytic solution and non-aqueous electrolyte secondary battery, the nonaqueous electrolytic solution has excellent discharge load characteristic, and it is excellent to inhibit gas generation characteristic, the charge-discharge characteristic under high current density, discharge load characteristic etc. when High temperature storage characteristic, cycle characteristics, high power capacity, trickle charge characteristic, preservation characteristics, trickle charge.By the present invention in that with containing mono-fluor phosphate and/or difluorophosphoric acid salt and containing the nonaqueous electrolytic solution with specified chemical structure or the compound of specific physical property, solves the above subject.

Description

Non-aqueous electrolyte for secondary battery and the nonaqueous electrolyte using the nonaqueous electrolytic solution Secondary cell
It is on April 4th, 2008, Application No. 201510207936.6, entitled " secondary electricity the applying date that the application, which is, The divisional application of the application of pond nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution ".
Technical field
Secondary cell the present invention relates to non-aqueous electrolyte for secondary battery and using the nonaqueous electrolytic solution, it is specific and Speech, the secondary electricity of lithium the present invention relates to the non-aqueous electrolytic solution used for lithium secondary batteries containing special component and using the nonaqueous electrolytic solution Pond.
Background technology
<Nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>Corresponding to claim 1~8,13,14,39~41
In recent years, with the miniaturization of electronic equipment, the requirement to the high capacity of secondary cell is continuously improved, energy Density attracts attention higher than the lithium secondary battery (non-aqueous electrolyte secondary battery) of nickel-cadmium cell and Ni-MH battery.
As the electrolyte of lithium secondary battery, adopted is to make LiPF6、LiBF4、LiClO4、LiCF3SO3、 LiAsF6、LiN(CF3SO2)2、LiCF3(CF2)3SO3Electrolyte dissolutions are waited in the cyclic carbonates such as ethylene carbonate or propylene carbonate The cyclic carboxylic acids such as ester, the linear carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, gamma-valerolactone Nonaqueous electrolytic solution obtained from the nonaqueous solvents such as ester, the chain carboxylic acid esters such as methyl acetate, methyl propionate.
First, in order to improve the battery behaviors such as the load characteristic of this kind of lithium secondary battery, cycle characteristics, preservation characteristics, Various researchs have been carried out for nonaqueous solvents and electrolyte.For example, in patent document 1, by using containing vinyl carbonic acid The electrolyte of ethyl compound can control the decomposition of electrolyte in bottom line, so as to prepare preservation characteristics, Xun Huan The battery of excellent；In patent document 2, by using the electrolyte containing propane sultone, the recovery after preservation can be made Capacity is increased.
But when making to contain above-claimed cpd in electrolyte, although achieving raising preservation characteristics to a certain extent And the effect of cycle characteristics, but since the higher epithelium of resistance can be formed in negative side, thus it is particularly present discharge load spy Property reduce the problem of.
<Nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>Corresponding to claim 9~14,39~41
Secondly, in order to improve the battery behaviors such as the load characteristic of above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, Various researchs have been carried out for the nonaqueous solvents for above-mentioned nonaqueous electrolytic solution and electrolyte.For example, such as institute in non-patent literature 1 It records, when the solvent for using dielectric constant higher, viscosity lower is as nonaqueous solvents, not only having can be by electrolyte Resistance inhibit in the various advantages such as lower degree, but also its can be made to improve the permeability of positive and negative anodes, therefore preferably.
But as one of preferred solvent when having the advantages that above-mentioned, ether compound, nitrile compound etc. have except carbonyl The solvent of " containing heteroatomic functional group (group for forming skeleton) " beyond base skeleton is since meeting in anode because aoxidizing Reaction occurs reduction reaction in cathode and triggers electrochemical decomposition, it is difficult to it uses, thus in practical applications, as , it is necessary to which being combined with the esters of oxidative resistance, reducing resistance good carbonic acid or carboxylic acid with backbone carbonyl makes as illustration With.
It on the other hand, in patent document 1, can by using the electrolyte containing vinylethylene carbonate compound Controlling the decomposition of electrolyte in bottom line, so as to which the excellent battery of preservation characteristics, cycle characteristics is made；In patent text In offering 2, by using the electrolyte containing propane sultone, the recovery capacity after preservation can be made to be increased.
But when making to contain above-claimed cpd in electrolyte, although achieving raising preservation characteristics to a certain extent And the effect of cycle characteristics, but when wanting fully to improve characteristic using these compounds, since electricity can be formed in negative side The higher epithelium of resistance, thus it is particularly present the problem of discharge load characteristic reduces；Particularly, when using above-mentioned dielectric constant The solvent with " containing heteroatomic functional group (group for forming skeleton) " in addition to backbone carbonyl high, viscosity is low When, the problem of can not showing there is its good characteristic.
Nowadays, the high performance requirement of non-aqueous electrolyte secondary battery is gradually stepped up, expects to realize Gao Rong with high level The various performances such as amount, High temperature storage characteristic, trickle charge characteristic, cycle characteristics.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>Corresponding to claim 15~17,39~41
3rd, in order to improve the battery behaviors such as the load characteristic of above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, Various researchs have been carried out to nonaqueous solvents and electrolyte.For example, in patent document 3, by using the electricity containing phosphinate Solve liquid, it is possible to produce degradation of cell performance when in High temperature storage, trickle charge is able to the battery inhibited；In patent document In 4, by using the electrolyte for being with the addition of the organic compound with 2 or more cyano, it can obtain more than 4.2V voltages The excellent secondary cell of lower charge and discharge circulation life.
Particularly, weak current, the trickle charge for keeping charged state are led to always in the self discharge in order to compensate for battery Under state, since electrode is always in the higher state of activity, thus can trigger the capacity deterioration of battery accelerate or it is easy because Electrolyte decomposition and lead to the problem of gas.In addition, particularly in high-capacity battery, due to the spatial volume of inside battery It is small, even if thus presence electrolyte decomposition generate a small amount of gas, but the problem of inner pressure of battery still significantly raises.As trickle charge Characteristic, not only capacity required deterioration is few, but also proposes high request to inhibiting gas generation.
But for the electrolyte containing the compound described in patent document 3 and patent document 4, although with certain The effect for improving preservation characteristics and cycle characteristics of degree, but inhibition gas during with regard to its trickle charge generates and to inhibit battery special For the deterioration of property, not enough fully.
<Nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>Corresponding to claim 18~25,39~41
In addition, the 4th, in order to improve the electricity such as the load characteristic of above-mentioned nonaqueous electrolyte battery, cycle characteristics, preservation characteristics Pond characteristic and improve its when heated or short circuit when battery security, various grind has been carried out to nonaqueous solvents and electrolyte Study carefully.For example, in nonaqueous solvents, since sulfolane not only has high-k and high electrochemical oxidation stability, but also have There is boiling point more higher than ethylene carbonate and propylene carbonate as 278 DEG C, thus by using sulfolane as solvent, it can Expectation makes contributions to the raising of battery security.But since the fusing point of sulfolane is up to 28 DEG C, using sulfolane as master The battery of solvent there are low-temperature characteristics it is bad the problem of.In addition, it is also known that：Due to the compatibility of sulfolane and graphite cathode not Good, when using sulfolane as main solvent, the capacity in charge and discharge is less than theoretical capacity.
Such as, it has been disclosed that following proposal：It is secondary in the nonaqueous electrolyte for having used the electrolyte described in patent document 5 In battery, prevent electrolyte from curing at low temperature by using the mixed solvent of sulfolane and methyl ethyl carbonate.
In addition, disclose following proposal in patent document 6：By as main solvent and being added using sulfolane and gamma-butyrolacton Add vinylethylene carbonate and vinylene carbonate, the high high-quality quilt of lithium ion permeability can be formed on graphite cathode surface Film, so as to improve initial charge/discharge efficiency.
<Nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>Corresponding to claim 26~32,39~41
In addition, the 5th, in order to improve initial capacity, speed characteristics, cycle characteristics, High temperature storage characteristic, low-temperature characteristics, company Continuous charge characteristic, self-discharge characteristics, overcharge prevention characteristics etc. have numerous on the addition various additives into electrolyte Report.For example, as the method for improving cycle characteristics, report and Isosorbide-5-Nitrae is added in oriented electrolyte, 8,11- tetraazacyclododecane tetradecanes Method (referring to patent document 7).
But the high performance requirement of non-aqueous electrolyte secondary battery is gradually stepped up, expects with high level while realizes The various performances such as high power capacity, High temperature storage characteristic, trickle charge characteristic, cycle characteristics.For example, as be described hereinafter shown in reference example, when Merely with for improve the effective patent document 7 of cycle characteristics the prior art when, can be generated when carrying out trickle charge largely Gas causes the recovery capacity after experiment to be greatly reduced.
<Nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery 6>Corresponding to claim 33~38,39~41
In addition, the 6th, in order to improve the batteries such as the load characteristic of above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics spy Property, various researchs have been carried out to nonaqueous solvents and electrolyte.For example, in patent document 1, by using containing vinyl carbonic acid The electrolyte of ethyl compound can control the decomposition of electrolyte in bottom line, so as to which preservation characteristics, Xun Huan is made The battery of excellent；In patent document 2, by using the electrolyte containing propane sultone, the recovery after preservation can be made Capacity is increased.
But when making to contain above-claimed cpd in electrolyte, although achieving raising preservation characteristics to a certain extent And the effect of cycle characteristics, but since the higher epithelium of resistance can be formed in negative side, thus it is particularly present discharge load spy Property reduce the problem of.
Patent document 1：Japanese Unexamined Patent Publication 2001-006729 publications
Patent document 2：Japanese Unexamined Patent Publication 10-050342 publications
Patent document 3：Japanese Unexamined Patent Publication 2004-363077 publications
Patent document 4：Japanese Unexamined Patent Publication 7-176322 publications
Patent document 5：Japanese Unexamined Patent Publication 2000-012078 publications
Patent document 6：Japanese Unexamined Patent Publication 2004-296389 publications
Patent document 7：Japanese Unexamined Patent Publication 9-245832 publications
Non-patent literature 1：Quarterly Gross says No.49, P.108
The content of the invention
The subject that the invention solves
<Nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>
The present invention is completed, and it is an object of the present invention to provide a kind of discharge load excellent in view of the aforementioned technical background, and is had Excellent High temperature storage characteristic, the non-aqueous electrolyte for secondary battery of cycle characteristics.
<Nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>
The present invention is completed, and it is an object of the present invention to provide a kind of discharge load excellent in view of the aforementioned technical background, and is had Excellent High temperature storage characteristic, the non-aqueous electrolyte for secondary battery of cycle characteristics.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>
The present invention is completed, and it is an object of the present invention to provide a kind of cycle characteristics, preservation characteristics, continuously filling in view of the aforementioned technical background Gas generation when electric inhibits, the non-aqueous electrolyte for secondary battery that battery behavior is excellent.
<Nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>
But in recent years to battery high performance requirement continuous improvement, it is desirable that with higher level realize high power capacity, Height output, High temperature storage characteristic, cycle characteristics, high security etc..
In the non-aqueous electrolyte secondary battery for using electrolyte that patent document 5 records, during due to initial stage charge and discharge The invertibity deficiency of electrode reaction, can not meet its charge/discharge capacity and efficiency for charge-discharge (referring to the comparative example of nonaqueous electrolytic solution 4 1).In addition, in the non-aqueous electrolyte secondary battery for using electrolyte that patent document 6 records, due to its main solvent, that is, γ-fourth Viscosity of the lactone at 25 DEG C is primary solvent, that is, low molecular weight chain carbonic acid in 1.73mPas, with conventional electrolysis liquid Ester is (for example, dimethyl carbonate：0.59mPa·s；Diethyl carbonate：0.75mPa·s；Methyl ethyl carbonate：0.65mPas) phase Compare high, therefore the viscosity of its electrolyte whole also increases, and can not meet efficiency for charge-discharge at higher current densities.Separately Outside, the thermal stability of gamma-butyrolacton in the charge state is poor, and the charge-discharge characteristic after being preserved at a high temperature of 85 DEG C is also deposited At problem (referring to the comparative example 2 of nonaqueous electrolytic solution 4 and the comparative example 3 of nonaqueous electrolytic solution 4).
Therefore, problem of the invention is to solve when using the nonaqueous electrolytic solution containing cyclic sulfones, in high electricity The problem of charge-discharge characteristic under current density reduces, and provide and a kind of the non-aqueous of high battery performance and high security can be achieved at the same time Electrolyte and the nonaqueous electrolyte battery using the nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>
The present invention completes in view of the aforementioned technical background, and it is an object of the present invention to provide one kind can keep high power capacity, imparting good The nonaqueous electrolytic solution and non-aqueous electrolyte secondary battery of trickle charge characteristic.
<Nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery 6>
The present invention is completed, and it is an object of the present invention to provide a kind of discharge load excellent in view of the aforementioned technical background, and is had Excellent High temperature storage characteristic, the non-aqueous electrolyte for secondary battery of cycle characteristics.
Solution to the problem
<Nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>Corresponding to claim 1~8,13,14,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：When containing in nonaqueous electrolytic solution At least one kind of carbonic ester with halogen atom and when being also added with specific compound, it is special can to obtain excellent discharge load Property, and good High temperature storage characteristic and cycle characteristics can be kept, and the present invention 1 is completed based on this.
That is, the present invention 1 provides nonaqueous electrolytic solution 1, which is used for non-aqueous electrolyte secondary battery, described non- Water-Electrolyte secondary cell has nonaqueous electrolytic solution and can occlude and release the cathode and anode of ion, wherein, the non-water power Solving liquid has electrolyte and nonaqueous solvents, which contains the carbonic ester with halogen atom, contains mono-fluor phosphate simultaneously And/or difluorophosphoric acid salt.
In addition, the present invention 1 also provides non-aqueous electrolyte secondary battery 1, which contains non-water power The cathode and anode of liquid and energy occlusion/releasing lithium ion are solved, wherein, which is above-mentioned nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>Corresponding to claim 9~14,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：It is added into nonaqueous electrolytic solution During specific compound, though use " high-k and low viscosity, have beyond backbone carbonyl containing hetero atom Functional group solvent " in the case of, it is also possible to obtain excellent discharge load characteristic, and good High temperature storage can be kept Characteristic and cycle characteristics, and the present invention 2 is completed based on this.
That is, the present invention 2 provides nonaqueous electrolytic solution 2, which mainly by electrolyte and dissolves the non-of the electrolyte Aqueous solvent is formed, wherein, the nonaqueous electrolytic solution contains at 25 DEG C for liquid and dielectric constant more than 5, viscosity exists Below 0.6cP, there is the compound for forming the group (except backbone carbonyl) containing heteroatomic skeleton, also contains mono-fluor phosphate And/or difluorophosphoric acid salt.
In addition, the present invention 2 also provides non-aqueous electrolyte secondary battery 2, which contains non-water power The cathode and anode of liquid and energy occlusion/releasing lithium ion are solved, wherein, the nonaqueous electrolytic solution used is above-mentioned nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>Corresponding to claim 15~17,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：When to containing mono-fluor phosphate It, can be with and/or when at least one kind of compound in following compounds is further added in the nonaqueous electrolytic solution of difluorophosphoric acid salt Inhibit gas when carrying out trickle charge to generate and keep good battery behavior, wherein, the compound includes：With general formula (1) represent compound, nitrile compound, isocyanate compound, phosphazene compound, disulfonate compound, sulfide compound, Disulfide compound, acid anhydrides, the α lactone compounds with substituent group and the compound with carbon-carbon triple bond, and be based on This completes the present invention 3.
That is, the present invention 3 provides nonaqueous electrolytic solution 3, which mainly by electrolyte and dissolves the non-of the electrolyte Aqueous solvent is formed, and in the nonaqueous electrolytic solution, containing mono-fluor phosphate and/or difluorophosphoric acid salt, is also contained selected from following chemical combination At least one kind of compound (hereinafter referred to as " the compound of the present invention A ") in object：The compound that is represented with the following general formula (1), nitrile Compound, isocyanate compound, phosphazene compound, disulfonate compound, sulfide compound, disulfide compound, acid anhydrides, The α lactone compounds with substituent group and the compound with carbon-carbon triple bond.
[chemical formula 1]
[in general formula (1), R1、R2And R3The carbon number 1 for each independently represent fluorine atom, being optionally replaced by fluorine atoms The alkoxy of~12 alkyl or the carbon number 1~12 being optionally replaced by fluorine atoms.]
In addition, the present invention 3 also provides non-aqueous electrolyte secondary battery 3, which has non-water power Solution liquid and the cathode and anode that can occlude and release lithium ion, wherein, the nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>Corresponding to claim 18~25,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：By using cyclic sulfones simultaneously Main solvent of the compound of compound and viscosity below certain upper limit as nonaqueous electrolytic solution, and make it further containing spy Determine compound, the reduction of charge-discharge characteristic at higher current densities can be inhibited, so as to simultaneously have high battery performance and High security, and the present invention 4 is completed based on this.
That is, the present invention 4 provides nonaqueous electrolytic solution 4, and the nonaqueous electrolytic solution 4 is containing electrolyte and dissolves the non-aqueous of the electrolyte Solvent, in the nonaqueous electrolytic solution, containing the cyclic sulfones for accounting for 10~70 volume % of the nonaqueous solvents total amount and at 25 DEG C Under viscosity be below 1.5mPas compound, and contain at least one kind of compound in following compounds： Carbonic ester with unsaturated bond, the carbonic ester with halogen atom and mono-fluor phosphate and difluorophosphoric acid salt.
In addition, the present invention 4 also provides non-aqueous electrolyte secondary battery 4, which contains non-water power Solution liquid and the cathode and anode that can occlude/release lithium ion, wherein, the nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>Corresponding to claim 26~32,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：By making in nonaqueous electrolytic solution Containing cyclic polyamine compounds and/or Cyclic polyamides compound, and make further to add in the nonaqueous electrolytic solution as needed The specific compounds such as unsaturated carbon acid ester, the trickle charge that can be greatly improved while high power capacity is kept at high temperature are special Property, and the present invention 5 is completed based on this.
That is, the present invention 5 provides nonaqueous electrolytic solution 5, which has containing lithium salts and the non-water system for dissolving the lithium salts Solvent, the non-water system organic solvent contain cyclic polyamine compounds and/or Cyclic polyamides compound, also contain selected from following At least one kind of compound in substance：Unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt.Hereinafter, will The invention is referred to as " embodiment 5-1 ".
In addition, the present invention 5 provides following nonaqueous electrolytic solutions, which contains lithium salts and dissolves the non-aqueous of the lithium salts It is organic solvent, which contains cyclic polyamine compounds, also contains and accounts for non-5 matter of water system organic solvent total amount Measure the cyclic carbonate of the mass % of %~40.Hereinafter, which is referred to as " embodiment 5-2 ".
In addition, the present invention 5 provides following nonaqueous electrolytic solutions, which contains lithium salts and dissolves the non-aqueous of the lithium salts It is organic solvent, which contains Cyclic polyamides compound.Hereinafter, which is referred to as " embodiment 5-3”。
In addition, the present invention 5 also provides non-aqueous electrolyte secondary battery 5, in the non-aqueous electrolyte secondary battery 5, use Above-mentioned nonaqueous electrolytic solution.
<Nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery 6>Corresponding to claim 33~38,39~41
The inventors of the present invention have made intensive studies to achieve the above object, it turns out that：It is added into nonaqueous electrolytic solution When specific di-sulfonyl imides salt and specific compound, excellent discharge load characteristic can be obtained, and can be kept good High temperature storage characteristic and cycle characteristics, and based on this complete the present invention 6.
That is, the present invention 6 provides nonaqueous electrolytic solution 6, which mainly by electrolyte and dissolves the non-of the electrolyte Aqueous solvent is formed, which contains the annular di-sulfonyl imides salt of at least one kind of the following general formula (2) expression, also containing single Fluorophosphate and/or difluorophosphoric acid salt.
[chemical formula 2]
[in formula, R is represented optionally by the alkylidene of alkyl-substituted carbon number 1~12, and the alkyl and alkylidene are also optional It is replaced by fluorine atoms；In addition, n is 1~3 integer, M be a kind in the 1st race of the periodic table of elements, the 2nd race and the 13rd race with Upper metal or season.]
In addition, the present invention 6 also provides non-aqueous electrolyte secondary battery 6, which contains non-water power Solution liquid and the cathode and anode that can occlude/release lithium ion, wherein, the nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
The effect of invention
<Nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>
According to the present invention 1, two with excellent discharge load characteristic, High temperature storage characteristic and cycle characteristics can be provided Primary cell nonaqueous electrolytic solution 1 and non-aqueous electrolyte secondary battery 1.
<Nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>
According to the present invention 2, can provide with excellent discharge load characteristic and with excellent High temperature storage characteristic and The nonaqueous electrolytic solution 2 of cycle characteristics and non-aqueous electrolyte secondary battery 2.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>
According to the present invention 3, inhibition gas when can provide cycle characteristics, preservation characteristics, trickle charge generates, battery is special The excellent nonaqueous electrolytic solution 3 of property and non-aqueous electrolyte secondary battery 3.
<Nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>
In the present invention 4, the solvent mixed with cyclic sulfones has the low viscosity of below 1.5mPas, non- The viscosity of water electrolysis liquid entirety can prevent at higher current densities less than the viscosity disclosed in patent document 6 The reduction of charge/discharge capacity.That is, according to the present invention 4, the height that can reach with usually used electrolyte equal extent can be provided Charge-discharge characteristic, preservation characteristics under capacity, high current density, and security is significantly excellent in usually used electrolyte Non-electrolyte battery 4.Thus, it is possible to realize high safety while the enlargement for realizing nonaqueous electrolyte battery, high performance Change.
<Nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>
According to the present invention 5, can be maintained high power capacity and with the nonaqueous electrolyte of excellent trickle charge characteristic etc. Secondary cell 5.
<Nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery 6>
According to the present invention 6, can obtain with excellent discharge load characteristic and with excellent High temperature storage characteristic, The non-aqueous electrolyte for secondary battery 6 of cycle characteristics and non-aqueous electrolyte secondary battery 6.
Specific embodiment
In the following, be specifically described for embodiments of the present invention, but following records is to the explanation of inscape An example (typical example) of embodiments of the present invention, the present invention, can be without departing from this hairs from the limitation of these particular contents Various modifications are carried out in the range of bright main points to implement the present invention.
<Nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>
[1. non-aqueous electrolyte for secondary battery 1]
The nonaqueous electrolytic solution 1 of the present invention is identical with common nonaqueous electrolytic solution, containing electrolyte and dissolves the electrolyte Nonaqueous solvents.
<1-1. electrolyte>
Electrolyte for the nonaqueous electrolytic solution 1 of the present invention is not particularly limited, and can be randomly mixed in target non-aqueous solution electrolysis The well known electrolyte used in electrolitc secondary cell as electrolyte.The nonaqueous electrolytic solution 1 of the present invention is used for nonaqueous electrolyte During secondary cell 1, electrolyte is preferably lithium salts.
As the specific example of electrolyte, it can be mentioned, for example：
LiClO4、LiAsF6、LiPF6、LiCO3、LiBF4Wait inorganic lithium salts；
LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、LiPF4 (CF3)2、LiPF4(C2F5)2、LiPF4(CF3SO2)2、LiPF4(C2F5SO2)2、LiBF3(CF3)、LiBF3(C2F5)、LiBF2 (CF3)2、LiBF2(C2F5)2、LiBF2(CF3SO2)2、LiBF2(C2F5SO2)2Etc. fluorine-containing organic lithium salt；
Two (oxalate conjunction) lithium borates, three (oxalate conjunction) lithium phosphates, difluoro oxalate root close the networks containing dicarboxylic acids such as lithium borate Close the lithium salts of object；
KPF6、NaPF6、NaBF4、CF3SO3The sodium salts such as Na or sylvite etc..
In above-mentioned electrolyte, preferably LiPF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2Or two (oxalic acid Root closes) lithium borate, particularly preferred LiPF6Or LiBF4。
Electrolyte can be used alone, can also in any combination and ratio use two or more.Wherein, when combination makes When with 2 kinds of specific inorganic lithium salts or inorganic lithium salt and fluorine-containing organic lithium salt is applied in combination, it can inhibit to produce in trickle charge Angry body or inhibition deteriorate after High temperature storage, therefore preferably.
LiPF particularly preferably is applied in combination6And LiBF4Or by LiPF6、LiBF4Wait inorganic lithium salts and LiCF3SO3、LiN (CF3SO2)2、LiN(C2F5SO2)2It is applied in combination etc. fluorine-containing organic lithium salt.
LiPF is applied in combination in addition, working as6And LiBF4When, contained LiBF4Shared ratio is usual in electrolyte total amount The mass % of preferably 0.01 mass %~20.Work as LiBF4Degree of dissociation it is too low, when ratio is excessively high, nonaqueous electrolytic solution 1 may be caused Resistance rise.
On the other hand, by LiPF6、LiBF4Wait inorganic lithium salts and LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2Etc. containing When fluorine organic lithium salt is applied in combination, inorganic lithium salt ratio shared in lithium salts total amount is preferably generally the matter of 70 mass %~99 Measure the scope of %.In general, when fluorine-containing organic lithium salt and inorganic lithium salt compared to molecular weight is excessive, ratio is excessively high when, sometimes result in Nonaqueous solvents ratio shared in 1 total amount of nonaqueous electrolytic solution reduces, so that the resistance rise of nonaqueous electrolytic solution 1.
In addition, unobvious destroy the present invention 1 effect in the range of, lithium salts the present invention nonaqueous electrolytic solution 1 most The concentration in composition can be arbitrary eventually, but usually in more than 0.5mol/L, preferably exist in more than 0.6mol/L, more preferably More than 0.8mol/L, in addition, usually in below 3mol/L, preferably in below 2mol/L, more preferably in the model of below 1.5mol/L It encloses.When the concentration is too low, the conductivity deficiency of nonaqueous electrolytic solution 1 may be caused；When the concentration is too high, since viscosity raises, Conductivity declines, and sometimes results in the reduced performance of the non-aqueous electrolyte secondary battery using nonaqueous electrolytic solution 1 of the invention.
Particularly, when the nonaqueous solvents of nonaqueous electrolytic solution 1 is with carbonations such as alkylene carbonates or dialkyl carbonates When conjunction object is main, LiPF can be used alone6, but preferably by LiPF6With LiBF4It is applied in combination, because can so inhibit because even Capacity deterioration caused by continuous charging.When LiPF is applied in combination6And LiBF4When, LiBF4With LiPF6Molar ratio usually exist More than 0.005, preferably more than 0.01, particularly preferably more than 0.05, and usually below 0.4, preferably below 0.2.When When the molar ratio is excessive, there is that the battery behavior after High temperature storage is caused to reduce, on the contrary, when molar ratio is too small, it is difficult to Obtain the effect for inhibiting gas generation and capacity deterioration in trickle charge.
In addition, the rings such as gamma-butyrolacton, gamma-valerolactone containing more than 50 volume % in the nonaqueous solvents of nonaqueous electrolytic solution 1 During shape carboxylate compound, preferably LiBF4Account for more than the 50mol% of electrolyte total amount.
<1-2. has the carbonic ester of halogen atom>
As " carbonic ester with halogen atom " in the present invention 1, without other special limits as long as with halogen atom System, can use arbitrary carbonic ester.As the preferred carbonic ester of " carbonic ester with halogen atom ", can enumerate with halogen atom Cyclic carbonate or the linear carbonate with halogen atom.
As the specific example of halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom etc. can be enumerated.Wherein, more preferably Fluorine atom or chlorine atom, particularly preferred fluorine atom.In addition, possessed halogen is former in every 1 molecule " carbonic ester with halogen atom " Subnumber is not particularly limited as long as more than 1, usually below 10, preferably below 6.When every 1 molecule " has halogen atom When having multiple halogen atoms in carbonic ester ", these halogen atoms can be mutually the same, can also be different.
<1-2-1. cyclic carbonate>
In the following, it is illustrated for the cyclic carbonate as " carbonic ester with halogen atom " in the present invention 1.Annular carbon The ring member nitrogen atoms number of acid esters is usually more than 4, is preferably more than 5, and the upper limit is preferably below 10, particularly preferably below 8.Deviate During the scope, may trigger compound chemical stability or industrial accessibility in terms of the problem of.As these rings of composition The atomicity of the ring of shape carbonic ester be 5~8 cyclic carbonate specific example, can enumerate ethylene carbonate, propylene carbonate, Butylene carbonate, pentylene.In addition, there can also be carbon-to-carbon unsaturated bond in the ring of cyclic carbonate.As concrete example Son can enumerate vinylene carbonate, cis-2-butene-Isosorbide-5-Nitrae-glycol carbonate etc..
Above-mentioned cyclic carbonate can also have the substituent group formed by alkyl.Wherein, it is not special for alkyl species Limitation, can be aliphatic alkyl or aromatic hydrocarbyl, can also be by aliphatic alkyl and aromatic hydrocarbyl bonding The alkyl formed.When the alkyl is aliphatic alkyl, it can be chain or ring-type, can also be by chain and ring The structure that shape bonding forms.Can be that straight-chain can also be branched when it is chain alkyl.Furthermore it is possible to it is saturation Alkyl, it is possible to have unsaturated bond.
As the specific example of above-mentioned alkyl, alkyl, cycloalkyl can be enumerated, there is the alkyl of unsaturated bond (below, by it Suitably referred to as " unsaturated alkyl ") etc..
As the specific example of alkyl, it can be mentioned, for example methyl, ethyl, 1- propyl, 1- Methylethyls, 1- butyl, 1- first Base propyl, 2- methyl-propyls, 1,1- dimethyl ethyls etc..
Wherein, preferably methyl or ethyl.
As the specific example of cycloalkyl, it can be mentioned, for example cyclopenta, 2- methylcyclopentyls, 3- methylcyclopentyls, 2,2- Dimethylcyclopentyl, 2,3- dimethylcyclopentyls, 2,4- dimethylcyclopentyls, 2,5- dimethylcyclopentyls, 3,3- diformazan basic rings Amyl, 3,4- dimethylcyclopentyls, 2- ethylcyclopentyls, 3- ethylcyclopentyls, cyclohexyl, 2- methylcyclohexyls, 3- methyl rings Hexyl, 4- methylcyclohexyls, 2,2- Dimethylcyclohexyls, 2,3- Dimethylcyclohexyls, 2,4- Dimethylcyclohexyls, 2,5- diformazans Butylcyclohexyl, 2,6- Dimethylcyclohexyls, 3,4- Dimethylcyclohexyls, 3,5- Dimethylcyclohexyls, 2- ethylcyclohexyls, 3- second Butylcyclohexyl, 4- ethylcyclohexyls, bicyclic [3,2,1] octyl- 1- bases, bicyclic [3,2,1] octyl- 2- bases etc..
Wherein, preferably cyclopenta or cyclohexyl.
In addition, the specific example as unsaturated alkyl, it can be mentioned, for example vinyl, 1- propylene -1- bases, 1- propylene -2- Base, pi-allyl, cyclobutenyl, acetenyl, propargyl, phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,3- diformazans Base phenyl, xylyl, phenyl methyl, 1- phenylethyls, 2- phenylethyls, diphenyl methyl, trityl group, cinnamyl Deng.
Wherein, preferred vinyl, pi-allyl, phenyl, phenyl methyl or 2- phenylethyls.
Above-mentioned alkyl can also be substituted by the substituent group of 1 or 2 or more.As long as destroy the effect of the present invention 1 in unobvious In the range of, it is not particularly limited for the species of substituent group, as example, hydroxyl, amino, nitro, cyano, carboxylic can be enumerated Base, ether, aldehyde radical etc..In addition, above-mentioned alkyl can also be mutually bonded by oxygen atom with cyclic carbonate.It should be noted that When above-mentioned alkyl has 2 or more substituent groups, above-mentioned substituent group can be mutually the same, can also be different.
To above-mentioned alkyl it is arbitrary two or more be compared when, they can be mutually the same, can also be different.When When above-mentioned alkyl has substituent group, the substituted hydrocarbon radical including these substituent groups can be mutually the same, can also be different. In addition, in above-mentioned alkyl it is arbitrary two or more can also be mutually bonded and form cyclic structure.
The carbon number of above-mentioned alkyl usually more than 1, and usually below 20, preferably below 10, more preferably 6 with Under.When the carbon number of alkyl is excessive, the molal quantity of Unit Weight is reduced, and sometimes results in the reduction of various effects.In addition, When above-mentioned alkyl has substituent group, the carbon number of the substituted hydrocarbon radical including these substituent groups meets above range.
With regard to it is above-mentioned with the cyclic carbonate of halogen atom for, halogen atom can Direct Bonding it is former in the hydrocarbon for forming cyclic structure On son, halogen atom can also be bonded on above-mentioned " substituent group formed by alkyl ", and halogen atom can also be bonded in described simultaneously It is formed on the carbon atom of cyclic structure and on " substituent group formed by alkyl ".
It, can as by the specific example of halogenated alkyl when halogen atom is bonded on " substituent group formed by alkyl " It enumerates for example：One methyl fluoride, difluoromethyl, trifluoromethyl, 1- fluoro ethyls, 2- fluoro ethyls, 1,1- bis-fluoro ethyls, 1,2- difluoro second Base, 2,2- bis-fluoro ethyls, 2,2,2- trifluoroethyls, perfluoro-ethyl, chloromethyl, dichloromethyl, trichloromethyl, 1- chloroethyls, 2- chloroethyls, 1,1- Dichloroethyls, 1,2- Dichloroethyls, 2,2- Dichloroethyls, 2,2,2- trichloroethyls, perchloro- ethyl etc..
Wherein, a preferably methyl fluoride, difluoromethyl, trifluoromethyl, 2,2- bis-fluoro ethyls, 2,2,2- trifluoroethyls or perfluor Ethyl.
When halogen atom is bonded on " substituent group formed by alkyl ", as by the specific example of halogenated cycloalkyl, It can be mentioned, for example：1- fluorine cyclopenta, 2- fluorine cyclopenta, 3- fluorine cyclopenta, Difluorocyclopentyl, trifluoro cyclopenta, 1- fluorine cyclohexyl, 2- fluorine cyclohexyl, 3- fluorine cyclohexyl, 4- fluorine cyclohexyl, difiuorocyclohexyl, trifluoro cyclohexyl, 1- chlorine cyclopenta, 2- chlorine cyclopenta, 3- chlorine cyclopenta, dichloro cyclopenta, trichlorine cyclopenta, 1- chlorine cyclohexyl, 2- chlorine cyclohexyl, 3- chlorine cyclohexyl, 4- chlorine cyclohexyl, Dichloro cyclohexyl, trichlorine cyclohexyl etc..
Wherein, preferably 1- fluorine cyclopenta, 2- fluorine cyclopenta, 3- fluorine cyclopenta, 1- fluorine cyclohexyl, 2- fluorine cyclohexyl, 3- fluorine Cyclohexyl or 4- fluorine cyclohexyl.
When halogen atom is bonded on " substituent group formed by alkyl ", as by the concrete example of halogenated unsaturated alkyl Son, it can be mentioned, for example：1- is fluoride-based, 2- is fluoride-based, 1,2- difluoroethylenes base, perfluorovinyl sulfide, 1- fluorine pi-allyl, 2- fluorine Pi-allyl, 3- fluorine pi-allyl, 2- fluorophenyls, 3- fluorophenyls, 4- fluorophenyls, 2,3- difluorophenyls, 2,4 difluorobenzene base, 2,5- bis- The fluoro- 1- phenyl methyls of fluorophenyl, 2,6- difluorophenyls, 3,4- difluorophenyls, 3,5- difluorophenyls, 1-, bis- fluoro- 1- phenyl of 1,1- Methyl, (2- fluorophenyls) methyl, (3- fluorophenyls) methyl, (4- fluorophenyls) methyl, (2- fluorophenyls) methyl fluoride, the fluoro- 2- benzene of 1- Base ethyl, bis- fluoro- 2- phenylethyls of 1,1-, bis- fluoro- 2- phenylethyls of 1,2-, 2- (2- fluorophenyls) ethyl, 2- (3- fluorophenyls) Ethyl, 2- (4- fluorophenyls) ethyl, the fluoro- 2- of 1- (2- fluorophenyls) ethyl, the fluoro- 2- of 1- (2- fluorophenyls) ethyl, 1- chlorovinyls, 2- chlorovinyls, 1,2- dichloroethylenes, perchloroethylene base, 1- chlorallyls, 2- chlorallyls, 3- chlorallyls, 2- chlorobenzenes Base, 3- chlorphenyls, 4- chlorphenyls, 2,3- dichlorophenyls, 2,4 dichloro benzene base, 2,5- dichlorophenyls, 2,6- dichlorophenyls, 3,4- Dichlorophenyl, 1,5- dichlorophenyls, 1- chloro-1-phenyls methyl, bis- chloro- 1- phenyl methyls of 1,1-, (2- chlorphenyls) methyl, (3- Chlorphenyl) methyl, (4- chlorphenyls) methyl, (2- chlorphenyls) chloromethyl, the chloro- 2- phenylethyls of 1-, bis- chloro- 2- phenyl second of 1,1- Base, bis- chloro- 2- phenylethyls of 1,2-, 2- (2- chlorphenyls) ethyl, 2- (3- chlorphenyls) ethyl, 2- (4- chlorphenyls) ethyl, 1- Chloro- 2- (2- chlorphenyls) ethyl, the chloro- 2- of 1- (2- chlorphenyls) ethyl etc..
Wherein, preferably 2- fluorophenyls, 3- fluorophenyls, 4- fluorophenyls, 2,4- difluorophenyls, 3,5- difluorophenyls, the fluoro- 1- of 1- Phenyl methyl, (2- fluorophenyls) methyl, (4- fluorophenyls) methyl, (2- fluorophenyls) methyl fluoride, the fluoro- 2- phenylethyls of 1-, 2- (2- Fluorophenyl) ethyl or 2- (4- fluorophenyls) ethyl.
As described above, as with halogen atom cyclic carbonate specific example, it can be mentioned, for example fluorine ethylene carbonate, Vinylene carbonate, 4,4- difluoros ethylene carbonate, 4,5- difluoros ethylene carbonate, bis- vinylene carbonates of 4,4-, 4,5- bis- The fluoro- 4- methyl carbonic acids ethyl of vinylene carbonate, 4-, the chloro- 4- methyl carbonic acids ethyls of 4-, the fluoro- 5- methyl carbonic acids Asia second of 4- The chloro- 5- methyl carbonic acids ethyl of ester, 4-, bis- fluoro- 4- methyl carbonic acids ethyls of 4,5-, bis- chloro- 4- methyl carbonic acids ethyls of 4,5-, The fluoro- 5- methyl carbonic acids ethyls of 4-, the chloro- 5- methyl carbonic acids ethyls of 4-, bis- fluoro- 5- methyl carbonic acids ethyls of 4,4-, 4,4- bis- Chloro- 5- methyl carbonic acids ethyl, 4- (methyl fluoride) ethylene carbonate, 4- (chloromethyl) ethylene carbonate, 4- (difluoromethyl) carbon Sour ethyl, 4- (dichloromethyl) ethylene carbonate, 4- (trifluoromethyl) ethylene carbonate, 4- (trichloromethyl) carbonic acid Asia second Ester, 4- (methyl fluoride) -4- fluorine ethylene carbonate, 4- (chloromethyl) -4- vinylene carbonates, 4- (methyl fluoride) -5- fluorine carbonic acid are sub- Ethyl ester, 4- (chloromethyl) -5- vinylene carbonates, the fluoro- 4,5- dimethyl ethylene carbonates of 4-, the chloro- 4,5- dimethyl carbonic acid of 4- Ethyl, bis- fluoro- 4,5- dimethyl ethylene carbonates of 4,5-, bis- chloro- 4,5- dimethyl ethylene carbonates of 4,5-, 4,4- bis- are fluoro- 5,5- dimethyl ethylene carbonate, bis- chloro- 5,5- dimethyl ethylene carbonates of 4,4- etc..
In addition, the specific example as " cyclic carbonate with halogen atom " with carbon-to-carbon unsaturated bond in ring, it can It enumerates for example：The fluoro- 5- methylvinylene carbonates of fluorine vinylene carbonate, 4-, the fluoro- 5- phenyl-carbonic acids vinylenes of 4-, 4- (three Methyl fluoride) vinylene carbonate, chlorine vinylene carbonate, the chloro- 5- phenyl-carbonic acids of the chloro- 5- methylvinylene carbonates of 4-, 4- be sub- Vinyl acetate, 4- (trichloromethyl) vinylene carbonate etc..
In addition, the specific example as the cyclic carbonate substituted by alkyl outside ring with carbon-to-carbon unsaturated bond, can arrange Citing is such as：The fluoro- 4- vinylethylene carbonates of 4-, the fluoro- 5- vinylethylene carbonates of 4-, bis- fluoro- 5- vinyl carbonic acid of 4,4- Ethyl, bis- fluoro- 4- vinylethylene carbonates of 4,5-, the chloro- 5- vinylethylene carbonates of 4-, bis- chloro- 5- vinyl of 4,4- Ethylene carbonate, bis- chloro- 4- vinylethylene carbonates of 4,5-, the fluoro- 4,5- divinyl ethylene carbonates of 4-, 4,5- bis- are fluoro- The chloro- 4,5- divinyls ethylene carbonate of 4,5- divinyl ethylene carbonate, 4-, bis- chloro- 4,5- divinyl carbonic acid of 4,5- are sub- The fluoro- 4- phenyl-carbonic acids ethyl of ethyl ester, 4-, the fluoro- 5- phenyl-carbonic acids ethyls of 4-, bis- fluoro- 5- phenyl-carbonic acids ethyls of 4,4-, 4, Bis- fluoro- 4- phenyl-carbonic acids ethyls of 5-, the chloro- 4- phenyl-carbonic acids ethyls of 4-, the chloro- 5- phenyl-carbonic acids ethyls of 4-, 4,4- bis- are chloro- 5- phenyl-carbonic acids ethyl, bis- chloro- 4- phenyl-carbonic acids ethyls of 4,5-, bis- fluoro- 4,5- diphenyl ethylene carbonates of 4,5-, 4,5- Two chloro- 4,5- diphenyl ethylene carbonates, the fluoro- 5- vinyl vinylene carbonates of 4-, the chloro- 5- vinyl vinylene carbonates of 4- Deng.
Above-mentioned sub- with the carbonic ester of fluorine atom, especially fluorine carbonic acid in the cyclic carbonate of halogen atom, is preferably had Ethyl ester, 4,4- difluoros ethylene carbonate, 4,5- difluoros ethylene carbonate, the fluoro- 4- methyl carbonic acids ethyls of 4-, the fluoro- 5- methyl of 4- Ethylene carbonate, 4- (methyl fluoride) ethylene carbonates or 4- (trifluoromethyl) ethylene carbonate, due to being easy to obtain with Industrial routes It takes, and with chemical stability, therefore more preferably use.
It should be noted that it is not particularly limited for the molecular weight of the cyclic carbonate with halogen atom, as long as not Can be arbitrary molecular weight in the range of the apparent effect for destroying the present invention 1, but usually more than 50, preferably more than 80, and Usually below 250, preferably below 150.When molecular weight is excessive, there is the cyclic carbonate of halogen atom in nonaqueous electrolytic solution Dissolubility in 1 reduces, and is sometimes difficult to that the effect of the present invention 1 is made fully to show.
In addition, being also not particularly limited for the manufacturing method of the cyclic carbonate with halogen atom, public affairs can be optionally selected The method known manufactures.
It, can be only containing a kind of cyclic carbonate with halogen atom as described above in the nonaqueous electrolytic solution 1 of the present invention Ester, can also in any combination and ratio contains two or more simultaneously.Do not have for the content of the cyclic carbonate with halogen atom It is specifically limited, usually using the mass % of 0.001 mass %~100.
Here, it is different to have the function of that the cyclic carbonate of halogen atom is believed to show due to content is different.On The details of this factor is not yet clear and definite, and the scope of the present invention 1 is from the limitation of this factor, it is believed that its mechanism is such as Under.That is, when using the cyclic carbonate with halogen atom compared with nonaqueous solvents total amount for the mass % of 0.001 mass %~10 During as additive, the cyclic carbonate with halogen atom can decompose in negative terminal surface and form negative terminal surface protective film；It is another Aspect, when using the cyclic carbonate with halogen atom of the mass % of 10 mass %~100 as nonaqueous solvents, then with halogen The cyclic carbonate of atom not only shows the above-mentioned effect as additive, can also show the resistance to of nonaqueous electrolytic solution 1 of sening as an envoy to The effect that oxidisability improves.
When using the cyclic carbonate with halogen atom as additive, compared with nonaqueous solvents total amount, content is led to Often more than 0.001 mass %, preferably more than 0.01 mass %, and usually below 10 mass %, preferably 5 mass % with Under.When content ratio is very few, based on their reduction decomposition, cathode epithelium can not be adequately formed, may lead to not fill Divide and show battery behavior.
When using the cyclic carbonate with halogen atom as nonaqueous solvents, compared with nonaqueous solvents total amount, content Usually more than 10 mass %, preferably more than 12 mass %, particularly preferably more than 15 mass %, and usually in 100 matter Measure below %, preferably below 80 mass %, particularly preferably below 50 mass %.If its content is less than above-mentioned lower limit, It is unable to reach for the inhibition of the oxygenolysis of 1 constituent of other nonaqueous electrolytic solutions except being carried out on positive electrode surface Desired level can not show the effect of the present invention 1 sometimes.It is in addition, when content is higher than the above-mentioned upper limit, then viscous due to electrolyte Degree increases, and the various characteristics in battery is caused to reduce sometimes.
In addition, the cyclic carbonate with halogen atom can be with arbitrary proportion and the aftermentioned chain carbonic acid with halogen atom Ester and/or " other nonaqueous solvents in addition to the carbonic ester with halogen atom " are used in mixed way.As group when being used in mixed way The example of conjunction, it can be mentioned, for example：It is cyclic carbonate with halogen atom and the cyclic carbonate without halogen atom, former with halogen The cyclic carbonate of son and the linear carbonate without halogen atom, the cyclic carbonate with halogen atom and with halogen atom Linear carbonate, the cyclic carbonate with halogen atom and cyclic carboxylic esters, the cyclic carbonate with halogen atom and chain carboxylic Acid esters, the cyclic carbonate with halogen atom and cyclic ether, the cyclic carbonate with halogen atom and chain ether, with halogen atom Cyclic carbonate and phosphorous organic solvent, there is halogen atom cyclic carbonate and cyclic carbonate without halogen atom and Linear carbonate without halogen atom, the cyclic carbonate with halogen atom and cyclic carbonate and tool without halogen atom There is the linear carbonate of halogen atom, there is the cyclic carbonate of halogen atom and the cyclic carbonate without halogen atom and annular carboxylic Acid esters, the cyclic carbonate with halogen atom and the cyclic carbonate without halogen atom and chain carboxylate, with halogen atom Cyclic carbonate and cyclic carbonate without halogen atom and cyclic ether, there is the cyclic carbonate of halogen atom and do not have The cyclic carbonate and chain ether of halogen atom, the cyclic carbonate with halogen atom and cyclic carbonate without halogen atom and Linear carbonate without halogen atom and the linear carbonate with halogen atom, the cyclic carbonate with halogen atom and do not have There are the cyclic carbonate of halogen atom and cyclic carboxylic esters and linear carbonate without halogen atom, the annular carbon with halogen atom Acid esters and cyclic carbonate without halogen atom and chain carboxylate and linear carbonate without halogen atom have the halogen former The cyclic carbonate and cyclic carbonate without halogen atom and cyclic ether of son and the linear carbonate without halogen atom, tool There are the cyclic carbonate of halogen atom and the cyclic carbonate without halogen atom and chain ether and the chain carbon without halogen atom Acid esters, the cyclic carbonate with halogen atom and cyclic carbonate without halogen atom and phosphorous organic solvent and without halogen The linear carbonate of atom, the cyclic carbonate with halogen atom and cyclic carbonate and cyclic carboxylic esters without halogen atom With the linear carbonate with halogen atom, the cyclic carbonate with halogen atom and cyclic carbonate and ring without halogen atom The shape carboxylate and linear carbonate without halogen atom, the cyclic carbonate with the halogen atom and ring-type without halogen atom Carbonic ester and cyclic carboxylic esters and chain carboxylate have the cyclic carbonate of halogen atom and the cyclic carbonate without halogen atom Ester and cyclic carboxylic esters and cyclic ether have the cyclic carbonate of halogen atom and cyclic carbonate and ring-type without halogen atom Carboxylate and phosphorous organic solvent have the cyclic carbonate of halogen atom and the cyclic carbonate without halogen atom and annular carboxylic Acid esters and the linear carbonate with halogen atom and the linear carbonate without halogen atom, the cyclic carbonate with halogen atom With the cyclic carbonate without halogen atom and cyclic ether and the linear carbonate with halogen atom and chain without halogen atom Shape carbonic ester, the cyclic carbonate with halogen atom and the cyclic carbonate without halogen atom and phosphorous organic solvent and with The linear carbonate of halogen atom and linear carbonate without halogen atom etc..
<1-2-2. linear carbonate>
In the following, it is illustrated for the linear carbonate as " carbonic ester with halogen atom " in the present invention 1.Chain Carbonic ester usually has 2 alkyl, they can be the same or different.The carbon number of these alkyl preferably respectively 1 with On, the upper limit is preferably below 10, particularly preferably below 6.When deviateing above range, the chemistry for triggering compound sometimes is steady The problem of in terms of qualitative or industrial accessibility.
As the example for the alkyl for forming the linear carbonate, can be with it is above-mentioned substitute on cyclic carbonate take For the identical substituent group of base or with the above-mentioned substituent group identical by halogenated substituent group.
As the specific example of linear carbonate, it can be mentioned, for example：Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Dibutyl carbonate, divinyl carbonate, diallyl carbonate, diphenyl carbonate, methyl ethyl carbonate, methylpropyl carbonate, carbon Acid methyl butyl ester, methyl vinyl esters, methyl allyl ester, methyl phenylester, ethylpropyl carbonate, Carbonic acid ethyl-butyl ester, carbonic acid cyclic olefin copolymers, ethylvinyl, carbonic acid allyl base ester, carbonic acid ethyl phenyl ester etc..
Wherein, it is contemplated that easy degree etc. that industry obtains, preferably dimethyl carbonate, diethyl carbonate, diphenyl carbonate, Methyl ethyl carbonate, methyl vinyl esters, carbonic acid cyclic olefin copolymers, ethylvinyl, methyl allyl ester, carbonic acid allyl ethyl Ester, methyl phenylester, carbonic acid ethyl phenyl ester etc..
As the specific example of above-mentioned linear carbonate linear carbonate obtained by halogenated, it can be mentioned, for example：Carbonic acid first Base methyl fluoride ester, methyl difluoromethyl ester, methyl methyl ester trifluoroacetate, carbonic acid two (methyl fluoride) ester, two (difluoro of carbonic acid Methyl) ester, carbonic acid two (trifluoromethyl) ester, methyl chloromethane base ester, methyl dichloromethane base ester, three chloromethane of methyl Base ester, carbonic acid two (chloromethyl) ester, carbonic acid two (dichloromethyl) ester, carbonic acid two (trichloromethyl) ester, methyl 2- fluoro ethyls Ester, carbonic acid methyl fluoride ethyl ester, methyl 2,2- bis-fluoro ethyls ester, carbonic acid methyl fluoride 2- fluoro ethyls ester, carbonic acid ethyl difluoro Methyl ester, methyl 2,2,2- trifluoroethyls ester, carbonic acid methyl fluoride 2,2- bis-fluoro ethyls ester, carbonic acid 2- fluoro ethyl difluoromethyls Ester, carbonic acid ethyl methyl ester trifluoroacetate, methyl 2- chloro-ethyl esters, carbonic acid ethyl chloride methyl ester, bis- chloroethenes of methyl 2,2- Base ester, carbonic acid chloromethyl 2- chloro-ethyl esters, carbonic acid ethyl dichloromethane base ester, methyl 2,2,2- trichloroethyls, carbonic acid chlorine Methyl 2,2- Dichloroethyls ester, carbonic acid 2- chloroethyl dichloromethanes base ester, carbonic acid ethyl trichloromethyl ester, carbonic acid ethyl (2- fluorine second Base) ester, carbonic acid ethyl (2,2- bis-fluoro ethyls) ester, carbonic acid two (2- fluoro ethyls) ester, carbonic acid ethyl (2,2,2- trifluoroethyls) ester, Carbonic acid 2,2- bis-fluoro ethyls -2 '-fluoro ethyl ester, carbonic acid two (2,2- bis-fluoro ethyls) ester, carbonic acid 2,2,2- trifluoroethyls -2 '-fluorine Ethyl ester, carbonic acid 2,2,2- trifluoroethyls -2 ', 2 '-bis-fluoro ethyls ester, carbonic acid two (2,2,2- trifluoroethyls) ester, carbonic acid ethyl (2- chloroethyls) ester, carbonic acid ethyl (2,2- Dichloroethyls) ester, carbonic acid two (2- chloroethyls) ester, carbonic acid ethyl (2,2,2- trichlorines Ethyl) ester, carbonic acid 2,2- Dichloroethyls -2 '-chloro-ethyl ester, carbonic acid two (2,2- Dichloroethyls) ester, tri- chloroethenes of carbonic acid 2,2,2- Base -2 '-chloro-ethyl ester, carbonic acid 2,2,2- trichloroethyls -2 ', 2 '-Dichloroethyl ester, carbonic acid two (2,2,2- trichloroethyls) ester, Ethylene carbonate base methyl fluoride ester, ethylene carbonate base 2- fluoro ethyls ester, ethylene carbonate base 2,2- bis-fluoro ethyls ester, ethylene carbonate base 2, 2,2- trifluoroethyls ester, ethylene carbonate base chloromethane base ester, ethylene carbonate base 2- chloro-ethyl esters, ethylene carbonate base 2,2- Dichloroethyls Ester, ethylene carbonate base 2,2,2- trichloroethyls, allyl methyl fluoride ester, allyl 2- fluoro ethyls ester, carbonic acid alkene Propyl 2,2- bis-fluoro ethyls ester, allyl 2,2,2- trifluoroethyls ester, allyl chloromethane base ester, allyl 2- Chloro-ethyl ester, allyl 2,2- Dichloroethyls ester, allyl 2,2,2- trichloroethyls, carbonate methyl fluoride Ester, carbonate 2- fluoro ethyls ester, carbonate 2,2- bis-fluoro ethyls ester, carbonate 2,2,2- trifluoroethyls ester, carbonic acid benzene Base chloromethane base ester, carbonate 2- chloro-ethyl esters, carbonate 2,2- Dichloroethyls ester, carbonate 2,2,2- trichloroethyls Deng.
The carbonic ester of fluorine atom is preferably had in the linear carbonate of halogen atom above-mentioned, particularly methyl Methyl fluoride ester, carbonic acid two (methyl fluoride) ester, methyl difluoromethyl ester, methyl 2,2- bis-fluoro ethyls ester, carbonic acid ethyl (2,2- bis-fluoro ethyls) ester, carbonic acid two (2,2- bis-fluoro ethyls) ester, methyl 2,2,2- trifluoroethyls ester, carbonic acid ethyl (2, 2,2- trifluoroethyls) ester, carbonic acid two (2,2,2- trifluoroethyl) ester, from it is industrial easily obtain degree, chemical stability from the aspect of, More preferably use.
It should be noted that it is not particularly limited for the molecular weight of the linear carbonate with halogen atom, as long as not It is apparent to destroy in the range of the effect of the present invention 1, can be arbitrary molecular weight, but usually more than 50, preferably more than 80, and Usually below 250, preferably below 150.When molecular weight is excessive, there is the linear carbonate of halogen atom in nonaqueous electrolytic solution Dissolubility in 1 reduces, and sometimes results in the effect that can not fully show the present invention 1.
In addition, being also not particularly limited for the manufacturing method of the linear carbonate with halogen atom, public affairs can be arbitrarily selected It is prepared by the method known.
It, can be only containing a kind of chain carbonic acid with halogen atom as described above in the nonaqueous electrolytic solution 1 of the present invention Ester, can also in any combination and ratio contains two or more simultaneously.
Here, it is different to have the function of that the linear carbonate of halogen atom is believed to occur due to content is different.On this The details of one factor is not yet clear and definite, and the scope of the present invention 1 is from the limitation of this factor, it is believed that its mechanism is as follows. That is, when using the work of the linear carbonate with halogen atom compared with nonaqueous solvents total amount for the mass % of 0.001 mass %~10 For additive when, have halogen atom linear carbonate can negative terminal surface decompose and form negative terminal surface protective film；The opposing party Face, it is when using the linear carbonate with halogen atom of the mass % of 10 mass %~100 as nonaqueous solvents, then former with halogen The linear carbonate of son not only shows the above-mentioned effect as additive, can also show the oxytolerant for nonaqueous electrolytic solution 1 of sening as an envoy to The effect that the property changed improves.
When using the linear carbonate with halogen atom as additive, compared with the total amount of nonaqueous solvents, content Usually more than 0.001 mass %, preferably more than 0.01 mass %, and usually below 10 mass %, preferably in 5 mass % Below.When content ratio is very few, cathode epithelium can not be adequately formed based on their reduction decomposition, sometimes results in nothing Method fully shows battery behavior.
When using the linear carbonate with halogen atom as nonaqueous solvents, compared with nonaqueous solvents total amount, content Usually more than 10 mass %, preferably more than 12 mass %, particularly preferably more than 15 mass %, and usually in 100 matter Measure below %, preferably below 80 mass %, particularly preferably below 50 mass %.If its content is less than above-mentioned lower limit, It is unable to reach for the inhibition of the oxygenolysis of 1 constituent of other nonaqueous electrolytic solutions except being carried out on positive electrode surface Desired level can not show the effect of the present invention 1 sometimes.In addition, when content is higher than the above-mentioned upper limit, then due to electrolyte Viscosity increases, and the various characteristics in battery is caused to reduce sometimes.
In addition, the linear carbonate with halogen atom can be with arbitrary proportion and the above-mentioned cyclic carbonate with halogen atom And/or aftermentioned " other nonaqueous solvents in addition to the carbonic ester with halogen atom " are used in mixed way.During as being used in mixed way Combination example, it can be mentioned, for example：Linear carbonate with halogen atom and the cyclic carbonate without halogen atom, with The linear carbonate of halogen atom and the cyclic carbonate with halogen atom, linear carbonate and cyclic carboxylic acids with halogen atom Ester, the linear carbonate with halogen atom and phosphorous organic solvent, the linear carbonate with halogen atom and without halogen atom Cyclic carbonate and linear carbonate, there is halogen atom linear carbonate and cyclic carbonate and tool without halogen atom There is the cyclic carbonate of halogen atom, there is the linear carbonate of halogen atom and the cyclic carbonate without halogen atom and annular carboxylic It is acid esters, the linear carbonate with halogen atom and the cyclic carbonate without halogen atom and phosphorous organic solvent, former with halogen The linear carbonate of son and cyclic carbonate and linear carbonate with halogen atom, the linear carbonate with halogen atom and tool There are cyclic carbonate and cyclic carboxylic esters, the linear carbonate with halogen atom and the cyclic carbonate with halogen atom of halogen atom Ester and phosphorous organic solvent have the linear carbonate of halogen atom and cyclic carbonate and linear carbonate without halogen atom Linear carbonate with cyclic carboxylic esters, with halogen atom and the cyclic carbonate without halogen atom and the ring with halogen atom Shape carbonic ester and cyclic carboxylic esters, the linear carbonate with halogen atom and cyclic carbonate without halogen atom and phosphorous have Solvent and cyclic carboxylic esters have the linear carbonate of halogen atom and cyclic carbonate and cyclic carboxylic acids without halogen atom The ester and linear carbonate without halogen atom, the linear carbonate with the halogen atom and cyclic carbonate without halogen atom With cyclic ether and the linear carbonate without halogen atom, there is halogen atom linear carbonate and ring-type without halogen atom Carbonic ester and phosphorous organic solvent and linear carbonate without halogen atom have the linear carbonate of halogen atom and do not have It is the cyclic carbonate of halogen atom and the cyclic carbonate with halogen atom and the linear carbonate without halogen atom, former with halogen The linear carbonate of son and cyclic carbonate without halogen atom and cyclic carbonate with halogen atom and cyclic carboxylic esters, Linear carbonate with halogen atom and the cyclic carbonate without halogen atom and cyclic carbonate and ring with halogen atom The shape carboxylate and linear carbonate without halogen atom, the linear carbonate with the halogen atom and ring-type without halogen atom Carbonic ester and cyclic carbonate with halogen atom and cyclic ether and linear carbonate without halogen atom, with halogen atom Linear carbonate and cyclic carbonate without halogen atom and cyclic carbonate with halogen atom and phosphorous organic solvent and Linear carbonate without halogen atom.
<Other nonaqueous solvents of the 1-3. in addition to the carbonic ester with halogen atom>
It is contained " other non-aqueous in addition to the carbonic ester with halogen atom in nonaqueous electrolytic solution 1 as the present invention Solvent " as long as not bringing harmful effect solvent to battery behavior when as battery, is then not particularly limited, but is preferably One or more of following " other nonaqueous solvents in addition to the carbonic ester with halogen atom " enumerated.
As the example of " other nonaqueous solvents in addition to the carbonic ester with halogen atom ", it can be mentioned, for example：Chain Or cyclic carbonate, chain or cyclic carboxylic esters, chain or cyclic ether, phosphorous organic solvent, sulfur-bearing organic solvent etc..
In addition, for the species of linear carbonate, also there is no limit but preferred dialkyl carbonate forms dialkyl carbonate The carbon number of the alkyl of ester is respectively preferably 1~5, and especially preferably 1~4.As specific example, it can be mentioned, for example：Carbonic acid Dimethyl ester, methyl ethyl carbonate, diethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, carbonic acid diη-propyl ester Deng.
In above-mentioned linear carbonate, dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate due to can industry obtain, and Various characteristics in non-aqueous electrolyte secondary battery are good, therefore preferably.
For the species of cyclic carbonate, there is no limit but the carbon number of alkylidene for forming cyclic carbonate is preferably 2~6, especially preferably 2~4.Specifically, it can be mentioned, for example：Ethylene carbonate, propylene carbonate, butylene carbonate (2- ethyls Ethylene carbonate, cis or trans 2,3- dimethyl ethylene carbonate) etc..
Wherein, ethylene carbonate or propylene carbonate due to the various characteristics in non-aqueous electrolyte secondary battery it is good, Therefore preferably.
In addition, for chain carboxylate species also there is no limit, as specific example, it can be mentioned, for example：Methyl acetate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, propionic acid Ethyl ester, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propanoic acid tert-butyl ester etc..
Wherein, ethyl acetate, methyl propionate or ethyl propionate due to can industry obtain, and in non-aqueous electrolyte secondary battery In various characteristics it is good, therefore preferably.
In addition, for cyclic carboxylic esters species also there is no limit, can as the example of usually used cyclic carboxylic esters Enumerate gamma-butyrolacton, gamma-valerolactone, δ-valerolactone etc..
Wherein, gamma-butyrolacton industrial can obtain, and the various characteristics in non-aqueous electrolyte secondary battery are good, therefore It is preferred that.
In addition, for chain ether species also there is no limit, as specific example, it can be mentioned, for example：Dimethoxymethane, Dimethoxy-ethane, diethoxymethane, diethoxyethane, (ethoxymethyl) oxygroup methane, ethyoxyl Ethyl Methyl Ether etc..
Wherein, dimethoxy-ethane or diethoxyethane industrial can obtain, and in non-aqueous electrolyte secondary battery Various characteristics are good, therefore preferably.
In addition, for cyclic ether species also there is no limit, as the example of usually used cyclic ether, tetrahydrochysene can be enumerated Furans, 2- methyltetrahydrofurans, oxinane etc..
In addition, be also not particularly limited for the species of phosphorous organic solvent, as specific example, it can be mentioned, for example：Phosphorus The phosphoric acid esters such as sour trimethyl, triethyl phosphate, triphenyl phosphate；Trimethyl phosphite, triethyl phosphite, phosphorous triphenyl phosphate The phosphorous acid esters such as ester；Phosphinoxides such as trimethyl phosphine oxide, triethyl group phosphine oxide, triphenylphosphine oxide etc..
In addition, being also not particularly limited for the species of sulfur-bearing organic solvent, as specific example, it can be mentioned, for example sulfurous Sour glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, ring fourth Alkene sulfone (sulfolene), dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, a sulphur Change tetra methylthiuram, N, N- dimethyl methyls sulfonamide, N, N- diethyl Methanesulfomides etc..
In above-mentioned nonaqueous solvents, chain or cyclic carbonate or chain or cyclic carboxylic esters are secondary in nonaqueous electrolyte Various characteristics in battery are good, therefore preferably, wherein, more preferable ethylene carbonate, propylene carbonate, dimethyl carbonate, carbon Sour methyl ethyl ester, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate or gamma-butyrolacton, particularly preferred dimethyl carbonate, Methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate or ethyl propionate.
Above-mentioned solvent may be used alone, two or more kinds can also be used in combination, but preferred compositions use of more than two kindsization Close object.Solvent and linear carbonate class or chain of such as cyclic carbonates with high-k is particularly preferably applied in combination The low viscosity solvents such as shape esters.
One of the preferred compositions of " other nonaqueous solvents in addition to the carbonic ester with halogen atom " are with cyclic carbonate Combination based on esters and linear carbonate class.Wherein, the total amount of cyclic carbonates and linear carbonate class is in nonaqueous solvents Shared ratio is usually more than 80 volume %, is preferably more than 85 volume %, more preferably more than 90 volume % in total amount.Separately Outside, the volume of cyclic carbonates ratio shared in the total amount of cyclic carbonates and linear carbonate class is preferably in 5 bodies Product more than %, more preferably more than 10 volume %, particularly preferably more than 15 volume %, and usually below 50 volume %, it is excellent It is selected in below 35 volume %, more preferably below 30 volume %.Due to when use it is above-mentioned " except the carbonic ester with halogen atom with During the combination of outer other nonaqueous solvents ", the thus cycle characteristics of prepared battery and High temperature storage characteristic (especially high temperature Remaining capacity and high load discharge capacity after preservation) can obtain it is well balanced, therefore preferably.
In addition, as above-mentioned cyclic carbonates and the specific example of the preferred compositions of linear carbonate class, example can be enumerated Such as：Ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, carbonic acid Ethyl and carbonic acid dimethyl and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate With diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc..
As preferred combination, can also enumerate into the combination of above-mentioned ethylene carbonate and linear carbonate class further Add the combination of propylene carbonate.When containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is preferably 99:1~40:60, especially preferably 95:5~50:50.In addition, the volume of propylene carbonate accounts for 0.1 in nonaqueous solvents total amount More than volume %, preferably more than 1 volume %, more preferable more than 2 volume %, and usually below 10 volume %, preferably in 8 bodies Product below %, more preferably below 5 volume %, since the characteristic of ethylene carbonate and linear carbonate class combination can be being kept On the premise of, excellent discharge load characteristic is further obtained, therefore preferably.
Wherein, the combination of further preferably asymmetric linear carbonate class, particularly, ethylene carbonate and dimethyl carbonate With methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and carbonic acid Contain ethylene carbonate and symmetrical linear carbonate class and asymmetric linear carbonate class as diethylester and methyl ethyl carbonate Combination or the further combination containing propylene carbonate, since good cycle characteristics and discharge load characteristic can be obtained Balance, therefore preferably.Wherein, preferably asymmetric linear carbonate class is methyl ethyl carbonate, additionally, it is preferred that forming dialkyl carbonate The carbon number of the alkyl of ester is 1~2.
As other examples of preferred mixed solvent, including the solvent containing chain ester.Particularly, from raising battery From the viewpoint of low-temperature characteristics, preferably contain chain ester in the in the mixed solvent of above-mentioned cyclic carbonates and linear carbonate class Situation, as chain ester, particularly preferred ethyl acetate, methyl propionate.Chain ester volume shared in nonaqueous solvents total amount Usually more than 5%, preferably more than 8%, more preferably more than 15%, and usually below 50%, preferably below 35%, More preferably below 30%, further preferably below 25%.
As the example of other preferred " other nonaqueous solvents in addition to the carbonic ester with halogen atom ", can enumerate It accounts for more than 60 volume % of solvent total amount and is selected from ethylene carbonate, propylene carbonate, butylene carbonate, gamma-butyrolacton and γ-penta The mixed solvent of a kind of organic solvent in lactone or two or more organic solvent in above-mentioned organic solvent.This kind of mixing The preferred flash-point of solvent at 50 DEG C or more, wherein, particularly preferably at 70 DEG C or more.Using the nonaqueous electrolytic solution 1 of the solvent in high temperature It is not easy to occur evaporation and the liquid leakage of solvent during lower use.Wherein, when the total amount for using ethylene carbonate and gamma-butyrolacton Shared ratio is more than 80 volume %, is preferably more than 90 volume % in nonaqueous solvents total amount, and ethylene carbonate and γ- The volume ratio of butyrolactone is 5:95~45:It is 80 during 55 solvent or when using ethylene carbonate and propylene carbonate total amount More than volume %, it is preferably more than 90 volume %, and the volume ratio of ethylene carbonate and propylene carbonate is 30:70~80:20 Solvent when, in general, the well balanced of cycle characteristics and discharge load characteristic etc. can be obtained.
<1-3. mono-fluor phosphates, difluorophosphoric acid salt>
The nonaqueous electrolytic solution 1 of the present invention contains mono-fluor phosphate and/or difluorophosphoric acid salt as its essential component.In this hair Bright middle " mono-fluor phosphate and/or the difluorophosphoric acid salt " used is as long as by single fluorophosphoric acid radical ion and/or difluoro phosphorus of 1 or more Acid ion and cation are formed, its species are not particularly limited, since the nonaqueous electrolytic solution being finally made must be It can be used as the electrolyte of non-aqueous electrolyte secondary battery, thus need to make choice accordingly.
As a result, the present invention in mono-fluor phosphate, difluorophosphoric acid salt be preferably 1 or more single fluorophosphoric acid radical ion, two Fluorophosphoric acid radical ion and in the periodic table of elements the 1st race, the 2nd race and the 13rd race a kind or more metal ion (it is following, suitably Referred to as " special metal ") formed salt or be with season formed salt.Mono-fluor phosphate and/or difluorophosphoric acid salt can make With a kind, can also be applied in combination it is arbitrary two or more.
<The mono- fluorophosphoric acid metal salts of 1-3-1., difluorophosphoric acid metal salt>
First, for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention be single fluorophosphoric acid radical ion, difluorophosphoric acid root from (following, also they are referred to as " single fluorophosphoric acid metal salt ", " difluorophosphoric acid metal to the salt that son is formed with special metal ion respectively Salt ") situation illustrate.
In the special metal for single fluorophosphoric acid metal salt of the present invention, difluorophosphoric acid metal salt, as period of element The specific example of 1st race's metal of table, can enumerate lithium, sodium, potassium, caesium etc..Wherein, preferably lithium or sodium, particularly preferred lithium.
As the specific example of group II metal in the periodic table of elements, magnesium, calcium, strontium, barium etc. can be enumerated.Wherein, preferably magnesium or Calcium, particularly preferred magnesium.
As the specific example of the 13rd race's metal in the periodic table of elements, aluminium, gallium, indium, thallium etc. can be enumerated.Wherein, preferred aluminium Or gallium, particularly preferred aluminium.
These specific gold possessed by single fluorophosphoric acid metal salt, difluorophosphoric acid metal salt for every 1 molecule present invention There is no limit can be only 1 atom, or more than 2 atoms to the atomicity of category.
Contain 2 atom more than special metals in single fluorophosphoric acid metal salt of every 1 molecule present invention, difluorophosphoric acid metal salt When, the species of these special metal atoms can be mutually the same, can also be different.It can in addition contain have 1 or 2 except Metallic atom beyond special metal.
As single fluorophosphoric acid metal salt, the specific example of difluorophosphoric acid metal salt, Li can be enumerated2PO3F、Na2PO3F、 MgPO3F、CaPO3F、Al2(PO3F)3、Ga2(PO3F)3、LiPO2F2、NaPO2F2、Mg(PO2F2)2、Ca(PO2F2)2、Al (PO2F2)3、Ga(PO2F2)3Deng.Wherein, preferably Li2PO3F、LiPO2F2、NaPO2F2、Mg(PO2F2)2Deng.
<The mono- fluorophosphoric acid quaternary salts of 1-3-2., difluorophosphoric acid quaternary salt>
Then, it is single fluorophosphoric acid radical ion, difluorophosphoric acid for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention 1~6 The salt (following, also they are referred to as " single fluorophosphoric acid quaternary salt ", " difluorophosphoric acid quaternary salt " respectively) that radical ion is formed with season Situation illustrates.
For the present invention 1~6 in single fluorophosphoric acid quaternary salt, difluorophosphoric acid quaternary salt season be usually cation, tool For body, the cation represented with the following general formula (3) can be enumerated.
[chemical formula 3]
In above-mentioned general formula (3), R1~R4Alkyl is represented independently.For alkyl species there is no limit.I.e., it is possible to It is aliphatic alkyl or aromatic hydrocarbyl, can also be the alkyl that aliphatic alkyl is bonded with aromatic hydrocarbyl. It can be chain or ring-type when it is aliphatic alkyl, can also be chain and the structure that annular bonding forms. Can be straight-chain or branched when it is chain alkyl.Furthermore, it is possible to it is saturated hydrocarbyl, it is possible to have no Saturated bond.
As R1~R4Alkyl specific example, alkyl, cycloalkyl, aryl, aralkyl etc. can be enumerated.
As the specific example of alkyl, it can be mentioned, for example：Methyl, ethyl, 1- propyl, 1- Methylethyls, 1- butyl, 1- first Base propyl, 2- methyl-propyls, 1,1- dimethyl ethyls etc..
Wherein, preferably methyl, ethyl, 1- propyl, 1- butyl etc..
As the specific example of cycloalkyl, it can be mentioned, for example：Cyclopenta, 2- methylcyclopentyls, 3- methylcyclopentyls, 2,2- Dimethylcyclopentyl, 2,3- dimethylcyclopentyls, 2,4- dimethylcyclopentyls, 2,5- dimethylcyclopentyls, 3,3- diformazan basic rings Amyl, 3,4- dimethylcyclopentyls, 2- ethylcyclopentyls, 3- ethylcyclopentyls, cyclohexyl, 2- methylcyclohexyls, 3- methyl rings Hexyl, 4- methylcyclohexyls, 2,2- Dimethylcyclohexyls, 2,3- Dimethylcyclohexyls, 2,4- Dimethylcyclohexyls, 2,5- diformazans Butylcyclohexyl, 2,6- Dimethylcyclohexyls, 3,4- Dimethylcyclohexyls, 3,5- Dimethylcyclohexyls, 2- ethylcyclohexyls, 3- second Butylcyclohexyl, 4- ethylcyclohexyls, bicyclic [3,2,1] octyl- 1- bases, bicyclic [3,2,1] octyl- 2- bases etc..
Wherein, preferably cyclopenta, 2- methylcyclopentyls, 3- methylcyclopentyls, cyclohexyl, 2- methylcyclohexyls, 3- methyl Cyclohexyl, 4- methylcyclohexyls etc..
As the specific example of aryl, it can be mentioned, for example：Phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,3- 3,5-dimethylphenyls etc..
Wherein, preferred phenyl.
As the specific example of aralkyl, it can be mentioned, for example：Phenyl methyl, 1- phenylethyls, 2- phenylethyls, diphenyl Methyl, trityl group etc..
Wherein, preferably phenyl methyl, 2- phenylethyls.
R1~R4Alkyl can also be substituted by the substituent group of 1 or 2 or more.For the species of substituent group, as long as unknown In the range of the aobvious effect for destroying the present invention 1 there is no limit, as the example of substituent group, can enumerate halogen atom, hydroxyl, amino, Nitro, cyano, carboxyl, ether, aldehyde radical etc..It should be noted that work as R1~R4Alkyl when there is the substituent group of 2 or more, this A little substituent groups can be mutually the same, can also be different.
To R more than any two1~R4When alkyl is compared, they can be mutually the same, can also be different. Work as R1~R4Alkyl have substituent group when, the substituted hydrocarbon radical including these substituent groups can be mutually the same, can also mutually not It is identical.In addition, R1~R4Alkyl in arbitrary 2 or more can also be mutually bonded and form cyclic structure.
R1~R4Alkyl carbon number usually more than 1, and its upper limit usually below 20, preferably below 10, More preferably below 5.When carbon number is excessive, the molal quantity of unit mass is reduced, and has the tendency of that various effects is caused to reduce. It should be noted that work as R1~R4Alkyl have substituent group when, the carbon number of the substituted hydrocarbon radical including these substituent groups Meet above range.
In addition, in above-mentioned general formula (3), the atom belonging in the 15th race of Q representative elements periodic table.Wherein, preferably nitrogen is former Son or phosphorus atoms.
So, the preferred embodiment as the season represented by above-mentioned general formula (3) can enumerate aliphatic chain quaternary salt Class, aliphatic cyclic ammonium, aliphatic Huan Zhuan Phosphonium, nitrogen heterocyclic ring aromatic series cation etc..
As aliphatic chain quaternary salt class, particularly preferred tetra-allkylammonium, four alkane base Phosphonium etc..
As the specific example of tetra-allkylammonium, it can be mentioned, for example：Tetramethyl-ammonium, ethyl trimethyl ammonium, diethyl-dimethyl Ammonium, triethylmethylammonium, tetraethyl ammonium, tetra-n-butyl ammonium etc..
As the specific example of Si Wan Ji Phosphonium, it can be mentioned, for example：Tetramethyl phosphonium, Yi base San Jia Ji Phosphonium, diethyl-dimethyl Phosphonium, triethyl group Jia Ji Phosphonium, tetraethylphosphonium, Si Zheng Ding Ji Phosphonium etc..
As aliphatic cyclic ammonium, particularly preferred pyrrolidines, morpholine class, imidazoles, tetrahydropyrimidine class, piperazine Piperazine class, piperidines etc..
As the specific example of pyrrolidines, it can be mentioned, for example：N, N- dimethyl pyrrolidine, N- ethyl-N-methyls Pyrrolidines, N, N- diethyl pyrrolidines etc..
As the specific example of morpholine class, it can be mentioned, for example：N, N- thebaine, N- ethyl-N-methylmorpholiniums , N, N- diethyl morpholines etc..
As the specific example of imidazoles, it can be mentioned, for example：N, N '-dimethyl imidazoles, N- ethyls-N '-methyl miaow Azoles, N, N '-diethyl imidazolium, 1,2,3- tri-methylimidazoliums etc..
As the specific example of tetrahydropyrimidine class, it can be mentioned, for example：N, N '-dimethyl tetrahydropyrimidine, N- ethyls- N '-methyl tetrahydropyrimidine, N, N '-diethyl tetrahydropyrimidine, 1,2,3- trimethyl tetrahydropyrimidines etc..
As the specific example of piperazines, it can be mentioned, for example：N, N, N ', N '-tetramethyl piperazine, N- ethyls-N, N ', N '-tri methyl piperazine, N, N- diethyl-N ', N '-dimethyl piperazine, N, N, N '-triethyl group-N '-methyl piperazine, N, N, N ', N '-tetraethyl piperazine etc..
As the specific example of piperidines, it can be mentioned, for example：N, N- lupetidine, N- ethyl-N-methyl piperidines , N, N- diethyl phenylpiperidines etc..
As nitrogen heterocyclic ring aromatic series cation, particularly preferred pyridines, imidazoles etc..
As the specific example of pyridines, it can be mentioned, for example：N- picolines, N- ethylpyridines, 1,2- diformazans Yl pyrimidines, 1,3- dimethyl pyrimidines, 1,4- dimethyl pyrimidines, 1- Ethyl-2-Methyl pyrimidines etc..
As the specific example of imidazoles, it can be mentioned, for example：N, N '-dimethyl imidazoles, N- ethyls-N '-methyl miaow Azoles, N, N '-diethyl imidazolium, 1,2,3- tri-methylimidazoliums etc..
That is, the salt that the above-mentioned Ji Yudan fluorophosphoric acid radical ion enumerated and/or difluorophosphoric acid radical ion are formed is the present invention In single fluorophosphoric acid quaternary salt, the preferred specific example of difluorophosphoric acid quaternary salt.
<1-3-3. contents, detection (source contained), technical scope etc.>
The present invention nonaqueous electrolytic solution in, can be used only a kind of mono-fluor phosphate or difluorophosphoric acid salt, can also with appoint Meaning combination and ratio are applied in combination mono-fluor phosphate and/or difluorophosphoric acid salt of more than two kinds, but from non-aqueous electrolyte secondary battery The angle that can effectively work is set out, and it is preferable to use a kind of mono-fluor phosphate or difluorophosphoric acid salt.
In addition, for the molecular weight of mono-fluor phosphate, difluorophosphoric acid salt, there is no restriction, and the effect of the present invention is destroyed in unobvious Can be arbitrary molecular weight in the range of fruit, but usually more than 100.In addition, being not particularly limited to upper molecular weight limit, but reflect In the reactivity of this reaction, it is more highly preferred to usually below 1000, when reaching below 500 from point of view of practicability.
The salt of single fluorophosphoric acid, the salt of difluorophosphoric acid are usually using a kind, but when nonaqueous electrolytic solution is made, preferably by 2 kinds with On salt be used in mixed way, at this point it is possible to which mono-fluor phosphate of more than two kinds, difluorophosphoric acid salt are used in mixed way.
In nonaqueous electrolytic solution, the total amount of mono-fluor phosphate and difluorophosphoric acid salt ratio shared in nonaqueous electrolytic solution total amount Example is preferably at more than 10ppm (more than 0.001 mass %), more preferably more than 0.01 mass %, particularly preferably in 0.05 matter Measure more than %, further preferably more than 0.1 mass %.In addition, the upper limit of its total amount preferably below 5 mass %, more preferably Below 4 mass %, further preferably below 3 mass %.When the concentration of mono-fluor phosphate and difluorophosphoric acid salt is too low, have When be difficult obtain discharge load characteristic improvement, on the other hand, when the concentration is too high, sometimes result in efficiency for charge-discharge drop It is low.
When mono-fluor phosphate and difluorophosphoric acid salt are actually used in as nonaqueous electrolytic solution the system of non-aqueous electrolyte secondary battery When standby, even if dismantling the battery and extracting nonaqueous electrolytic solution again, mono-fluor phosphate therein and two in most cases The content of fluorophosphate can significantly reduce.Therefore, even if only being detected in the nonaqueous electrolytic solution extracted from battery few At least one kind of in the mono-fluor phosphate of amount and/or difluorophosphoric acid salt, which is regarded as belonging to the present invention.In addition, when single fluorine When phosphate and difluorophosphoric acid salt are actually used in the preparation of non-aqueous electrolyte secondary battery as nonaqueous electrolytic solution, even if dismantling In the case of mono-fluor phosphate and/or difluorophosphoric acid salt are not contained in the nonaqueous electrolytic solution extracted again after the battery, greatly Mostly also it can detect single fluorophosphoric acid on the anode, cathode or partition plate of other building blocks as non-aqueous electrolyte secondary battery The presence of salt and/or difluorophosphoric acid salt.Therefore, even if being detected at least one kind of building block in anode, cathode, partition plate At least one kind of in mono-fluor phosphate and/or difluorophosphoric acid salt, which is regarded as belonging to the present invention.
In addition, for making mono-fluor phosphate and/or difluorophosphoric acid salt is not only contained in nonaqueous electrolytic solution while also includes Situation in anode, cathode, partition plate at least one kind of building block is also regarded as belonging to the present invention.
On the other hand, the anode of non-aqueous electrolyte secondary battery is interior made of can also making or positive electrode surface contains in advance Mono-fluor phosphate and/or difluorophosphoric acid salt.At this point, it can expect the portion of the mono-fluor phosphate contained in advance and/or difluorophosphoric acid salt Divide or be all dissolved in nonaqueous electrolytic solution and function, which is also regarded as belonging to the present invention.
For making in anode or the positive electrode surface method containing mono-fluor phosphate and/or difluorophosphoric acid salt in advance, spy is had no Different limitation, as specific example, can enumerate it is as described later, make mono-fluor phosphate and/or difluorophosphoric acid salt when anode is made The method being dissolved in the slurry of preparation；Or mono-fluor phosphate and/or difluorophosphoric acid salt is made to be dissolved in arbitrary nonaqueous solvents in advance In, after solution made from recycling is to manufactured anode is coated or is impregnated with, solvent used in dry, removing, from And make method that in anode or positive electrode surface contains mono-fluor phosphate and/or difluorophosphoric acid salt etc..
In addition, when actually preparing non-aqueous electrolyte secondary battery, can also by comprising at least one kind of mono-fluor phosphate and/ Or the nonaqueous electrolytic solution of difluorophosphoric acid salt makes in anode or positive electrode surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.It is making During standby non-aqueous electrolyte secondary battery, since nonaqueous electrolytic solution to be made is impregnated into anode, in most cases in anode Interior or positive electrode surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Thus, for can be from being recovered to when dismantling the battery Anode at least detect the situation of mono-fluor phosphate and/or difluorophosphoric acid salt, be considered as belonging to the present invention.
Further, it is also possible to the cathode of non-aqueous electrolyte secondary battery made of making is interior or negative terminal surface is in advance containing single fluorine phosphorus Hydrochlorate and difluorophosphoric acid salt.At this point, it can expect the part or all of molten of the mono-fluor phosphate contained in advance and/or difluorophosphoric acid salt Solution functions in nonaqueous electrolytic solution, which is considered as belonging to the present invention.For making in cathode or negative terminal surface is advance Method containing mono-fluor phosphate and difluorophosphoric acid salt, have no it is specifically limited, as specific example, can enumerate it is as described later, Make the method or make single fluorophosphoric acid in advance that mono-fluor phosphate and difluorophosphoric acid salt are dissolved in the slurry of preparation when cathode is made Salt and difluorophosphoric acid salt are dissolved in arbitrary nonaqueous solvents, solution made from recycling manufactured cathode is coated or After being impregnated with, solvent used in dry, removing, so that cathode is interior or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid salt Method etc..
It, can also be from including at least one kind of mono-fluor phosphate and two in addition, when actually preparing non-aqueous electrolyte secondary battery The nonaqueous electrolytic solution of fluorophosphate makes in cathode or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid salt.Preparing secondary electricity Chi Shi, since nonaqueous electrolytic solution to be made is impregnated into cathode, in most cases in cathode or negative terminal surface can contain Mono-fluor phosphate and difluorophosphoric acid salt.Thus, for can at least detect list from the cathode being recovered to when dismantling the battery The situation of fluorophosphate and difluorophosphoric acid salt is considered as belonging to the present invention.
Further, it is also possible to the partition plate of non-aqueous electrolyte secondary battery made of making is interior or baffle surface is in advance containing single fluorine phosphorus Hydrochlorate and/or difluorophosphoric acid salt.At this point, it can expect the part or all of molten of the mono-fluor phosphate contained in advance and difluorophosphoric acid salt Solution functions in nonaqueous electrolytic solution, which is considered as belonging to the present invention.For making in partition plate or baffle surface is advance Method containing mono-fluor phosphate and/or difluorophosphoric acid salt, has no specifically limited, as specific example, can enumerate：Be made every Make the method or make mono-fluor phosphate and the dissolving of difluorophosphoric acid salt in office in advance that mono-fluor phosphate and difluorophosphoric acid salt mix during plate In meaning nonaqueous solvents, and partition plate is coated or is impregnated with using solution obtained before non-aqueous electrolyte secondary battery is prepared Afterwards, it is dry, remove solvent so that in partition plate or method that baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.
It, can also be from including mono-fluor phosphate and/or difluoro phosphorus in addition, when actually preparing non-aqueous electrolyte secondary battery The nonaqueous electrolytic solution of hydrochlorate makes in partition plate or baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.Preparing non-water power When solving electrolitc secondary cell, since nonaqueous electrolytic solution to be made is impregnated into partition plate, in most cases in partition plate or partition plate Surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Therefore, for can be from the partition plate of recycling at least when dismantling the battery It detects the situation of mono-fluor phosphate and difluorophosphoric acid salt, is considered as belonging to the present invention.
It is considered that：When making in nonaqueous electrolytic solution containing above-mentioned mono-fluor phosphate and difluorophosphoric acid salt and " there is halogen atom Carbonic ester " when, can be improved using the High temperature storage characteristic of the non-aqueous electrolyte secondary battery of the nonaqueous electrolytic solution.It closes It is still not clear in the details of this factor, and the scope of the present invention is from the limitation of this factor, but can consider its tool There are following mechanism.That is, contained mono-fluor phosphate and/or difluorophosphoric acid salt and the " carbonic acid with halogen atom in nonaqueous electrolytic solution Ester " can form good protection by film layer on the surface of negative electrode active material, thus can inhibit side reaction by reacting, And inhibit the deterioration generated due to High temperature storage.In addition, by making to exist simultaneously mono-fluor phosphate and/or difluoro phosphorus in electrolyte Hydrochlorate and " carbonic ester with halogen atom " can improve the characteristic of protection envelope by certain form.
<1-4. additive>
In the range of unobvious destroy the effect of the present invention 1, the nonaqueous electrolytic solution of the present invention 1 can also contain various add Add agent.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that add Agent is added to can be used alone, it can also in any combination and two or more is applied in combination in ratio.
As the example of additive, overcharge preventing agent can be enumerated, for improving the capacity maintenance characteristics after High temperature storage And auxiliary agent of cycle characteristics etc..In these additives, as improving the capacity maintenance characteristics after High temperature storage and cycling The auxiliary agent of characteristic is preferably added to the carbonic ester with unsaturated bond (hereinafter sometimes referred to simply as " specific carbonic ester ").In the following, respectively Specific carbonic ester and other additives are illustrated.
<The specific carbonic esters of 1-4-1.>
Specific carbonic ester is the carbonic ester for having unsaturated bond.Specific carbonic ester optionally has halogen atom.
It is not particularly limited for the molecular weight of specific carbonic ester, in the range of unobvious destroy the effect of the present invention 1 Can be arbitrary molecular weight, but usually more than 50, preferably more than 80, and usually below 250, preferably below 150.Point When son amount is excessive, dissolubility of the specific carbonic ester in nonaqueous electrolytic solution reduces, and is difficult fully to show effect sometimes.
In addition, being also not particularly limited for the manufacturing method of specific carbonic ester, well known method can arbitrarily be selected to make It makes.
In addition, the present invention 1 nonaqueous electrolytic solution in, can individually contain arbitrary a kind of specific carbonic ester, can also with times Meaning combination and ratio contain two or more simultaneously.
In addition, for specific carbonic ester compared with the present invention 1 nonaqueous electrolytic solution combined amount there is no limit, in unobvious Can be arbitrary combined amount in the range of the effect of the destruction present invention 1, but compared with the nonaqueous electrolytic solution of the present invention 1, it is contained The ideal concentration of specific carbonic ester is usually more than 0.01 mass %, is preferably more than 0.1 mass %, more preferably 0.3 matter Measure more than %, and usually below 70 mass %, preferably below 50 mass %, more preferably below 40 mass %.
When less than the lower limit of above range, when the nonaqueous electrolytic solution of the present invention 1 is used for non-aqueous electrolyte secondary battery, Sometimes the non-aqueous electrolyte secondary battery is difficult to show sufficient cycle characteristics improvement effect.In addition, when specific carbonic ester When ratio is excessive, when the nonaqueous electrolytic solution of the present invention 1 is used for non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery High temperature storage characteristic and trickle charge characteristic have the tendency of reduction, particularly, it is sometimes gas generated to increase, capacity keep Rate declines.
As the specific carbonic ester that the present invention 1 is related to, as long as with carbon-to-carbons insatiable hungers such as carbon-to-carbon double bond, carbon-carbon triple bonds Carbonic ester with key can use arbitrary unsaturated carbon acid ester then without other limitations.It is pointed out that with aromatic rings Carbonic ester fall within the carbonic ester with unsaturated bond.
As the example of unsaturated carbon acid ester, vinylene carbonate derivative species can be enumerated, by with aromatic rings or carbon-to-carbon Ethylene carbonate derivative class, carbonic acid phenyl ester class, ethylene carbonate esters, the allyl esters of the substituent group substitution of unsaturated bond Deng.
As the specific example of vinylene carbonate derivative species, vinylene carbonate, methyl carbonic acid Asia ethylene can be enumerated Ester, 4,5- dimethyl vinylene carbonate, phenyl-carbonic acid vinylene, 4,5- diphenyl vinylene carbonate, catechol carbonic acid Ester etc..
As the specific of the ethylene carbonate derivative class substituted by the substituent group with aromatic rings or carbon-to-carbon unsaturated bond Example can enumerate vinylethylene carbonate, 4,5- divinyl ethylene carbonate, phenyl-carbonic acid ethyl, 4,5- diphenyl Ethylene carbonate etc..
As the specific example of carbonic acid phenyl ester class, diphenyl carbonate, carbonic acid ethyl phenyl ester, methyl phenyl can be enumerated Ester, carbonic acid tert-butyl benzene base ester etc..
As the specific example of ethylene carbonate esters, divinyl carbonate, methyl vinyl esters etc. can be enumerated.
As the specific example of allyl esters, diallyl carbonate, methyl allyl ester etc. can be enumerated.
In above-mentioned specific carbonic ester, preferably vinylene carbonate derivative species, by unsaturated with aromatic rings or carbon-to-carbon The ethylene derivative species of the substituent group substitution of key, particularly vinylene carbonate, 4,5- diphenyl vinylene carbonate, 4,5- bis- Methylvinylene carbonate, vinylethylene carbonate protect envelope due to that can form stable interface, thus more preferably make With.
<The other additives of 1-4-2.>
In the following, it is illustrated for other additives beyond specific carbonic ester.As other beyond specific carbonic ester Additive can enumerate overcharge preventing agent, for improving auxiliary agent of the capacity maintenance characteristics after High temperature storage and cycle characteristics etc..
<1-4-2-1. overcharge preventing agent>
As the specific example of overcharge preventing agent, it can be mentioned, for example：The toluene derivatives such as toluene, dimethylbenzene；Biphenyl, 2- Methyl biphenyl, 3- methyl biphenyls, 4- methyl biphenyls etc. are non-substituted or by alkyl-substituted biphenyl derivatives；Ortho-terphenyl, three Biphenyl, para-terpheny etc. are non-substituted or by alkyl-substituted terphenyl derivatives；It is non-substituted or spread out by alkyl-substituted terphenyl The part hydride of biology；The cycloalkyl benzene derivative such as cyclopenta benzene, cyclohexyl benzene；Isopropylbenzene, 1,3- diisopropyl benzenes, 1,4- Diisopropyl benzene etc. has the benzene derivative of tertiary carbon of the Direct Bonding on phenyl ring；Tert-butyl benzene, tert-amyl benzene, tertiary hexyl Benzene etc. has the benzene derivative of quaternary carbon of the Direct Bonding on phenyl ring；Diphenyl ether, dibenzofurans etc. have oxygen atom The aromatic compounds such as aromatic compound.
In addition, the specific example as other overcharge preventing agents, can also enumerate for example：Fluorobenzene, toluene fluoride, trifluoro Toluene, 2- fluorine biphenyl, adjacent cyclohexyl fluorobenzene, the partially fluorinated object to the above-mentioned aromatic compound such as cyclohexyl fluorobenzene；2,4- bis- Fluorine-containing benzyl ether compounds such as fluoroanisole, 2,5- difluoroanisoles, 1,6- difluoroanisoles etc..
Wherein, these overcharge preventing agents can be used alone a kind, can also use two or more simultaneously in any combination.Separately Outside, simultaneously in use, can be combined using same category of compound is belonged in above-mentioned example, can also combine in any combination Use different classes of compound.
As specific example when being applied in combination different classes of compound, can enumerate：Toluene derivative and biphenyl derive Object；Toluene derivative and terphenyl derivatives；The part hydride of toluene derivative and terphenyl derivatives；Toluene derivative and Cycloalkyl benzene derivative；Toluene derivative and the benzene derivative with tertiary carbon of the Direct Bonding on phenyl ring；Toluene derives Object and the benzene derivative with quaternary carbon of the Direct Bonding on phenyl ring；Toluene derivative and the aromatic series with oxygen atom Close object；The partially fluorinated object of toluene derivative and aromatic compound；Toluene derivative and fluorine-containing benzyl ether compounds；Biphenyl spreads out Biology and terphenyl derivatives；The part hydride of biphenyl derivatives and terphenyl derivatives；Biphenyl derivatives and cycloalkyl benzene Derivative；Biphenyl derivatives and the benzene derivative with tertiary carbon of the Direct Bonding on phenyl ring；Biphenyl derivatives and have The benzene derivative of quaternary carbon of the Direct Bonding on phenyl ring；Biphenyl derivatives and the aromatic compound with oxygen atom；Connection Benzene derivative and the partially fluorinated object of aromatic compound；Biphenyl derivatives and fluorine-containing benzyl ether compounds；Terphenyl derivatives With the part hydride of terphenyl derivatives；Terphenyl derivatives and cycloalkyl benzene derivative；Terphenyl derivatives and with straight Connect the benzene derivative for being bonded in the tertiary carbon on phenyl ring；Terphenyl derivatives and with quaternary carbon of the Direct Bonding on phenyl ring Benzene derivative；Terphenyl derivatives and the aromatic compound with oxygen atom；Terphenyl derivatives and aromatic compound The partially fluorinated object of object；Terphenyl derivatives and fluorine-containing benzyl ether compounds；The part hydride and cycloalkanes of terphenyl derivatives Base benzene derivative；The part hydride of terphenyl derivatives and the alkyl benzenesulfonamide derivative with tertiary carbon of the Direct Bonding on phenyl ring Object；The part hydride of terphenyl derivatives and the benzene derivative with quaternary carbon of the Direct Bonding on phenyl ring；Terphenyl The part hydride of derivative and the aromatic compound with oxygen atom；The part hydride and aromatic series of terphenyl derivatives The partially fluorinated object of compound；The part hydride and fluorine-containing benzyl ether compounds of terphenyl derivatives；Cycloalkyl benzene derivative With the benzene derivative of the tertiary carbon with Direct Bonding on phenyl ring；Cycloalkyl benzene derivative and with Direct Bonding in phenyl ring On quaternary carbon benzene derivative；Cycloalkyl benzene derivative and the aromatic compound with oxygen atom；Cycloalkyl benzenesulfonamide derivative The partially fluorinated object of object and aromatic compound；Cycloalkyl benzene derivative and fluorine-containing benzyl ether compounds；Exist with Direct Bonding The benzene derivative of tertiary carbon on phenyl ring and the benzene derivative with quaternary carbon of the Direct Bonding on phenyl ring；With direct It is bonded in the benzene derivative of the tertiary carbon on phenyl ring and the aromatic compound with oxygen atom；With Direct Bonding in phenyl ring On the benzene derivative of tertiary carbon and the partially fluorinated object of aromatic compound；Tertiary carbon with Direct Bonding on phenyl ring Benzene derivative and fluorine-containing benzyl ether compounds；The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and with The aromatic compound of oxygen atom；The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and aromatic compound Partially fluorinated object；The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and fluorine-containing benzyl ether compounds；With oxygen The aromatic compound of atom and the partially fluorinated object of aromatic compound；Aromatic compound with oxygen atom and containing fluorobenzene Methyl ether compound；The partially fluorinated object and fluorine-containing benzyl ether compounds of aromatic compound.
As the specific example of said combination, can be listed below：Combination, biphenyl and the meta-terphenyl of biphenyl and ortho-terphenyl Combination, the combination of part hydride, the combination of biphenyl and isopropylbenzene, biphenyl and the cyclopenta benzene of biphenyl and terphenyl derivatives Combination, the combination of biphenyl and cyclohexyl benzene, the combination of biphenyl and tert-butyl benzene, the combination of biphenyl and tert-amyl benzene, biphenyl and The combination of diphenyl ether, the combination of biphenyl and dibenzofurans, the combination of biphenyl and fluorobenzene, the combination of biphenyl and benzotrifluoride, The combination of biphenyl and 2- fluorine biphenyl, combination, biphenyl and the combination to fluorine cyclohexyl benzene of biphenyl and adjacent fluorine cyclohexyl benzene, biphenyl and The combination of 2,4 difluorobenzene methyl ether；
The combination of the part hydride of ortho-terphenyl and terphenyl derivatives, the combining of ortho-terphenyl and isopropylbenzene, neighbour three The combination of biphenyl and cyclopenta benzene, the combination of ortho-terphenyl and cyclohexyl benzene, the combining of ortho-terphenyl and tert-butyl benzene, neighbour three The combination of benzene and tert-amyl benzene, the combination of ortho-terphenyl and diphenyl ether, the combining of ortho-terphenyl and dibenzofurans, neighbour three The combination of benzene and fluorobenzene, the combination of ortho-terphenyl and benzotrifluoride, combination, ortho-terphenyl and the neighbour of ortho-terphenyl and 2- fluorine biphenyl The combination of the combination of fluorine cyclohexyl benzene, ortho-terphenyl and the combination to fluorine cyclohexyl benzene, ortho-terphenyl and 2,4 difluorobenzene methyl ether；
The combination of the part hydride of meta-terphenyl and terphenyl derivatives, the combination of meta-terphenyl and isopropylbenzene, three The combination of biphenyl and cyclopenta benzene, the combination of meta-terphenyl and cyclohexyl benzene, the combination of meta-terphenyl and tert-butyl benzene, three The combination of benzene and tert-amyl benzene, the combination of meta-terphenyl and diphenyl ether, the combination of meta-terphenyl and dibenzofurans, three The combination of benzene and fluorobenzene, the combination of meta-terphenyl and benzotrifluoride, combination, meta-terphenyl and the neighbour of meta-terphenyl and 2- fluorine biphenyl The combination of the combination of fluorine cyclohexyl benzene, meta-terphenyl and the combination to fluorine cyclohexyl benzene, meta-terphenyl and 2,4 difluorobenzene methyl ether；
The combination of part hydride and isopropylbenzene, the part hydride of terphenyl derivatives and the ring penta of terphenyl derivatives The combination of base benzene, the combination of the part hydride of terphenyl derivatives and cyclohexyl benzene, the part hydride of terphenyl derivatives The combination of the part hydride and tert-amyl benzene of combination, terphenyl derivatives with tert-butyl benzene, the part of terphenyl derivatives The combination of hydride and diphenyl ether, the combination of the part hydride of terphenyl derivatives and dibenzofurans, terphenyl derive The combination of part hydride and fluorobenzene of object, the combination of the part hydride of terphenyl derivatives and benzotrifluoride, terphenyl spread out The part hydride of biology and the group of the combination of 2- fluorine biphenyl, the part hydride of terphenyl derivatives and adjacent fluorine cyclohexyl benzene It closes, the part hydride of terphenyl derivatives and the part hydride and 2 to the combination of fluorine cyclohexyl benzene, terphenyl derivatives, The combination of 4- difluoroanisoles；
The combination of isopropylbenzene and cyclopenta benzene, the combination of isopropylbenzene and cyclohexyl benzene, the combination of isopropylbenzene and tert-butyl benzene, The combination of isopropylbenzene and tert-amyl benzene, the combination of isopropylbenzene and diphenyl ether, combination, the isopropylbenzene of isopropylbenzene and dibenzofurans The combination of combination, isopropylbenzene and benzotrifluoride, the combination of isopropylbenzene and 2- fluorine biphenyl, isopropylbenzene and adjacent fluorine cyclohexyl with fluorobenzene The combination of the combination of benzene, isopropylbenzene and the combination to fluorine cyclohexyl benzene, isopropylbenzene and 2,4 difluorobenzene methyl ether；
The combination of cyclohexyl benzene and tert-butyl benzene, the combination of cyclohexyl benzene and tert-amyl benzene, cyclohexyl benzene and diphenyl ether Combination, the combination of cyclohexyl benzene and dibenzofurans, the combination of cyclohexyl benzene and fluorobenzene, the group of cyclohexyl benzene and benzotrifluoride Close, the combination of cyclohexyl benzene and 2- fluorine biphenyl, the combination of cyclohexyl benzene and adjacent fluorine cyclohexyl benzene, cyclohexyl benzene and to fluorine cyclohexyl The combination of the combination of benzene, cyclohexyl benzene and 2,4 difluorobenzene methyl ether；
The combination of tert-butyl benzene and tert-amyl benzene, the combination of tert-butyl benzene and diphenyl ether, tert-butyl benzene and dibenzo furan The group of the combination of combination, tert-butyl benzene and fluorobenzene, the combination of tert-butyl benzene and benzotrifluoride, tert-butyl benzene and the 2- fluorine biphenyl muttered Conjunction, combination, tert-butyl benzene and the combination to fluorine cyclohexyl benzene of tert-butyl benzene and adjacent fluorine cyclohexyl benzene, tert-butyl benzene and 2,4- bis- The combination of fluoroanisole；
The combination of tert-amyl benzene and diphenyl ether, the combination of tert-amyl benzene and dibenzofurans, tert-amyl benzene and fluorobenzene Combination, tert-amyl benzene and the combination of benzotrifluoride, the combination of tert-amyl benzene and 2- fluorine biphenyl, tert-amyl benzene and adjacent fluorine cyclohexyl benzene Combination, the combination of tert-amyl benzene and the combination to fluorine cyclohexyl benzene, tert-amyl benzene and 2,4 difluorobenzene methyl ether；
The combination of diphenyl ether and dibenzofurans, the combination of diphenyl ether and fluorobenzene, diphenyl ether and benzotrifluoride Combination, the combination of diphenyl ether and 2- fluorine biphenyl, the combination of diphenyl ether and adjacent fluorine cyclohexyl benzene, diphenyl ether and to fluorine hexamethylene The combination of base benzene, the combination of diphenyl ether and 2,4 difluorobenzene methyl ether, the combination of dibenzofurans and fluorobenzene, dibenzofurans and The combination of benzotrifluoride, the combination of dibenzofurans and 2- fluorine biphenyl, combination, the hexichol of dibenzofurans and adjacent fluorine cyclohexyl benzene And the combination of furans and the combination to fluorine cyclohexyl benzene, dibenzofurans and 2,4 difluorobenzene methyl ether；
The combination of fluorobenzene and benzotrifluoride, the combination of fluorobenzene and 2- fluorine biphenyl, combination, the fluorine of fluorobenzene and adjacent fluorine cyclohexyl benzene Benzene and the combination of the combination to fluorine cyclohexyl benzene, fluorobenzene and 2,4 difluorobenzene methyl ether；
The combination of benzotrifluoride and 2- fluorine biphenyl, the combination of benzotrifluoride and adjacent fluorine cyclohexyl benzene, benzotrifluoride and to fluorine The combination of the combination of cyclohexyl benzene, benzotrifluoride and 2,4 difluorobenzene methyl ether；
Combination, 2- fluorine biphenyl and the combination to fluorine cyclohexyl benzene of 2- fluorine biphenyl and adjacent fluorine cyclohexyl benzene, 2- fluorine biphenyl and The combination of 2,4 difluorobenzene methyl ether；
Adjacent fluorine cyclohexyl benzene and to the combination of the combining of fluorine cyclohexyl benzene, adjacent fluorine cyclohexyl benzene and 2,4 difluorobenzene methyl ether, Combination to fluorine cyclohexyl benzene and 2,4- difluoroanisole, etc..
When the nonaqueous electrolytic solution 1 of the present invention contains overcharge preventing agent, the model of the effect of the present invention 1 is destroyed in unobvious In enclosing, concentration can be any concentration, but compared with nonaqueous electrolytic solution total amount, ideal concentration is usually 0.1 mass %~5 The scope of quality %.
Prevent in the nonaqueous electrolytic solution 1 for making the present invention in the range of unobvious destroy the effect of the present invention 1 containing overcharge Only agent, even if application method mistake or charging unit exception etc. can occur in additives for overcharge protection circuit non-normal working in contingency Situation and when causing overcharge, can also improve the security of non-aqueous electrolyte secondary battery, therefore preferably.
<1-4-2-2. is used to improve the auxiliary agent of the capacity maintenance characteristics after High temperature storage and cycle characteristics>
As for improving the specific example of the auxiliary agent of the capacity maintenance characteristics after High temperature storage and cycle characteristics, can enumerate Such as：The acid anhydrides of the dicarboxylic acids such as succinic acid, maleic acid, phthalic acid；Carbonic acid erythrite ester (エ リ ス リ タ ン カ ー ボ ネ ー ト), carbonic acid spiral shell-bis--dimethylene ester (ス ピ ロ-ビ ス-ジ メ チ レ ン カ ー ボ ネ ー ト) etc. is specific except being equivalent to Carbonate products beyond the carbonic ester of carbonic ester；
Sulfurous acid glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, 1,4-dimethane sulfonoxybutane, Sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, a sulphur Change tetra methylthiuram, the sulfur-containing compounds such as N, N- dimethyl methyls sulfonamide, N, N- diethyl Methanesulfomides；
1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2-Oxazolidone, 1,3- dimethyl -2- imidazoles The nitrogenous compounds such as alkanone, N- methyl succimides；
The hydrocarbon compounds such as heptane, octane, cycloheptane；
Aromatic fluorine compounds such as fluorobenzene, difluorobenzene, benzotrifluoride etc..
[2. non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery of the present invention has the nonaqueous electrolytic solution of the invention described above and can occlude and release The anode and cathode of ion and form.In addition, the non-aqueous electrolyte secondary battery of the present invention can also have other structures.
<2-1. battery structure>
For other structures in addition to cathode and nonaqueous electrolytic solution in the non-aqueous electrolyte secondary battery of the present invention, with Known non-aqueous electrolyte secondary battery is identical, usually has the perforated membrane for clipping and being saturated with the nonaqueous electrolytic solution of the present invention Anode and cathode are laminated and they are accommodated in the form in shell (packaging body) by (partition plate).Thus, for the non-of the present invention The shape of Water-Electrolyte secondary cell is not particularly limited, and can be that cylindrical shape, square, stacking shape, coin-shaped, large size etc. are any Shape.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution of the invention described above can be used.It should be noted that without departing from this hair In the range of bright main points, other nonaqueous electrolytic solutions can also be mixed into the nonaqueous electrolytic solution of the present invention.
<2-3. cathode>
In the following, it is illustrated for for the negative electrode active material of cathode.
As negative electrode active material, as long as the negative electrode active material of lithium ion can be occluded electrochemically/released, then do not have Have specifically limited.As its specific example, carbonaceous material, alloy type material, the composite oxide of metal material containing lithium can be enumerated Material etc..
<2-3-1. carbonaceous material>
As the carbonaceous material as negative electrode active material, since the carbonaceous material being selected from following (1)~(4) can obtain Initial stage irreversible capacity, high current density charge-discharge characteristic it is well balanced, thus preferably.In addition, the carbonaceous material of (1)~(4) Material can be used alone, can also in any combination and two or more is applied in combination in ratio.
(1) native graphite；
(2) heat more than once is carried out to artificial carbonaceous material and Delanium substance in the range of 400~3200 DEG C Carbonaceous material obtained from processing；
(3) negative electrode active material layer above has that different crystalline carbonaceous are formed, and/or its difference is tied by least two kinds of The carbonaceous of crystalline substance has the carbonaceous material at the interface being in contact；
(4) negative electrode active material layer is made of at least two kinds of above carbonaceous with different orientation, and/or its difference takes The carbonaceous of tropism has the carbonaceous material at the interface being in contact.
As the artificial carbonaceous material of above-mentioned (2) and the specific example of Delanium substance, native graphite, coal can be enumerated Class coke, petroleum-type coke, coal class pitch, petroleum-type pitch or to these pitches carry out oxidation processes obtained from substance, Needle coke, pitch coke and by they part be graphitized obtained from carbon material；Furnace black, acetylene black, pitch-based carbon fiber It waits thermal decomposition product, the organic matter that can be carbonized and their carbide of organic matters or is dissolved in the organic matter that can be carbonized Solution and their carbide etc. obtained from the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane.
Wherein, the specific example as the organic matter carbonized, can enumerate the coal tar from maltha to pitch The coals class heavy oil such as pitch or destructive distillation liquefaction oil；The thermal decompositions such as the direct currents class heavy oil such as atmospheric resids, decompression residual oil, crude oil, naphtha When by-product ethylene bottom oil etc. decompose class black petroleum products；And the aromatic hydrocarbon such as acenaphthylene, decacyclene, anthracene, phenanthrene；Azophenlyene or acridine etc. contain There is the heterocyclic compound of nitrogen-atoms；The heterocyclic compounds containing sulphur atom such as thiophene, di- thiophene；The polyphenyl such as biphenyl, terphenyl； Polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, their insoluble processed material, nitrogenous polyacrylonitrile, polypyrrole etc. are organic high Molecule；The organic polymers such as polythiophene, the polystyrene of sulfur-bearing；With cellulose, lignin, mannocarolose, polygalacturonic acid, Chitosan, sucrose are the natural polymers such as the polysaccharide of representative；The thermoplastic resins such as polyphenylene sulfide, polyphenylene oxide；Furfuryl alcohol resin, phenol Thermosetting resins such as urea formaldehyde, imide resin etc..
<Structure, physical property, the preparation method of 2-3-2. carbonaceous cathode>
Property on carbonaceous material, the negative electrode containing carbonaceous material and electric polarization method, collector, nonaqueous electrolyte Secondary cell preferably meets wantonly 1 or multinomial in (1) as follows~(21) simultaneously.
(1) X-ray parameter
By using learn shake method to carbonaceous material carry out X-ray diffraction calculated by lattice plane (002 face) d value (interlayers Distance) it is usually 0.335~0.340nm, is preferably 0.335~0.338nm, especially preferably 0.335~0.337nm.In addition, By using to learn the crystallite dimension (Lc) that shakes calculated by the X-ray diffraction of method be usually more than 1.0nm, be preferably more than 1.5nm, Especially preferably more than 2nm.
As carbonaceous material, the crystalline substance being preferably obtained with X-ray diffraction obtained from amorphous carbon coating graphite surface The d values in lattice face (002 face) are that the graphite of 0.335~0.338nm is asked as nuclear material, and in its surface attachment by X-ray diffraction The d values of the lattice plane (002 face) gone out are more than the carbonaceous material of the nuclear material, and nuclear material and the lattice that is obtained by X-ray diffraction The d values in face (002 face) be more than the nuclear material carbonaceous material ratio using weight ratio meter as 99/1~80/20 carbonaceous material. During using this carbonaceous material, it is possible to produce there is high power capacity and be not easy the cathode with electrolyte reaction.
(2) ash content
Compared with the gross mass of carbonaceous material, contained ash content is below 1 mass %, is wherein preferably in carbonaceous material Below 0.5 mass %, especially preferably below 0.1 mass %, lower limit is preferably in more than 1ppm.If the weight ratio of ash content More than above range, battery performance can be caused ignorable deterioration occur when being reacted with nonaqueous electrolytic solution in charge and discharge. On the other hand, when less than above range, then be necessary for manufacture take a significant amount of time, energy and for prevent pollution set It is standby, further result in cost increase.
(3) volume-based average particle size
The volume-based average particle size of carbonaceous material is the average grain for the volume reference being obtained using laser diffraction/scattering method Footpath (median particle diameter), it typically is 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, especially preferably 7 μm or more, And usually less than 100 μm, be preferably less than 50 μm, more preferably less than 40 μm, be more preferably less than 30 μm, it is especially excellent Elect less than 25 μm as.If volume-based average particle size is less than above range, irreversible capacity is made to increase and cause sometimes Initial cell capacitance loss.In addition, when being more than above range, when preparing electrode, easily formed non-uniform using coating Coated face is sometimes undesirable in battery production process.
Volume-based average particle size is measured using following methods：Carbon dust is made to be dispersed in as the poly- of surfactant In the 0.2 mass % aqueous solutions (about 10mL) of ethylene oxide (20) Span-20, and utilize laser diffraction/scattering Formula particle size distribution meter (LA-700 of Ku Chang manufacturing companies manufacture) is measured.The median particle diameter being obtained by the measure is determined Justice is the volume-based average particle size of the carbonaceous material of the present invention.
(4) Raman R value, Raman half breadth
The Raman R value of carbonaceous material is the value measured using argon laser Raman spectroscopy, it typically is more than 0.01, Preferably more than 0.03, be more preferably more than 0.1, and usually less than 1.5, be preferably less than 1.2, more preferably less than 1, it is outstanding It is preferably less than 0.5.
When Raman R value is less than above range, the crystallinity of particle surface is excessively high, Li may be caused to enter with charge and discharge The site (サ イ ト) of interlayer tails off.That is, charge acceptance may be caused to reduce.In addition, after being coated on the current collector, pass through When compacting carries out densification to cathode, crystallize readily along the direction orientation parallel with electrode plate, load characteristic may be caused It reduces.When on the other hand, more than above range, the crystallinity of particle surface reduces, and the reactivity with nonaqueous electrolytic solution is caused to increase Add, the gas that may cause efficiency reduces or generate increases.
In addition, for carbonaceous material in 1580cm-1Neighbouring Raman half breadth is not particularly limited, and is usually 10cm-1 Above, it is preferably 15cm-1More than, and usually 100cm-1Below, it is preferably 80cm-1Below, it is more preferably 60cm-1Below, especially It is preferably 40cm-1Below.When Raman half breadth is less than above range, the crystallinity of particle surface is excessively high, with charge and discharge The site that electricity may cause Li to enter interlayer tails off.That is, charge acceptance may be caused to reduce.In addition, it is coated on the current collector Afterwards, when carrying out densification to cathode by compacting, crystallize readily along the direction orientation parallel with electrode plate, may cause Load characteristic reduces.When on the other hand, more than above range, the crystallinity of particle surface reduces, and causes and nonaqueous electrolytic solution Reactivity increases, and the gas that may cause efficiency reduces or generate increases.
Being determined as follows for Raman spectrum is described：Using raman splitter (Japanese light splitting company manufacture raman splitter), Sample is made to fall naturally and is filled in cell (cell), argon laser is irradiated to the surface of sample in pond, while makes survey Determine pond to rotate in the face with laser vertical, thus be measured.For the Raman spectrum of acquisition, measure in 1580cm-1Near Peak PAIntensity IAAnd in 1360cm-1Neighbouring peak PBIntensity IB, and calculate the intensity ratio R (R=I of the twoB/IA).It will The Raman R value being obtained using the measure is defined as the Raman R value of carbonaceous material in the present invention.In addition, measure obtained Raman Spectrum is in 1580cm-1Neighbouring peak PAHalf breadth, be defined as the Raman half breadth of carbonaceous material in the present invention.
In addition, the condition that above-mentioned Raman measures 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 (background) processing
Smoothly (smoothing) is handled：Simple average, 5 points of convolution (convolution 5point)
(5) BET specific surface area
The value of the BET specific surface area of the carbonaceous material measured using BET method is usually 0.1m2·g-1Above, it is preferably 0.7m2·g-1Above, it is more preferably 1.0m2·g-1Above, it is especially preferably 1.5m2·g-1More than, and usually 100m2·g-1 Below, it is preferably 25m2·g-1Below, it is more preferably 15m2·g-1Below, it is especially preferably 10m2·g-1Below.When BET compares table When the value of area is less than the scope, the acceptance variation of lithium, lithium are easy when being easy to cause charging when being used as negative material It is precipitated to electrode surface, and then stability may be caused to reduce.When on the other hand, more than the scope, cathode material is being used as Cause to increase with the reactivity of nonaqueous electrolytic solution during material, be easy to generate more gas, and then be likely difficult to obtain preferable battery.
It is carried out by the following method using during BET method measurement the specific area：Using surface area meter, (Okura development is made complete Automatic surface accumulate measurement device), under nitrogen flowing, at 350 DEG C to sample carry out predrying in 15 minutes after, using nitrogen compared with The relative pressure of atmospheric pressure is accurately adjusted to 0.3 nitrogen helium mixed gas, by using the N2 adsorption BET 1 of gas flow method Point method is measured.The specific surface area being obtained using the measure is defined as to the BET specific surface area of carbonaceous material in the present invention.
(6) micropore diameter is distributed
The micropore diameter distribution of carbonaceous material is obtained by measuring mercury intrusion.By using mercury porosimeter (water Silver-colored plunging) measure understand, in carbonaceous material, draw by the particle internal pore of carbonaceous material, due to particle surface is uneven Micropore caused by concave-convex and interparticle contact surface risen etc. is equivalent to a diameter of 0.01 μm~1 μm of micropore, carbonaceous material In preferably have the distribution of following micropore diameters：Usually 0.01cm3·g-1Above, it is preferably 0.05cm3·g-1Above, more preferably 0.1cm3·g-1More than, and usually 0.6cm3·g-1Below, it is preferably 0.4cm3·g-1Below, it is more preferably 0.3cm3·g-1 Below.When micropore diameter distribution is more than above range, substantial amounts of adhesive may be needed when carrying out pole plate.On the other hand, If less than above range, high current density charge-discharge characteristic may be caused to reduce and electricity can not be obtained in charge and discharge The alleviation effects of pole dilation.
In addition, be obtained using mercury porosimeter (mercury penetration method), diameter be equivalent to 0.01 μm~100 μm of micropore Micropore total measurement (volume) be usually 0.1cm3·g-1Above, it is preferably 0.25cm3·g-1Above, it is more preferably 0.4cm3·g-1With On, and usually 10cm3·g-1Below, it is preferably 5cm3·g-1Below, it is more preferably 2cm3·g-1Below.When micropore total measurement (volume) During more than above range, substantial amounts of adhesive may be needed when carrying out pole plate.On the other hand, if being less than above range, The dispersion effect that thickener or binding agent are unable to reach when carrying out pole plate may then be caused.
In addition, mean pore footpath is usually 0.05 μm or more, is preferably 0.1 μm or more, more preferably 0.5 μm or more, and Usually less than 50 μm, preferably less than 20 μm, more preferably less than 10 μm.It, can when mean pore footpath is more than above range It can need substantial amounts of adhesive.On the other hand, if less than above range, high current density charge-discharge characteristic may be caused to drop It is low.
Mercury intrusion is measured using following methods：Using mercury void determination instrument (AutoPore 9520, Micrometritics companies manufacture) as the device as mercury porosimeter.As pre-treatment, about 0.2g samples are enclosed In powder container, (50 μm of below Hg) deaerate within 10 minutes in vacuum at room temperature.Then, it is decompressed to 4psia (about 28kPa), and import mercury, make pressure from 4psia (about 28kPa) is stage rise to 40000psia (about 280MPa) after, then drop To 25psia (about 170kPa).Number of stages in boost process is arranged on 80 grades or more, in each stage in, pass through 10 seconds Equilibration time after measure mercury intrusion.
Curve is pressed by the mercury obtained in said determination using Washburn formulas and calculates micropore diameter distribution.This In, the surface tension (γ) of mercury is set as 485dynecm-1(1dyne=10 μ N), contact angle (φ) are 140 °.It is average micro- Aperture uses the micropore diameter accumulated when micro pore volume reaches 50%.
(7) circularity
Circularity is being measured come when evaluating the spherical degree of carbonaceous material, circular degree is within following ranges.It needs Illustrate, circularity is defined with following formula：Circularity=(there is the week of the equivalent circular of the area identical with particle projection of shape It is long)/(perimeter of particle projection of shape).When circularity is 1, become theoretical proper sphere.
Grain size is more preferable closer to 1 for the circularity of the particle of 3~40 μ ms in carbonaceous material, also, it is circular Degree is preferably more than 0.1, is wherein preferably more than 0.5, is more preferably more than 0.8, is more preferably more than 0.85, is especially excellent Elect more than 0.9 as.
When circularity is bigger, high current density charge-discharge characteristic is more excellent.Thus, when circularity is less than above range, The fillibility of negative electrode active material reduces, resistance increases between particle, and short time high current density charge-discharge characteristic may be caused to drop It is low.
Circularity is measured using flow-type particle image analysis device (FPIA of Sysmex companies manufacture).It will about The 0.2 mass % that 0.2g samples are dispersed in polyoxyethylene (20) Span-20 as surfactant is water-soluble In liquid (about 50mL), and after being irradiated 1 minute with the output power of 60W with the ultrasonic wave of 28kHz, 0.6~400 μm is specified as detection Scope is measured particle of the grain size in 3~40 μ ms.The circularity being obtained using the measure is defined as in the present invention The circularity of carbonaceous material.
It is had no for the method for improving circularity specifically limited, but particle is converted into spherical shape by implementing spheroidization processing It is applied to realize that the shape of inter-particle voids is neat uniform during electrode body afterwards, therefore preferably.Reality as spheroidization processing Example, can enumerate and be had in itself come method mechanically close to a spherical shape, using adhesive or particle by applying shearing force, compression stress Some adhesive force carries out machinery/physical treatment method of granulation of multiple particles etc..
(8) real density
The real density of carbonaceous material is usually 1.4gcm-3Above, it is preferably 1.6gcm-3Above, more preferably 1.8g·cm-3Above, it is especially preferably 2.0gcm-3More than, and usually 2.26gcm-3Below.When real density is less than upper When stating scope, the crystallinity of carbon is too low, and initial stage irreversible capacity may be caused to increase.It should be noted that above range is upper It is limited to the theoretical upper limit value of graphite real density.
The real density of carbonaceous material is measured by using the Liquid displacement methods (hydrometer method) of butanol.The survey will be utilized Surely the value being obtained is defined as the real density of carbonaceous material in the present invention.
(9) tap density
The tap density of carbonaceous material is usually 0.1gcm-3Above, it is preferably 0.5gcm-3Above, more preferably 0.7g·cm-3Above, it is especially preferably 1gcm-3More than, and preferably 2gcm-3Below, it is more preferably 1.8gcm-3With Under, especially preferably 1.6gcm-3Below.If tap density is less than above range, as cathode when is difficult to improve filling Density may lead to not the battery for obtaining high power capacity.In addition, when more than above range, the inter-particle voids in electrode become It obtains very few, it is difficult to ensure interparticle electric conductivity, may lead to not obtain preferable battery behavior.
Tap density is measured by following methods：Sample is made to drop into 20cm after by mesh for 300 μm of sieve3's In jolt ramming container, after sample is filled to the upper surface of container, using powder density analyzer (for example, Seishin enterprises The Tap densor of company's manufacture) carry out the vibration that 1000 lengths of stroke are 10mm, thus when volume and sample weight ask Calculate tap density.The tap density calculated using the measure is defined as to the tap density of carbonaceous material in the present invention.
(10) orientation ratio
The orientation ratio of carbonaceous material is usually more than 0.005, is preferably more than 0.01, is more preferably more than 0.015, and logical It is often less than 0.67.If orientation ratio is less than above range, the reduction of high density charge-discharge characteristic may be caused.Need what is illustrated It is that the upper limit of above range is the theoretical upper limit value of carbonaceous material orientation ratio.
Orientation ratio is to be measured after being press-formed to sample using X-ray diffraction.It is to be filled in 0.47g samples In the forming machine of a diameter of 17mm, in 58.8MNm-2Lower compression obtains formed body, then fixes the formed body with clay, make its with The face of measurement sample frame is same face, so as to carry out X-ray diffraction measure.By obtained carbon (110) diffraction with (004) peak intensity of diffraction calculates the ratio represented with (110) diffraction peak intensity/(004) diffraction peak intensity.The survey will be utilized Surely the orientation ratio being obtained is defined as the orientation ratio of carbonaceous material in the present invention.
The determination condition of X-ray diffraction is as described below.Wherein, " 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 Dus≤2 1 degree of θ≤80 degree/60 seconds
(004) face：52 Dus≤2 1 degree of θ≤57 degree/60 seconds
(11) draw ratio (powder)
The draw ratio of carbonaceous material is usually more than 1, and usually less than 10, be preferably less than 8, more preferably less than 5. If draw ratio is more than above range, striped may be generated when carrying out pole plate, uniform coated face, high electricity can not be obtained Current density charge-discharge characteristic reduces.It should be noted that the lower limit of above range is the theory lower bound value of carbonaceous material draw ratio.
The measure of draw ratio is amplified observation to the particle of carbonaceous material by using scanning electron microscope and carries out.Selection is solid Arbitrary 50 graphite particles being scheduled on metal end face less than 50 microns thick, rotation tilt the loading for being fixed with these samples Platform measures most major diameter A and perpendicular most minor axis B in the carbonaceous material particle observed during 3-dimensional observation respectively, and The average value of A/B is obtained.The draw ratio (A/B) being obtained using the measure is defined as to the draw ratio of carbonaceous material in the present invention.
(12) auxiliary material mixes
So-called auxiliary material mixing, refers to different containing two or more property in negative electrode and/or in negative electrode active material Carbonaceous material.The property therein refers to：Selected from X-ray diffraction parameter, median particle diameter, draw ratio, BET specific surface area, take To than one or more of, Raman R value, tap density, real density, micropore distribution, circularity, ash amount characteristic.
As the particularly preferred example of above-mentioned auxiliary material mixing, can enumerate：Volume reference size distribution is with intermediate value grain It is left-right asymmetry when centered on footpath, contain the different carbonaceous material of two or more Raman R value and X-ray parameter difference etc..
One of example of effect as auxiliary material mixing, can enumerate：By containing the graphite such as native graphite, Delanium The carbonaceous materials such as the amorphous carbon such as the carbon blacks such as (graphite), acetylene black, needle coke can enable resistance to drop as conductive material It is low.
When hybrid conductive material is mixed as auxiliary material, a kind can be individually mixed, it can also in any combination and ratio Mix two or more.In addition, the mixing ratio of conductive material and carbonaceous material is usually more than 0.1 mass %, is preferably 0.5 matter Measure more than %, more preferably more than 0.6 mass %, and usually below 45 mass %, preferably below 40 mass %.It is if mixed Composition and division in a proportion is less than above range, then may cause to be difficult to obtain the effect for improving electric conductivity.In addition, if it is more than above range, then Initial stage irreversible capacity may be caused to increase.
(13) prepared by electrode
In the range of the effect of the present invention is not significantly limited, any known method may be employed to prepare electrode.Example It such as, can be by adding adhesive, solvent into negative electrode active material, the thickener added as needed, conductive material, filling out Fill material etc., slurry be made, and be coated on the current collector, it is dry after suppressed to form electrode.
Battery close on nonaqueous electrolytic solution injection process before stage, negative electrode active material layer on each face on battery Thickness be usually 15 μm or more, be preferably more than 20 μm, more preferably 30 μm or more, and usually less than 150 μm, preferably Less than 120 μm, more preferably less than 100 μm.The thickness of negative electrode active material is if it exceeds the scope, then due to nonaqueous electrolytic solution It is difficult to be impregnated into collector near interface, it is thus possible to cause the reduction of high current density charge-discharge characteristic.On the other hand, it is if low In the scope, then the volume ratio of collector and negative electrode active material may be caused to increase, battery capacity is reduced.It furthermore it is possible to will Negative electrode active material carries out roller shaping to make pellet electrode or make mosaic electrode by compression forming.
(14) collector
As the collector that can be maintained negative electrode active material, well known collector can be arbitrarily used.As negative The collector of pole, it can be mentioned, for example the metal materials such as copper, nickel, stainless steel, nickel-plated steel, are examined in terms of processing simplification and cost Consider, particularly preferred copper.
In addition, the shape as collector, when collector is metal material, it can be mentioned, for example metal foil, metal cylinder, Wire coil, metallic plate, metallic film, expansion alloy, perforated metal, foaming metal etc..Wherein, preferred metallic film, more excellent Copper foil is selected, further preferably using the obtained rolled copper foil of rolling process and the electrolytic copper foil obtained using electrolysis, is appointed in above-mentioned One can use as collector.
In addition, when copper thickness is less than 25 μm, copper alloy (phosphor bronze, titanium copper, the section of fine copper can be higher than with use intensity Gloomy alloy, Cu-Cr-Zr alloys etc.).
In the collector formed in the copper foil by being made using rolling process, arranged since copper is crystallized along rolling direction, because Even if this is at an acute angle by cathode crimping very close or curling, still it is not easily broken, is applicable to small cylinder shape battery.
Electrolytic copper foil is obtained by following methods：Such as：Metal drum is immersed in the non-water power dissolved with copper ion It solves in liquid, galvanization while rotating the drum, so that copper is precipitated on drum surface, is removed to obtain electrolytic copper foil.May be used also Using electrolysis copper to be made to be precipitated on above-mentioned rolled copper foil surface.The one or both sides of copper foil can also be roughened Or surface treatment (for example, thickness is in base treatments such as the chromic acid salt treatment of several nm~1 μm or so, Ti etc.).
Current collection structure base board further preferably has following physical property.
(14-1) average surface roughness (Ra)
The negative electrode active material film forming face of current collection structure base board specified in the method recorded for JISB0601-1994 Average surface roughness (Ra) be not particularly limited, be usually more than 0.05 μm, be preferably 0.1 μm or more, be more preferably 0.15 μm or more, and usually less than 1.5 μm, preferably less than 1.3 μm, more preferably less than 1.0 μm.This is because：Work as collection The average surface roughness (Ra) of electric structure base board within the above range when, can expect good charge/discharge cycle characteristics；Also, with The interfacial area of negative electrode active material film becomes larger, and is improved with the adhesiveness of negative electrode active material film.It is it should be noted that right Had no in the upper limit value of average surface roughness (Ra) it is specifically limited, when average surface roughness (Ra) is more than 1.5 μm, usually It is difficult to obtain the paper tinsel of thickness practicality when being used as battery, therefore the average surface roughness (Ra) below 1.5 μm of generally use.
(14-2) tensile strength
So-called tensile strength, refer to the sectional area of required maximum pull divided by test film when test film is broken and Obtained value.Tensile strength in the present invention uses the dress identical with the record of JISZ2241 (material during tensile test method) It puts and method measures.
It is not particularly limited for the tensile strength of current collection structure base board, is usually 100Nmm-2More than, it is preferably 250N mm-2More than, more preferably 400Nmm-2More than, especially preferably 500Nmm-2More than.The value of tensile strength is more high then more It is preferred that, it is contemplated that industrial accessibility is usually 1000Nmm-2Below.If the current collection structure base board that tensile strength is high, then It can inhibit the cracking of the current collection structure base board as caused by negative electrode active material film expansion/contraction in charge/discharge process, It is hereby achieved that good cycle characteristics.
(14-3) 0.2% yield strength
So-called 0.2% yield strength, load necessary to referring to (permanent) strain of the plasticity for generating 0.2%, applies After the load of the size, even if except unloading, 0.2% deformation is still kept.0.2% yield strength is utilized with measuring tensile strength Identical device and method measures.
Had no for 0.2% yield strength of current collection structure base board it is specifically limited, be usually 30Nmm-2Above, it is preferably 150N·mm-2Above, it is especially preferably 300Nmm-2More than.The value of 0.2% yield strength is more high then more preferred, from industry The angle of accessibility is set out, it is often preferred that 900Nmm-2Below.If the current collection structure base board that 0.2% yield strength is high, The modeling of the current collection structure base board as caused by negative electrode active material film expansion/contraction in charge/discharge process can then be inhibited Property deformation, it is hereby achieved that good cycle characteristics.
The thickness of (14-4) collector
Collector can be any thickness, but usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and Usually below 1mm, preferably less than 100 μm, more preferably less than 50 μm.When the thickness of collector is less than 1 μm, due to strong Degree declines, thus coating may be caused to become difficult.In addition, when thickness is more than 100 μm, then it may cause electrode shape The deformations such as curling.It should be noted that collector can be netted.
(15) thickness ratio of collector and negative electrode active material layer
Had no for the thickness ratio of collector and negative electrode active material layer it is specifically limited, but " (closing on nonaqueous electrolytic solution note The thickness of the negative electrode active material layer on single face before entering)/(thickness of collector) " value be preferably less than 150, it is more excellent Elect less than 20, especially preferably less than 10, and preferably more than 0.1, more preferably more than 0.4, especially preferably more than 1 as.
If the thickness ratio of collector and negative electrode active material layer is more than above range, in high current density charge and discharge When, collector may trigger heat release due to Joule heat.In addition, when thickness ratio is less than above range, collector is compared with negative The volume ratio of pole active material increases, and battery capacity may be caused to reduce.
(16) electrode density
It is not particularly limited, is present in negative on collector for electrode structure when negative electrode active material to be made to electrode The density of pole active material is preferably 1gcm-3Above, it is more preferably 1.2gcm-3Above, it is especially preferably 1.3gcm-3 More than, and preferably 2gcm-3Below, it is more preferably 1.9gcm-3Below, it is more preferably 1.8gcm-3Below, especially It is preferably 1.7gcm-3Below.When the density for the negative electrode active material being present on collector is more than above range, cathode Active material particle can be destroyed, and cause the increase of initial stage irreversible capacity, nonaqueous electrolytic solution in collector/negative electrode active material The impregnability of near interface reduces, and then high current density charge-discharge characteristic is caused to deteriorate.In addition, if less than above-mentioned model It encloses, then the electric conductivity between negative electrode active material may be caused to reduce, cell resistance increases, and the capacity of unit volume reduces.
(17) adhesive
As the adhesive for bonding negative electrode active material, as long as used when being manufactured compared with nonaqueous electrolytic solution and electrode The material of solvent-stable, then be not particularly limited.
As specific example, polyethylene, polypropylene, polyethylene terephthalate, poly-methyl methacrylate can be enumerated The resins family macromolecule such as ester, aromatic polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), isoprene rubber, fourth The rubber-like macromolecules such as diene rubber, fluorubber, NBR (nitrile rubber), EP rubbers；S-B-S block Copolymer or its hydride；EPDM (ethylene/propylene/diene terpolymer), styrene ethylene butadiene-styrene are common The thermoplastic elastomer (TPE)s shape macromolecule such as polymers, styrene-isoprene-styrene block copolymer or its hydride；Between advise it is vertical The soft resins such as structure 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers Shape macromolecule；The fluorine class high scores such as Kynoar, polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer Son；Polymeric composition with ionic conductivity of alkali metal containing ion (particularly lithium ion) etc..Above-mentioned material can be single It, can also in any combination and two or more is applied in combination in ratio solely using a kind.
As for forming the solvent of slurry, as long as it can dissolve or disperse negative electrode active material, adhesive, Yi Jigen The thickener and the solvent of conductive material used according to needs, is not particularly limited its species, can use aqueous molten Any one of agent or organic solvent.
As the example of aqueous solvent, water, alcohol etc. can be enumerated；As the example of organic solvent, N- methyl pyrroles can be enumerated Pyrrolidone (NMP), dimethylformamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl Base triamine, N, N- dimethylamino propylamines, tetrahydrofuran (THF), toluene, acetone, ether, dimethyl acetamide, hempa Amide, dimethyl sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc..
Particularly, when using aqueous solvent, preferably make while thickener is used wherein containing dispersant etc., and adopt It is carried out with latex such as SBR slurried.It, can also in any combination and ratio combination makes in addition, above-mentioned solvent can be used alone a kind Use two or more.
Adhesive is preferably more than 0.1 mass % compared with the ratio of negative electrode active material, more preferably 0.5 mass % with Upper, especially preferably more than 0.6 mass %, and it is preferably below 20 mass %, more preferably below 15 mass %, further excellent It elects as below 10 mass %, especially preferably below 8 mass %.If adhesive is more than compared with the ratio of negative electrode active material Above range, the then ratio for not having contributive adhesive in amount of binder to battery capacity increase, and battery capacity may be caused to drop It is low.In addition, when being less than above range, the strength reduction of negative electrode may be caused.
Particularly, when containing in main component using rubber-like macromolecules of the SBR as representative, adhesive is lived compared with cathode Property substance ratio be usually more than 0.1 mass %, be preferably more than 0.5 mass %, more preferably more than 0.6 mass %, and Usually below 5 mass %, preferably below 3 mass %, more preferably below 2 mass %.
In addition, when containing in main component using fluorine class macromolecule of the Kynoar as representative, live compared with cathode Property substance ratio be usually more than 1 mass %, be preferably more than 2 mass %, more preferably more than 3 mass %, and be usually Below 15 mass %, it is preferably below 10 mass %, more preferably below 8 mass %.
Thickener is commonly used in adjusting the viscosity of slurry.As thickener, have no it is specifically limited, it is specific enumerable：Carboxylic first Base cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, enzyme egg Their salt of bletilla etc..Above-mentioned thickener can be used alone, can also in any combination and ratio be applied in combination 2 kinds with On.
In addition, when using thickener, thickener compared with the ratio of negative electrode active material be usually 0.1 mass % with Upper, preferably more than 0.5 mass %, more preferably more than 0.6 mass %, and usually below 5 mass %, preferably 3 matter Measure below %, more preferably below 2 mass %.If thickener is less than above range compared with the ratio of negative electrode active material, Significantly reducing for coating may then be caused.On the other hand, when more than above range, negative electrode active in negative electrode active material layer Resistance increase between the problem of ratio shared by substance declines, battery capacity may be triggered to reduce and negative electrode active material.
(18) pole plate orientation ratio
Pole plate orientation ratio is usually more than 0.001, is preferably more than 0.005, is more preferably more than 0.01, and is usually Less than 0.67.If pole plate orientation ratio is less than above range, the reduction of high density charge-discharge characteristic may be caused.Need what is illustrated It is that the upper limit of above range is the theoretical upper limit value of carbonaceous material pole plate orientation ratio.
The measure of pole plate orientation ratio carries out by the following method：Negative electrode is suppressed to target density, is spread out using X-ray Penetrate the negative electrode active material orientation ratio for measuring electrode at this time.It is not particularly limited for specific method, as standard method, adopts By the use of asymmetric Pearson (ピ ア ソ Application) VII as distribution (profile) function, (110) to the carbon obtained by X-ray diffraction Diffraction maximum and (004) diffraction maximum are fitted, and thus carry out peak separation, are spread out so as to calculate (110) diffraction maximum and (004) respectively Penetrate the integrated intensity at peak.It is calculated by the integrated intensity of gained with (110) diffraction integral intensity/(004) diffraction integral intensity table The ratio shown.The negative electrode active material orientation ratio for the electrode being obtained using the measure is defined as by carbonaceous material shape in the present invention Into electrode pole plate orientation ratio.
X-ray diffraction measure condition is as described below.Wherein, " 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 Dus≤2 0.01 degree of θ≤78.5 degree/3 seconds
(004) face：53.5 Dus≤2 0.01 degree of θ≤56.0 degree/3 seconds
It is prepared by sample：Electrode is fixed on a glass with the double faced adhesive tape of 0.1mm thickness
<2-3-3. metal compound species materials and used metal compound species material cathode structure, physical property, system Preparation Method>
As the metal compound species material as negative electrode active material, as long as energy occlusion/releasing lithium, then can be to be formed The changes such as the metal simple-substance or alloy or their oxide, carbide, nitride, silicide, sulfide, phosphide of lithium alloy Any materials in object are closed, are had no specifically limited.As the metallic compound, can enumerate containing Ag, Al, Ba, Bi, Cu, Ga, The compound of the metals such as Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn.Wherein, metal simple-substance or the conjunction of lithium alloy are preferably formed as Gold preferably comprises the material of the 13rd race and the 14th race's metal/metalloid element (i.e., in addition to carbon), further preferably silicon (Si), tin (Sn), the metal simple-substance of lead (Pb) (following, be referred to as sometimes " special metal element ") or comprising these atoms Alloy/compound.Above-mentioned material can be used alone, can also in any combination and two or more is applied in combination in ratio.
As the example of the negative electrode active material at least one kind of atom in special metal element, it can enumerate and appoint Anticipate a kind of special metal element metal simple-substance, be made of two or more special metal element alloy, by one kind or two or more spy The alloy and contain one kind or two or more special metal member that metallic element and other one kind or two or more metallic elements are formed The Composite of the compound of element or oxide, carbide, nitride, silicide, sulfide, the phosphide etc. of the compound Close object.As negative electrode active material, the Gao Rong of battery can be realized by using these metal simple-substances, alloy or metallic compound Quantify.
In addition, the example as above-mentioned complex chemical compound, can also enumerate and metal simple-substance, alloy or nonmetalloid Wait the compound of multiple elements complex combination.More specifically, such as silicon or tin, can be used these elements with that cathode can not be used as to send out Wave the alloy of the metal of effect.In addition, such as tin, can be used and made by combining tin and can be used as cathode in addition to silicon to play By the use of metal and can not as obtained from the metal and nonmetalloid that cathode plays a role containing 5~6 kinds of elements Complex compound.
In above-mentioned negative electrode active material, metal simple-substance, two or more special metal of preferably wantonly a kind of special metal element The alloy of element, the oxide of special metal element, carbide or nitride etc., this is because they are every single when battery is made The capacity of position weight is larger, and in view of the capacity of per unit weight and the load caused by environment, particularly preferred silicon and/or tin Metal simple-substance, alloy, oxide, carbide or nitride etc..
In addition, during using metal simple-substance or alloy, although the capacity of per unit mass is deteriorated, since cycle characteristics is excellent It is different, thus still preferably comprise following compounds of silicon and/or tin.
The oxide of silicon and/or tin, wherein, silicon and/or the element ratio of tin and oxygen are usually more than 0.5, are preferably 0.7 Above, be more preferably more than 0.9, and usually less than 1.5, be preferably less than 1.3, more preferably less than 1.1.
The nitride of silicon and/or tin, wherein, silicon and/or the element ratio of tin and nitrogen are usually more than 0.5, are preferably 0.7 Above, be more preferably more than 0.9, and usually less than 1.5, be preferably less than 1.3, more preferably less than 1.1.
The carbide of silicon and/or tin, wherein, silicon and/or the element ratio of tin and carbon are usually more than 0.5, are preferably 0.7 Above, be more preferably more than 0.9, and usually less than 1.5, be preferably less than 1.3, more preferably less than 1.1.
It, can also in any combination and ratio group it should be noted that above-mentioned negative electrode active material can be used alone wantonly a kind It closes and uses two or more.
Cathode in the non-aqueous electrolyte secondary battery of the present invention can be used well known any means and prepare.Specifically, As the manufacturing method of cathode, it can be mentioned, for example：Binding agent and conductive material etc. are added in into above-mentioned negative electrode active material, then it is right The method that obtained material directly carries out roller shaping pellet electrode is made；The side of mosaic electrode is made up of compression forming Method.But generally use be using the methods of rubbing method, vapour deposition method, sputtering method, plating cathode collector (it is following, Be called " negative electrode collector ") on formed containing above-mentioned negative electrode active material film layer (negative electrode active material layer) method. At this point, add in binding agent, thickener, conductive material, solvent etc. into above-mentioned negative electrode active material, be made pulp-like, then by its It is coated on negative electrode collector and dry, is then suppressed so that its densification, negative so as to be formed on negative electrode collector Pole active material layer.
As the material of negative electrode collector, steel, copper alloy, nickel, nickel alloy, stainless steel etc. can be enumerated.In these materials, In view of film property easy to process and cost aspect, preferably copper foil.
The thickness of negative electrode collector is usually 1 μm or more, is preferably 5 μm or more, and usually less than 100 μm, preferably Less than 50 μm.If the thickness of negative electrode collector is blocked up, the capacity of entire battery may become too low, whereas if it is excessively thin, Operating difficulties may then be caused.
It is pointed out that in order to be improved the bond effect of the negative electrode active material layer of surface formation, preferably in advance First the surface of above-mentioned negative electrode collector is roughened.As the method for surface roughening, following methods can be enumerated：Spray Sand processing, is rolled using rough surface roller, be fixed with the abrasive cloth paper of abrasive particle, sandstone, Carborundum wheel, with steel Mechanical milling method, electrolytic polishing method, chemical grinding method that wire brush of line etc. etc. is ground collector surface etc..
In addition, in order to reduce the weight of negative electrode collector to improve the energy density of battery per unit weight, can also make With the negative electrode collector of the open-cells such as expansion alloy or perforated metal.Such negative electrode collector can also be by changing it Aperture opening ratio carrys out arbitrary change weight.In addition, when forming negative electrode active material layer on the two sides of such negative electrode collector, Due to there is the anchoring effect through the hole, it can be more difficult to negative electrode active material layer peeling-off.But if aperture opening ratio mistake Height, it will cause the contacts area between negative electrode active material layer and negative electrode collector to become smaller, and may instead result in adhesion strength It reduces.
For formed the slurry of negative electrode active material layer usually by added into negative material binding agent, thickener etc. and It is made.It should be noted that " negative material " described in this specification refers to that including negative electrode active material and conductive material exists Interior material.
Content of the negative electrode active material in negative material is usually more than 70 mass %, especially preferably 75 mass % with On, and usually below 97 mass %, especially preferably below 95 mass %.It, can when the content of negative electrode active material is very few It can cause to have used the capacity of the secondary cell of the cathode obtained to tend to deficiency；It is viscous due to that can cause if content is excessive The content relative deficiency of agent etc. is tied, the intensity of obtained cathode may be caused to tend to deficiency.It should be noted that when combination makes During with two or more negative electrode active material, as long as the total amount of negative electrode active material is made to meet above range.
As the conductive material for cathode, the metal materials such as copper, nickel can be enumerated；Carbon materials such as graphite, carbon black etc..These Conductive material can be used alone, can also in any combination and two or more is applied in combination in ratio.Particularly, when using carbon When material is as conductive material, since carbon material can also play the effect of active material, preferably.Leading in negative material The content of electric material is usually more than 3 mass %, particularly preferably more than 5 mass %, and usually below 30 mass %, especially Preferably below 25 mass %.If conductive material content is very few, electric conductivity may be caused to tend to deficiency, when excessive, due to It can make the content relative deficiency of negative electrode active material etc., thus battery capacity and intensity may be caused to have a declining tendency.It needs Illustrate, when conductive material of more than two kinds is applied in combination, as long as the total amount of conductive material is made to meet above range.
As the binding agent for cathode, as long as making the solvent and the material of electrolyte safety to being used when manufacturing electrode , arbitrary binding agent can be used.Such as it can enumerate：Kynoar, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, butylbenzene Rubber, isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc..It is above-mentioned viscous Knot agent can be used alone, can also in any combination and two or more is applied in combination in ratio.Compared with 100 weight of negative material Measure part, the content of binding agent is usually more than 0.5 parts by weight, more than particularly preferably 1 parts by weight, and usually 10 parts by weight with Under, particularly preferably below 8 parts by weight.If the content of binding agent is very few, the intensity of obtained cathode may be caused to become In deficiency, when excessive, due to the content relative deficiency of negative electrode active material etc., battery capacity and electric conductivity may be caused to tend to not Foot.It should be noted that when two or more binding agent is applied in combination, as long as the total amount of binding agent is made to meet above range.
As the thickener for cathode, carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl can be enumerated Cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein etc..These thickeners can be used alone, can also In any combination and two or more is applied in combination in ratio.Thickener can use as needed, during using thickener, thickener Content in negative electrode active material layer is preferably generally the scope of the mass % of 0.5 mass %~5.
Slurry for forming negative electrode active material layer can be by mixing required conduction into above-mentioned negative electrode active material Material and binding agent, thickener, and be formulated using aqueous solvent or organic solvent as decentralized medium.As aqueous solvent, Usually using water, but can also be the alcohols such as ethyl alcohol or N- first is applied in combination compared with ratio of the water as below 30 mass % left and right Other solvents than water such as cyclic amides such as base pyrrolidones.In addition, as organic solvent, N- methyl can be usually enumerated The cyclic amides such as pyrrolidones；The straight-chains amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；Methyl phenyl ethers anisole, The arenes such as toluene, dimethylbenzene；The alcohols such as butanol, cyclohexanol.Wherein, preferred cyclic amides such as N-Methyl pyrrolidone； Straight-chains amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..Wherein, above-mentioned solvent can be used alone any Kind, it can also in any combination and two or more is applied in combination in ratio.
As long as the viscosity of slurry reaches the viscosity that can be coated on collector, have no specifically limited.As can apply The viscosity of cloth can suitably be adjusted by changing solvent dosage etc. when preparing slurry.
After obtained slurry is coated on above-mentioned negative electrode collector and is dried, cathode is formed by being suppressed Active material layer.It is had no for the method for coating specifically limited, itself known method can be used.For dry method Also it is not particularly limited, the known methods such as natural drying, heat drying can be used, be dried under reduced pressure.
It is not particularly limited, but exists for electrode structure when negative electrode active material to be made up to electrode of the above method In the density of the active material on collector be preferably 1gcm-3Above, it is more preferably 1.2gcm-3Above, especially preferably 1.3g·cm-3More than, and preferably 2gcm-3Below, it is more preferably 1.9gcm-3Below, it is more preferably 1.8g cm-3Below, it is especially preferably 1.7gcm-3Below.Density if present in the active material on collector is more than above-mentioned model It encloses, then active material particle can be destroyed, and may cause the increase of initial stage irreversible capacity and nonaqueous electrolytic solution in current collection Impregnability near body/reactive species interface reduces, and then high current density charge-discharge characteristic is caused to deteriorate.On the other hand, such as Fruit is less than above range, the electric conductivity between active material may be caused to reduce, cell resistance increase, the capacity drop of unit volume It is low.
<The knot of the cathode of 2-3-4. lithium metal composite oxides material and use lithium metal composite oxide material Structure, physical property, preparation method>
As the lithium metal composite oxide material as negative electrode active material, as long as energy occlusion/releasing lithium, then do not have It is specifically limited, but the lithium-contained composite metal oxide material of titanium is preferably comprised, composite oxides (the following letter of more preferable lithium and titanium Referred to as " lithium-titanium composite oxide ").That is, when make in anode for nonaqueous electrolyte secondary battery active material contain have spinelle During the lithium-titanium composite oxide of structure, output resistance can decline to a great extent, thus particularly preferably.
It is also preferable to the lithium or titanium in lithium-titanium composite oxide be by other metallic elements, for example, selected from Na, K, Co, Al, Composite oxides obtained from least one kind of element in Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb replaces.
Above-mentioned metal oxide is the lithium-titanium composite oxide represented with general formula (4), meet in the general formula (4) 0.7≤x≤ 1.5th, when 1.5≤y≤2.3,0≤z≤1.6, stable structure of the lithium ion in doping/dedoping, therefore preferably.
LixTiyMzO4(4)
[in general formula (4), M represents at least one kind of in Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element.]
In the composition represented by above-mentioned general formula (4), following (a), (b), the battery performance of (c) structure can obtain well Balance, therefore particularly preferably.
(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
As particularly preferred typical composition in above-claimed cpd, can be listed below：(a) it is Li in4/3Ti5/3O4、(b) In be Li1Ti2O4, in (c) be Li4/5Ti11/5O4.In addition, for the structure of Z ≠ 0, it can be mentioned, for example Li4/3Ti4/3Al1/3O4Make To preferably constitute.
It is used as the lithium-titanium composite oxide of negative electrode active material in the present invention in addition to above-mentioned requirements to be met, further preferably Further meet at least one kind of in the features such as physical property and the shape described in following (1)~(13), particularly preferred 2 kinds of satisfaction simultaneously More than.
(1) BET specific surface area
The value of the BET specific surface area of lithium-titanium composite oxide measured using BET method, as negative electrode active material is preferred For 0.5m2·g-1Above, it is more preferably 0.7m2·g-1Above, it is more preferably 1.0m2·g-1Above, especially preferably 1.5m2·g-1More than, and preferably 200m2·g-1Below, it is more preferably 100m2·g-1Below, it is more preferably 50m2·g-1Below, it is especially preferably 25m2·g-1Below.If BET specific surface area is less than above range, during as negative material with it is non- The response area of water electrolysis liquid phase contact reduces, and output resistance may be caused to increase.When on the other hand, more than above range, meeting The plane of crystal and end face part for causing titanium-containing metal oxide increase, and thus trigger crystal defect (askew), and then can cause Irreversible capacity becomes very important, so as to obtain preferable battery.
It is carried out as follows using during BET method measurement the specific area：Using surface area meter (Okura development make it is complete from Dynamic surface area determination unit), after carrying out predrying in 15 minutes to sample at nitrogen stream, 350 DEG C, using nitrogen compared with air The relative pressure of pressure is accurately adjusted to 0.3 nitrogen helium mixed gas, by using 1 method of N2 adsorption BET of gas flow method It is measured.The specific surface area being obtained using the measure is defined as to the BET specific surface area of lithium-titanium composite oxide in the present invention.
(2) volume-based average particle size
It is compound that the average grain diameter (median particle diameter) of the volume reference measured using laser diffraction/scattering method is defined as lithium titanium The volume-based average particle size (being secondary particle size in the case of primary particle agglomeration forms secondary) of oxide.
The volume-based average particle size of lithium-titanium composite oxide is usually 0.1 μm or more, is preferably 0.5 μm or more, is more excellent Elect 0.7 μm or more, and usually less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm, especially preferably 25 μm as Below.
Volume-based average particle size is measured using following methods：Lithium-titanium composite oxide is dispersed in live as surface Property agent polyoxyethylene (20) Span-20 0.2 mass % aqueous solutions (about 10mL) in, and using laser Diffraction/scattering formula particle size distribution meter (LA-700 of Ku Chang manufacturing companies manufacture) is measured.By what is be obtained by the measure Median particle diameter is defined as the volume-based average particle size of carbonaceous material in the present invention.
If the volume average particle size of lithium-titanium composite oxide is less than above range, needed when preparing electrode a large amount of viscous Agent is tied, as a result, battery capacity may be caused to reduce.When on the other hand, more than above range, when preparing electrode pad, hold Non-uniform applicator surface is easily formed, on battery preparation section not preferably.
(3) primary particle average grain diameter
In the case where primary particle agglomeration forms secondary, the primary particle average grain diameter of lithium-titanium composite oxide is led to Often it is 0.01 μm or more, is preferably 0.05 μm or more, more preferably 0.1 μm or more, especially preferably 0.2 μm or more, and usually For less than 2 μm, preferably less than 1.6 μm, more preferably less than 1.3 μm, especially preferably less than 1 μm.If at the beginning of volume reference Grade average particle size is more than above range, then is difficult to the glomerate secondary of shape, brings harmful effect to powder fillibility, Or specific surface area reduces, and thus may cause the reduction of the battery performances such as output characteristics.In addition, if volume reference primary particle is put down Equal grain size is less than above range, then due to usually crystallizing not exclusively, thus may cause the secondary electricity such as poorly reversible of charge and discharge The problem of pond hydraulic performance decline.
It should be noted that primary particle diameter is observed to measure by using scanning electron microscope (SEM).Specifically, exist It confirms under the multiplying power of particle, in the photo that such as multiplying power is 10000~100000 times, for arbitrary 50 primary grains Son, is obtained the greatest length of intercept obtained by the left bounding lines straight line relative to horizontal direction of primary particle, then is averaged and Primary particle average grain diameter is obtained.
(4) shape
The shape of particle of lithium-titanium composite oxide can be used the bulk used in the past, polyhedral, it is spherical, oval it is spherical, Plate, needle-shaped, column etc., wherein, preferably primary particle agglomeration formed secondary, and secondary be preferably shaped to it is spherical It is or oval spherical.
In general, electrochemical element, with charge and discharge process, the active material in electrode can expand contraction, therefore, Easily trigger the destruction of active material and the deterioration of conductive break-make etc. in the presence of the stress.As a result, with only existing primary grain The single particle active material of son is compared, and preferably primary particle agglomeration forms the situation of secondary, this is because, being formed secondary During particle, dilation stress is mitigated, and can prevent from deteriorating.
In addition, compared with the isometric orientation particle of plate, the situation of more preferably spherical or oval spherical particle, this be by In, orientation of the spherical or oval spherical particle in electrode moulding is weaker, and the dilation of electrode is also less during charge and discharge, and The also uniform mixing easy to implement when carrying out the mixing with conductive material when preparing electrode.
(5) tap density
The tap density of lithium-titanium composite oxide is preferably 0.05gcm-3Above, it is more preferably 0.1gcm-3Above, Further preferably 0.2gcm-3Above, it is especially preferably 0.4gcm-3More than, and preferably 2.8gcm-3Below, it is more excellent Elect 2.4gcm as-3Below, it is especially preferably 2gcm-3Below.If tap density is less than above range, it is used as During cathode, packed density is difficult to improve, and interparticle contact area is reduced, thus interparticle resistance may be caused to increase, Output resistance increases.In addition, when being more than above range, interparticle gap is very few in electrode, and the flow path of nonaqueous electrolytic solution is reduced, Thus output resistance may be caused to increase.
Tap density can be measured by following methods：Sample is made to drop into 20cm after by mesh for 300 μm of sieve3 Jolt ramming container in, until sample is filled to the upper surface of container, then using powder density analyzer (for example, Seishin is looked forward to The Tap densor of industry company manufacture) carry out the vibration that 1000 lengths of stroke are 10mm, thus when volume and sample weight Density is obtained in amount.The tap density calculated using the measure is defined as to the tap density of lithium-titanium composite oxide in the present invention.
(6) circularity
When measuring spherical degree of the circularity as lithium-titanium composite oxide, circular degree is within following ranges. Circularity is defined with following formula：Circularity=(there is the perimeter with particle projection of shape equivalent circular of the same area)/(particle projects The perimeter of shape).When circularity is 1, become theoretical proper sphere.
The circularity of lithium-titanium composite oxide closer to 1 then more preferably, be usually more than 0.10, be preferably 0.80 with Above, more preferably more than 0.85, especially preferably more than 0.90.The more big then high current density charge-discharge characteristic of circularity is higher. Thus, when circularity is less than above range, the fillibility decline of negative electrode active material, interparticle resistance increase, and may lead Short time high current density charge-discharge characteristic is caused to reduce.
Circularity is by using flow-type particle image analysis device (for example, what Sysmex Industrial companies manufactured FPIA) it is measured.About 0.2g samples are dispersed in polyoxyethylene (20) sorbitan list bay as surfactant In 0.2 mass % aqueous solutions (about 50mL) of acid esters, and after being irradiated 1 minute with the output power of 60W with the ultrasonic wave of 28kHz, It is detection range to specify 0.6~400 μm, and particle of the grain size in 3~40 μ ms is measured.By what is be obtained using the measure Circularity is defined as the circularity of lithium-titanium composite oxide in the present invention.
(7) draw ratio
The draw ratio of lithium-titanium composite oxide is usually more than 1, and usually less than 5, be preferably less than 4, more preferably 3 Below, less than 2 are especially preferably.When draw ratio is more than above range, striped may be generated when pole plate is made, can not be obtained Uniform coated face is obtained, causes the reduction of short time high current density charge-discharge characteristic.It should be noted that the lower limit of above range For the theory lower bound value of the draw ratio of lithium-titanium composite oxide.
Draw ratio is amplified observation to measure by using scanning electron microscope to lithium-titanium composite oxide particle.Selection is fixed Arbitrary 50 particles on metal end face less than 50 μm thick, rotation tilt the objective table for being fixed with sample, measure respectively The most major diameter A and perpendicular most minor axis B of particle when 3-dimensional is observed, and the average value of A/B is obtained.It will be obtained using the measure Draw ratio (A/B) be defined as the draw ratio of lithium-titanium composite oxide in the present invention.
(8) manufacturing method of negative electrode active material
As the manufacturing method of lithium-titanium composite oxide, if having no without departing from the gist of the present invention it is special Limitation, can enumerate several method.As the manufacturing method of inorganic compound, usual way can be used.
For example, can enumerate the titanium materials such as titanium oxide substance, as needed and the raw material of other elements that uses and LiOH、Li2CO3、LiNO3Li sources is waited uniformly to mix and are sintered the method for obtaining active material at high temperature.
Particularly, it is contemplated that various methods prepare spherical or oval spherical active material.It, can as an example therein Enumerate following methods：By the titanium materials such as titanium oxide substance and the as needed dissolving of the raw material of other elements for using or powder It is broken to be scattered in water equal solvent, pH value is adjusted while being stirred, is made and collects spherical precursor, as needed by it It is dry, then add in LiOH, Li2CO3、LiNO3Li sources are waited, and are sintered at high temperature, so as to obtain the method for active material.
In addition, as another example, following methods can be enumerated：By the titanium materials such as titanium oxide substance and as needed and use Other elements raw material dissolving or grinding dispersion in water equal solvent, be dried shaping using spray dryer etc., Spherical or oval spherical precursor is made, adds in LiOH, Li thereto2CO3、LiNO3Li sources are waited, and are sintered at high temperature, so as to The method for obtaining active material.
Alternatively method can also enumerate following methods：By the titanium materials such as titanium oxide substance, LiOH, Li2CO3、 LiNO3Wait Li sources and as needed and the dissolving of the raw material of other elements for using or grinding dispersion in water equal solvent, profit Shaping is dried with spray dryer etc., spherical or oval spherical precursor is made, it is sintered at high temperature, so as to obtain The method of active material.
In addition, in above-mentioned operation, can also in the metal oxide structures of titaniferous and/or with phase containing titanyl compound There are other elements in addition to Ti in the form of contact, such as：Al、Mn、Ti、V、Cr、Mn、Fe、Co、Li、Ni、Cu、Zn、 Mg、Ga、Zr、C、Si、Sn、Ag.By containing above-mentioned element, the control of the operating voltage, capacity to battery can be realized.
(9) making of electrode
Any known method may be employed to make electrode.For example, electrode can be formed by following methods：To negative Adhesive, as needed solvent, thickener, conductive material, packing material of addition etc. are added in the active material of pole, slurry is made Material is coated on the current collector and is dried, then forms electrode by suppressing.
Battery close on nonaqueous electrolytic solution injection process before stage, the reason of the negative electrode active material layer on each face Think that thickness is usually 15 μm or more, is preferably 20 μm or more, more preferably 30 μm or more, the upper limit is less than 150 μm, is preferably Less than 120 μm, more preferably less than 100 μm.During more than the scope, due to nonaqueous electrolytic solution be difficult to infiltrate into current collection body interface it is attached Closely, the reduction of high current density charge-discharge characteristic may be caused.In addition, if less than the scope, then collector may be caused opposite Increase in the volume ratio of negative electrode active material, battery capacity is reduced.Furthermore it is possible to negative electrode active material is subjected to roller shaping to make Make pellet electrode or mosaic electrode is made by compression forming.
(10) collector
As the collector that can be maintained negative electrode active material, any known collector can be used.As cathode Collector, the metal materials such as copper, nickel, stainless steel, nickel-plated steel can be enumerated, wherein, from processing simplification and cost from the aspect of, Particularly preferred copper.
In addition, the shape as collector, when collector is metal material, it can be mentioned, for example metal foil, metal cylinder, Wire coil, metallic plate, metallic film, expansion alloy, perforated metal, foaming metal etc..Wherein, preferably comprise copper (Cu) and/ Or the metal foil film of aluminium (Al), more preferable copper foil, aluminium foil, further preferably utilize rolled copper foil and utilize electricity that rolling process obtains The electrolytic copper foil that solution obtains, it is above-mentioned in any one can be used as collector.
In addition, when copper foil thickness be less than 25 μm when, can with use intensity higher than fine copper copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu-Cr-Zr alloys etc.).Further, since the proportion of aluminium foil is lighter, as collector in use, can make electricity The weight in pond is reduced, thus is preferably used.
In the collector formed in the copper foil by being prepared using rolling process, arranged since copper is crystallized along rolling direction, because Even if this is at an acute angle by cathode crimping very close or curling, still it is not easily broken, is applicable to small cylinder shape battery.
Electrolytic copper foil can be obtained by following methods：For example, metal drum is immersed in dissolved with the non-aqueous of copper ion In electrolyte, galvanization while rotating the drum so that copper is precipitated on drum surface, is removed to obtain electrolytic copper foil.Also It can utilize electrolysis that copper is made to be precipitated on above-mentioned rolled copper foil surface.The one or both sides of copper foil can also be carried out at roughening Reason or surface treatment (for example, thickness is in base treatments such as the chromic acid salt treatment of several nm~1 μm or so, Ti etc.).
In addition, current collection structure base board further preferably has following physical property.
(10-1) average surface roughness (Ra)
The negative electrode active material film forming face of current collection structure base board specified in the method recorded for JISB0601-1994 Average surface roughness (Ra) be not particularly limited, be usually more than 0.01 μm, be preferably 0.03 μm or more, and usually Less than 1.5 μm, preferably less than 1.3 μm, more preferably less than 1.0 μm.
This is because, when current collection structure base board average surface roughness (Ra) within the above range when, can expect good Charge/discharge cycle characteristics.In addition, increasing with the interfacial area of active material film, carried with the adhesiveness of negative electrode active material film It is high.Wherein, had no for the upper limit value of average surface roughness (Ra) it is specifically limited, when average surface roughness (Ra) is more than At 1.5 μm, it is difficult to the paper tinsel of thickness practicality when being used as battery is obtained, therefore the average surface below 1.5 μm of generally use is thick Rugosity (Ra).
(10-2) tensile strength
So-called tensile strength, refer to the sectional area of required maximum pull divided by test film when test film is broken and Obtained value.Tensile strength in the present invention uses the dress identical with the record of JISZ2241 (material during tensile test method) It puts and method measures.
It is not particularly limited for the tensile strength of current collection structure base board, is usually 50Nmm-2Above, it is preferably 100N mm-2Above, it is more preferably 150Nmm-2More than.Tensile strength values are more high then more preferred, it is contemplated that industrial accessibility is led to It is often 1000Nmm-2Below.If the current collection structure base board that tensile strength is high, then can inhibit in charge/discharge process by The cracking of active material film expansion/current collection structure base board caused by contraction, can obtain good cycle characteristics.
(10-3) 0.2% yield strength
So-called 0.2% yield strength, load necessary to referring to (permanent) strain of the plasticity for generating 0.2%, applies After the load, even if except unloading, 0.2% deformation is still kept.0.2% yield strength utilizes identical with measuring tensile strength Device and method measures.
Had no for 0.2% yield strength of current collection structure base board it is specifically limited, be usually 30Nmm-2Above, it is preferably 100N·mm-2Above, it is especially preferably 150Nmm-2More than.The value of 0.2% yield strength is more high then more preferred, from industry The angle of accessibility is set out, it is often preferred that 900Nmm-2Below.If the current collection structure base board that 0.2% yield strength is high, The plastic deformation of the current collection structure base board as caused by active material film expansion/contraction in charge/discharge process can then be inhibited, Good cycle characteristics can be obtained.
The thickness of (10-4) collector
Collector can be any thickness, but usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and Usually below 1mm, preferably less than 100 μm, more preferably less than 50 μm.When the thickness of collector is less than 1 μm, due to strong Degree can decline, thus coating may be caused to become difficult.In addition, when thickness is more than 100 μm, then electrode shape may be caused to send out The deformations such as raw curling.It should be noted that collector can be netted.
(11) thickness ratio of collector and active material layer
It is had no for the thickness ratio of collector and active material layer specifically limited, but " (injects it closing on nonaqueous electrolytic solution The thickness of active material layer on preceding single face)/(thickness of collector) " value be usually less than 150, be preferably 20 with Under, more preferably less than 10, and usually more than 0.1, be preferably more than 0.4, more preferably more than 1.If collector is with bearing The thickness ratio of pole active material layer is more than above range, then during high current density charge and discharge, collector may be due to Joule heat Trigger heat release.In addition, when thickness ratio is less than above range, collector increases compared with the volume ratio of negative electrode active material, can Battery capacity can be caused to reduce.
(12) electrode density
It is not particularly limited, is present in negative on collector for electrode structure when negative electrode active material to be made to electrode The density of pole active material is preferably 1gcm-3Above, it is more preferably 1.2gcm-3Above, it is more preferably 1.3gcm-3Above, it is especially preferably 1.5gcm-3More than, and preferably 3gcm-3Below, it is more preferably 2.5gcm-3Below, into one Step is preferably 2.2gcm-3Below, it is especially preferably 2gcm-3Below.When the density for the active material being present on collector During more than above range, the bonding of collector and negative electrode active material dies down, and electrode may be caused to be separated with active material.Separately Outside, if less than above range, the electric conductivity between negative electrode active material may be caused to reduce, cell resistance increases.
(13) adhesive
As the adhesive for bonding negative electrode active material, as long as used when being manufactured compared with nonaqueous electrolytic solution and electrode The material of solvent-stable, then be not particularly limited.
As specific example, polyethylene, polypropylene, polyethylene terephthalate, poly-methyl methacrylate can be enumerated The resins family macromolecule such as ester, polyimides, aromatic polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), isoamyl two The rubber-like macromolecules such as alkene rubber, butadiene rubber, fluorubber, NBR (nitrile rubber), EP rubbers；Styrene-butadiene- Styrene block copolymer and its hydride；EPDM (ethylene/propylene/diene terpolymer), styrene-ethylene-fourth two The thermoplastic elastomer (TPE)s such as alkene-styrol copolymer, styrene-isoprene-styrene block copolymer and its hydride shape is high Molecule；Syndiotactic 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymerization The soft resinous macromolecule such as object；Kynoar, polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer The fluorine class macromolecule such as object；Polymeric composition with ionic conductivity of alkali metal containing ion (particularly lithium ion) etc..On Material is stated to can be used alone, it can also in any combination and two or more is applied in combination in ratio.
As for forming the solvent of slurry, as long as it can dissolve or disperse negative electrode active material, adhesive, Yi Jigen The thickener and the solvent of conductive material used according to needs, is not particularly limited its species, can use aqueous molten Any one of agent or organic solvent.
As the example of aqueous solvent, water, alcohol etc. can be enumerated；As the example of organic solvent, N- methyl pyrroles can be enumerated Pyrrolidone (NMP), dimethylformamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl Base triamine, N, N- dimethylamino propylamines, tetrahydrofuran (THF), toluene, acetone, dimethyl ether, dimethyl acetamide, hexamethyl Phosphamide, dimethyl sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc..Particularly, it is excellent when using aqueous solvent It is selected in using addition dispersant etc. while thickener, and it is slurried that the latex such as SBR is used to carry out.In addition, above-mentioned solvent can be with 1 kind is used alone, it can also in any combination and two or more is applied in combination in ratio.
Adhesive is usually more than 0.1 mass % compared with the ratio of negative electrode active material, be preferably 0.5 mass % with Upper, more preferably more than 0.6 mass %, and usually below 20 mass %, preferably below 15 mass %, more preferably 10 matter Measure below %, especially preferably below 8 mass %.If adhesive is more than above-mentioned model compared with the ratio of negative electrode active material It encloses, then the ratio for not having contributive adhesive in amount of binder to battery capacity increases, and battery capacity may be caused to reduce.Separately When outside, less than above range, the strength reduction of negative electrode may be caused, it is not preferred from the aspect of the manufacture craft of battery.
Particularly, when containing in main component using rubber-like macromolecules of the SBR as representative, adhesive is compared with active matter The ratio of matter is usually more than 0.1 mass %, is preferably more than 0.5 mass %, more preferably more than 0.6 mass %, and usual For below 5 mass %, preferably below 3 mass %, more preferably below 2 mass %.
In addition, when containing in main component using fluorine class macromolecule of the Kynoar as representative, compared with active matter The ratio of matter for more than 1 mass %, be preferably more than 2 mass %, more preferably more than 3 mass %, be usually 15 mass % with Under, be preferably below 10 mass %, more preferably below 8 mass %.
Thickener is commonly used in adjusting the viscosity of slurry.As thickener, specifically limited, specific enumerable carboxymethyl is had no Cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein And their salt etc..Above-mentioned thickener can be used alone, can also in any combination and two or more is applied in combination in ratio.
In addition, when using thickener, thickener compared with the ratio of negative electrode active material be usually 0.1 mass % with Upper, preferably more than 0.5 mass %, more preferably more than 0.6 mass %, and usually below 5 mass %, preferably 3 matter Measure below %, more preferably below 2 mass %.If thickener is less than above range compared with the ratio of negative electrode active material, Significantly reducing for coating may then be caused.On the other hand, when more than above range, active material in negative electrode active material layer Shared ratio reduces, and resistance increases between the problem of battery capacity may being triggered to reduce and negative electrode active material.
<2-4. anode>
It is illustrated below for the anode used in the non-aqueous electrolyte secondary battery of the present invention.
<2-4-1. positive active material>
It is illustrated below for for the positive active material of anode.
(1) form
As a positive electrode active material, it is not particularly limited as long as it can electrochemically occlude/release lithium ion, for example, excellent Select the substance containing lithium and at least one kind of transition metal.As specific example, lithium-compound transition metal oxide can be enumerated, contained The transition metal phosphate compound of lithium.
As the transition metal in lithium-compound transition metal oxide, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc., make For the specific example of lithium-compound transition metal oxide, LiCoO can be enumerated2Wait lithium-cobalt composite oxides, LiNiO2Wait lithiums-nickel Composite oxides, LiMnO2、LiMn2O4、Li2MnO4Wait lithium-manganese composite oxides, with Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Transition metal in the above-mentioned lithium-compound transition metal oxide of other metal substitutes such as Cu, Zn, Mg, Ga, Zr, Si as main body Composite oxides etc. obtained from a part in atom.
As the specific example of composite oxides obtained from replacement, it can be mentioned, for example LiNi0.5Mn0.5O2、 LiNi0.85Co0.10Al0.05O2、LiNi0.33Co0.33Mn0.33O2、LiMn1.8Al0.2O4、LiMn1.5Ni0.5O4Deng.
As the transition metal in the transition metal phosphate compound containing lithium, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu Deng as the specific example of the transition metal phosphate compound containing lithium, it can be mentioned, for example LiFePO4、Li3Fe2(PO4)3、 LiFeP2O7Wait ferric phosphates class, LiCoPO4Wait cobalt phosphates class, with Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, As one in the transition metal atoms of main body in the above-mentioned lithium of other metal substitutes such as Zr, Nb, Si-transition metal phosphate compound Compound obtained from part etc..
(2) surface coats
Can also use has the object with forming positive active material as main body in above-mentioned positive active material surface attachment Matter forms different substance (following, suitably referred to as " surface attachment ").As the example of surface attachment, can enumerate The oxides such as aluminium oxide, silica, titanium oxide, zirconium oxide, magnesia, calcium oxide, boron oxide, antimony oxide, bismuth oxide, sulfuric acid The sulfate such as lithium, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, the carbonate such as lithium carbonate, calcium carbonate, magnesium carbonate etc..
These surface attachments can be made to be attached to positive active material surface by following methods, for example, making surface Attachment material is dissolved or suspended in solvent, and makes its impregnation addition in positive active material, the side being then dried again Method；Surface attachment precursor is made to be dissolved or suspended in solvent, and makes its impregnation addition in positive active material, Ran Houtong Cross the method that heating etc. reacts it；Surface attachment is added in positive active material precursor, is carried out at the same time sintering Method etc..
Compared with the quality of positive active material, the quality for being attached to the surface attachment on positive active material surface is led to Often be more than 0.1ppm, be preferably more than 1ppm, more preferably more than 10ppm, and usually less than 20%, be preferably 10% with Under, more preferably less than 5%.
Nonaqueous electrolytic solution can be inhibited by surface attachment, oxidation reaction occurs on positive active material surface, and then Improve battery life.But if adhesion amount is less than above range, effect can not fully demonstrate；And when more than above-mentioned model When enclosing, the discrepancy of lithium ion can be caused to hinder, resistance may be caused to increase, therefore preferred above range.
(3) shape
The shape of particle as a positive electrode active material, can use bulk, polyhedral, spherical, the spherical, plate of ellipse, Shape used by needle-shaped, column etc. is previous, wherein, preferably primary particle agglomeration forms secondary, the secondary It is preferably shaped to spherical or oval spherical.
In general, electrochemical element, with charge and discharge, the active material in electrode can expand contraction, therefore easily exist Trigger the destruction of active material and the deterioration of conductive break-make etc. under the stress.As a result, with only existing the single of primary particle Particle active material is compared, and preferably primary particle agglomeration forms the situation of secondary, this is because, aggregation forms secondary When, dilation stress is mitigated, and can prevent from deteriorating.
In addition, compared with the isometric orientation particle of plate, the situation of more preferably spherical or oval spherical particle, this be by In, orientation of the spherical or oval spherical particle in electrode moulding is weaker, and the dilation of electrode is also less during charge and discharge, and The also uniform mixing easy to implement when carrying out the mixing with conductive material when preparing electrode.
(4) tap density
The tap density of positive active material is usually 1.3gcm-3Above, it is preferably 1.5gcm-3Above, more preferably For 1.6gcm-3Above, it is especially preferably 1.7gcm-3More than, and usually 2.5gcm-3Below, it is preferably 2.4g cm-3Below.
By using the high metal compound oxide powder of tap density, highdensity positive electrode active material layer can be formed. Thus, if the tap density of positive active material is less than above range, necessary to positive electrode active material layer is formed The amount of decentralized medium increases, while the necessary amount of conductive material and binding agent increases, and positive active material is in positive active material Filling rate in layer is restricted, and battery capacity may be caused to be restricted.In addition, tap density is usually more big more preferably, There is no the special upper limit, but if less than above range, then in positive electrode active material layer using nonaqueous electrolytic solution as medium lithium from The diffusion of son becomes the factor for determining speed, load characteristic may be caused to reduce.
Tap density measures as follows：Sample is made to drop into 20cm after by mesh for 300 μm of sieve3Shake In real container, until volume of the sample full of container, then using powder density analyzer (for example, Seishin enterprise-like corporations system The Tap densor made) carry out the vibration that 1000 lengths of stroke are 10mm, thus when volume and sample weight jolt ramming is obtained Density.The tap density calculated using the measure is defined as to the tap density of positive active material in the present invention.
(5) median particle diameter d50
The median particle diameter d50 of the particle of positive active material is (when primary particle agglomeration forms secondary, for secondary grain Footpath) it is measured using laser diffraction/scattering formula particle size distribution device.
Median particle diameter d50 is usually 0.1 μm or more, is preferably 0.5 μm or more, more preferably 1 μm or more, especially preferably 3 μm or more, and usually less than 20 μm, preferably less than 18 μm, more preferably less than 16 μm, especially preferably less than 15 μm. If median particle diameter d50 is less than above range, the high product of volume density possibly can not be obtained, and when more than above range When, then since the diffusion of lithium in particle needs the time, battery behavior may be caused to reduce or anode is being made, is adopting It is with solvent that active material and conductive material or adhesive is slurried and then when being coated into film-form when carrying out, generate striped etc. Situation.
It it should be noted that can also be by the way that two or more positive active material with different median particle diameter d50 be appointed Meaning ratio mixes to improve the fillibility when anode is made.
Median particle diameter d50 can be measured by following methods：It is situated between using the sodium hexametaphosphate solution of 0.1 mass % to be scattered Matter, using the LA-920 that Ku Chang manufacturing companies manufacture as particle size distribution meter, after the ultrasonic wave carried out 5 minutes disperses, if Location survey is determined refractive index and is measured for 1.24.
(6) primary particle average grain diameter
When primary particle agglomeration forms secondary, the primary particle average grain diameter of positive active material is usually 0.01 μm or more, be preferably more than 0.05 μm, more preferably 0.08 μm or more, be especially preferably 0.1 μm or more, and usually 3 μm with Under, be preferably less than 2 μm, more preferably less than 1 μm, be especially preferably less than 0.6 μm.This is because, if primary particle is put down Equal grain size is more than above range, then is hardly formed spherical secondary, can cause harmful effect, Huo Zhehui to powder fillibility Specific surface area is caused significantly to reduce, thus may cause the reduction of the battery performances such as output characteristics；In addition, if primary particle is averaged Grain size is less than above range, then normally results in that crystallization is incomplete, and then may trigger the secondary electricity such as poorly reversible of charge and discharge The reduced performance in pond.
In addition, primary particle average grain diameter can be observed by using scanning electron microscope (SEM) and measured.Specifically, In multiplying power is 10000 times of photo, for arbitrary 50 primary particles, be obtained the left bounding lines of primary particle compared with The greatest length of intercept obtained by the straight line of horizontal direction, then be averaged that primary particle average grain diameter is obtained.
(7) BET specific surface area
The value of the BET specific surface area of the positive active material measured using BET method is usually 0.2m2·g-1Above, preferably For 0.3m2·g-1Above, it is more preferably 0.4m2·g-1More than, and usually 4.0m2·g-1Below, it is preferably 2.5m2·g-1With Under, more preferably 1.5m2·g-1Below.If the value of BET specific surface area is less than above range, battery performance is easily reduced. On the other hand, if it exceeds above range, then tap density is not easy to improve, and may cause the painting when forming positive active material Cloth reduces.
BET specific surface area is measured using surface area meter (the full-automatic surface area determination unit that Okura development is made). Predrying in 30 minutes is carried out to sample at nitrogen stream, 150 DEG C, is then used nitrogen is accurate compared with the relative pressure of atmospheric pressure 0.3 nitrogen helium mixed gas is really adjusted to, 1 method of N2 adsorption BET carried out by using gas flow method is measured.It will The specific surface area being obtained using the measure is defined as the BET specific surface area of positive active material in the present invention.
(8) manufacturing method of positive active material
Manufacturing method as a positive electrode active material, without departing from the present invention main points scope then without special limit System, can enumerate several method, but as the manufacturing method of inorganic compound, usual way can be used.
Particularly, it is contemplated that various methods prepare spherical or oval spherical active material.For example, as one of method, Following methods can be enumerated：By the transition metal such as transition metal nitrate, sulfate raw material with as needed and use its The raw material dissolving of its element or grinding dispersion in water and other solvents, adjust pH while being stirred, prepare and collect Spherical precursor is as needed dried the precursor, then adds in LiOH, Li2CO3、LiNO3Li sources are waited, and at high temperature Sintering, so as to obtain the method for active material.
In addition, the example as another method, can enumerate following methods：By transition metal nitrate, sulfate, hydroxide The transition metal such as object, oxide raw material and the as needed dissolving of the raw material of other elements for using or grinding dispersion In water equal solvent, using spray dryer etc. to its drying and moulding, spherical or oval spherical precursor is made, then adds thereto Enter LiOH, Li2CO3、LiNO3Li sources are waited, are sintered at high temperature, so as to obtain the method for active material.
Alternatively method can also enumerate following methods：By transition metal nitrate, sulfate, hydroxide, The transition metal such as oxide raw material and LiOH, Li2CO3、LiNO3Wait Li sources and other elements that are as needed and using Raw material dissolving or grinding dispersion in water equal solvent, shaping is dried to it using spray dryer etc., ball is made Shape or oval spherical precursor, it are sintered at high temperature, so as to obtain the method for active material.
<2-4-2. electrode structure and production method>
Hereinafter, illustrated for structure of anode being used in the present invention and preparation method thereof.
(1) production method of anode
Anode by formed on the current collector the positive electrode active material layer containing positive active material particle and binding agent and It is made.It can be prepared using the manufacture of the anode of positive active material using well known any means.I.e., it is possible to by positive-active Substance and binding agent and as needed and conductive material and thickener for using etc. carry out dry type mixing and sheet are made, then The flaky material is attached on positive electrode collector or these materials are dissolved or dispersed in liquid medium, slurry is made, and The slurry is coated on positive electrode collector and is dried, so as to form positive electrode active material layer on the current collector, and then is obtained Obtain anode.
Content of the positive active material in positive electrode active material layer is usually more than 10 mass %, is preferably 30 mass % Above, more than 50 mass %, and usually below 99.9 mass %, preferably below 99 mass % are especially preferably.This be by In, when the positive active material content in positive electrode active material layer be less than above range when, capacitance may be caused to become inadequate； And when content is more than above range, the intensity deficiency of anode may be caused.It should be noted that the positive-active in the present invention Material powder can be used alone, can also in any combination and ratio be applied in combination two or more with it is different composition or not With the positive electrode active material powder of powder property.
(2) conductive material
As conductive material, any known conductive material can be used.As specific example, it can be mentioned, for example copper, nickel etc. Metal material；The graphite such as native graphite, Delanium (graphite)；The carbon blacks such as acetylene black；The carbonaceous such as the amorphous carbon such as needle coke Material etc..Wherein, above-mentioned conductive material can be used alone, can also in any combination and ratio be applied in combination 2 kinds with On.
In positive electrode active material layer contained conductive material be usually more than 0.01 mass %, be preferably 0.1 mass % with Upper, more preferably more than 1 mass %, and usually below 50 mass %, preferably below 30 mass %, more preferably 15 matter Measure below %.When content is less than above range, electric conductivity may be caused insufficient.And when more than above range, it may cause Battery capacity reduces.
(3) binding agent
As long as the binding agent used when manufacturing positive electrode active material layer is compared in manufacture nonaqueous electrolytic solution or electrode When used solvent-stable binding agent, then be not particularly limited.
During using rubbing method, as long as the material being dissolved or dispersed in the liquid medium used during manufacture electrode is i.e. Can, as specific example, it can be mentioned, for example polyethylene, polypropylene, polyethylene terephthalate, poly-methyl methacrylates The resins family macromolecule such as ester, aromatic polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), NBR (nitrile rubber), The rubber-like macromolecule such as fluorubber, isoprene rubber, butadiene rubber, EP rubbers；S-B-S is embedding Section copolymer or its hydride, EPDM (ethylene/propylene/diene terpolymer), styrene ethylene butadiene-ethylene are common The thermoplastic elastomer (TPE)s shape macromolecule such as polymers, styrene-isoprene-styrene block copolymer or its hydride；Between advise it is vertical The soft resins such as structure 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers Shape macromolecule；The fluorine such as Kynoar (PVdF), polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer Family macromolecule；Polymeric composition of ionic conductivity with alkali metal ion (particularly lithium ion) etc..Above-mentioned substance can It, can also in any combination and two or more is applied in combination in ratio to be used alone a kind.
Ratio in positive electrode active material layer shared by binding agent is usually more than 0.1 mass %, be preferably 1 mass % with Upper, more preferably more than 3 mass %, and usually below 80 mass %, preferably below 60 mass %, more preferably 40 matter Measure below %, especially preferably below 10 mass %.If the ratio of binding agent be less than above range, positive active material without Method is sufficiently maintained, and may cause the degradation of cell performance such as mechanical strength deficiency, the cycle characteristics of anode.In addition, more than upper When stating scope, then battery capacity or electric conductivity may be triggered to reduce.
(4) liquid medium
As for forming the liquid medium of slurry, as long as can dissolve or disperse positive active material, conductive material, Binding agent and the as needed solvent of thickener that uses, are not particularly limited its species, can use aqueous Any one of solvent and organic solvent.
The example of aqueous medium, it can be mentioned, for example blending agents of water, alcohol and water etc..As the example of organic medium, It can enumerate：The fat hydrocarbons such as hexane；The arenes such as benzene,toluene,xylene, methyl naphthalene；The heterocyclic compounds such as quinoline, pyridine； The ketones such as acetone, methyl ethyl ketone, cyclohexanone；The esters such as methyl acetate, methyl acrylate；Diethylenetriamines, N, N- dimethylaminos The amines such as base propylamine；The ethers such as ether, tetrahydrofuran (THF)；N-Methyl pyrrolidone (NMP), dimethylformamide, dimethyl The amides such as acetamide；Aprotic polar solvents such as hexamethyl phosphoramide, dimethyl sulfoxide etc..It is given an account of on it should be noted that Matter can be used alone, can also in any combination and two or more is applied in combination in ratio.
(5) thickener
When using aqueous medium as forming the liquid medium of slurry, it is preferable to use thickeners and butadiene-styrene rubber (SBR) etc. latex is slurried to carry out.Thickener usually can be used to adjust the viscosity of slurry.
As thickener, system limit, specific enumerable carboxymethyl are had no in the range of the effect of the present invention is not significantly limited Cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein And their salt etc..Above-mentioned thickener can be used alone, can also in any combination and two or more is applied in combination in ratio.
In addition, during using thickener, thickener is usually more than 0.1 mass %, preferably compared with the ratio of active material For more than 0.5 mass %, more preferably more than 0.6 mass %, and usually below 5 mass %, be preferably below 3 mass %, More preferably below 2 mass %.If less than above range, significantly reducing for coating may be caused, and when more than above-mentioned During scope, the problem of active material ratio shared in positive electrode active material layer declines, battery capacity may be caused to reduce or The problem of resistance increases between positive active material.
(6) it is compacted
In order to improve the packed density of positive active material, preferably manually forcing press, roll squeezer etc. to by coating, Positive electrode active material layer is compacted obtained from drying.The density of positive electrode active material layer is preferably 1gcm-3Above, it is more excellent Elect 1.5gcm as-3Above, it is especially preferably 2gcm-3More than.Also, its upper limit is preferably 4gcm-3Below, more preferably In 3.5gcm-3Below, particularly preferably in 3gcm-3Below.If the density of positive electrode active material layer is more than above range, Then impregnability of the nonaqueous electrolytic solution near collector/reactive species interface reduces, and particularly, may cause in high current density Under charge-discharge characteristic reduce.And when the density of positive electrode active material layer is less than above range, it may cause between active material Electric conductivity reduce, cell resistance increase.
(7) collector
It as the material of positive electrode collector, is not particularly limited, can arbitrarily use well known material.As specific example, The metal materials such as aluminium, stainless steel, nickel plating, titanium, tantalum can be enumerated；The carbonaceous materials such as carbon cloth, carbon paper.Wherein, preferred metal materials, especially Its preferred aluminium.
As the shape of collector, when material is metal material, metal foil, metal cylinder, wire coil, gold can be enumerated Belong to plate, metallic film, expansion alloy, perforated metal, foaming metal etc.；When material is carbonaceous material, it is thin that carbon plate, carbon can be enumerated Film, carbon cylinder etc..In these materials, preferred metallic film.It should be noted that film can be suitably formed to be netted.
Collector can be any thickness, but usually more than 1 μm, be preferably 3 μm or more, be more preferably 5 μm or more, and Usually below 1mm, preferably less than 100 μm, more preferably less than 50 μm.If film thickness is less than above range, can It can cause the necessary intensity deficiency as collector.And when film thickness is more than above range, operability may be destroyed.
<2-5. partition plate>
It is short-circuit in order to prevent, partition plate is usually sandwiched between a positive electrode and a negative electrode.At this point, usually make the non-aqueous solution electrolysis of the present invention Liquid is soaked in the partition plate and uses.
It is not particularly limited for the material and shape of partition plate, as long as in the scope for the effect for not destroying the present invention significantly It is interior, it can arbitrarily use well known material and shape.Wherein, the material shape to stablize to the nonaqueous electrolytic solution of the present invention can be used Into resin, glass fibre, inorganic matter etc., it is preferable to use the porous sheet with excellent guarantor's fluidity or non-woven fabric-like forms Material etc..
As resin, the separator material of glass fibre, polyolefin, polytetrafluoroethyl-ne such as polyethylene, polypropylene can be used Alkene, polyether sulfone, glass filter etc..Wherein, preferably glass filter, polyolefin, particularly preferred polyolefin.These materials can be with 1 kind is used alone, it can also in any combination and two or more is applied in combination in ratio.
Aforementioned barriers can be any thickness, but usually 1 μm or more, be preferably more than 5 μm, be more preferably 10 μm with On, and usually less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm.If block board thickness is less than above range, Insulating properties or mechanical strength may then be caused to reduce.In addition, when block board thickness is more than above range, then it is not only possible to cause speed Spending the battery performances such as characteristic reduces, it is also possible to the energy density of non-aqueous electrolyte secondary battery entirety be triggered to decline.
In addition, when using porous sheet or non-woven fabrics, when porous materials are as partition plate, the voidage of partition plate is arbitrary , but usually more than 20%, be preferably more than 35%, more preferably more than 45%, and usually less than 90%, be preferably Less than 85%, it is more preferably less than 75%.If voidage is less than above range, film resistance increase may cause speed special Property be deteriorated.And when voidage is excessive compared with above range, the mechanical strength of partition plate may be caused to reduce, insulating properties declines.
In addition, the average pore size of partition plate is also arbitrary, but usually less than 0.5 μm, preferably less than 0.2 μm, and it is logical It is often 0.05 μm or more.If average pore size is more than above range, short circuit easily occurs.On the other hand, if average pore size Less than above range, then film resistance increase, speed characteristics may be caused to reduce.
On the other hand, as inorganic material, can be used the oxide-based, aluminium nitride such as aluminium oxide or silica or The Sulfateses such as silicon nitride etc. is nitride-based, barium sulfate or calcium sulfate can use the inorganic matter of shape of particle or fiber shape Material.
As form, the film shapes such as non-woven fabrics, woven fabric, microporous membrane can be used.As film shape, it is suitble to use hole The film that footpath is 0.01~1 μm, thickness is 5~50 μm.In addition to above-mentioned independent film shape, can also use it is following every Plate：It is formed using the binding agent of resin on the surface layer of anode and/or cathode and contains the compound porous of above-mentioned inorganic particles Partition plate obtained from layer.It is, for example, possible to use fluororesin makes aluminium oxide particles of 90% grain size less than 1 μm exist as binding agent Porous layer is formed on the two sides of anode.
<2-6. battery design>
[electrode group]
Electrode group can clip laminar structure obtained from aforementioned barriers are laminated above-mentioned positive plate and negative plate and folder Any one that above-mentioned positive plate and negative plate are wound into spiral helicine structure by aforementioned barriers.The volume of electrode group is in electricity Shared ratio (hereinafter referred to as electrode group occupancy rate) is usually more than 40%, is preferably more than 50% in the internal volume of pond, and logical Often it is less than 90%, is preferably less than 80%.If electrode group occupancy rate is less than above range, battery capacity can be caused to subtract It is small.And when electrode group occupancy rate be more than above range when, void space is small, when battery is in high temperature, can cause component expand or Trigger the vapour pressure rise of the liquid component of electrolyte, internal pressure rises, repeated charge performance and high temperature as battery The various characteristics such as preservation reduce, and then gas release valve may be needed to work that internal pressure is helped to discharge to outside.
[current collecting]
It is not particularly limited for current collecting, but in order to more effectively realize as caused by the nonaqueous electrolytic solution of the present invention The raising of flash-over characteristic is preferably made the structure for reducing wiring part and bonding part resistance.So, internal resistance is made During reduction, especially can excellently it be played using the effect of the nonaqueous electrolytic solution of the present invention.
In the case where electrode group is above-mentioned laminar structure, it is preferred to use following structures：By the steel core of each electrode layer Divide the structure for tying together that simultaneously welding is formed on terminal.Since when increasing the area of 1 piece of electrode, internal resistance increases therewith Add, thus it is also preferred that dropping low-resistance method using multiple terminals are set in electrode.It is above-mentioned winding-structure in electrode group In the case of, multiple pin configurations on anode and cathode can be respectively set, and be bundled on terminal to reduce internal resistance.
[battery case (exterior ケ ー ス)]
As the material of battery case, as long as to the substance that the nonaqueous electrolyte used is stablized, special limit is had no System.Specifically, the folded of the metals such as nickel-clad steel plate, stainless steel, aluminum or aluminum alloy, magnesium alloy class or resin and aluminium foil can be used Tunic (stacked film).From the aspect of lightweight, metal, stacked film it is preferable to use aluminum or aluminum alloy.
In the battery case for using above-mentioned metal class, the shell with following structures can be enumerated：By laser welding, Resistance welding, ultrasonic bonding are by mutual welding forms between metal sealing closed structure；Or it is used through resin washer upper The riveted structure stated metal class and formed.In the battery case for using above-mentioned stacked film, it can enumerate by will be between resin bed Mutual heat fusion and manufactured sealing closed structure etc..In order to improve leakproofness, can also be sandwiched between above-mentioned resin bed with For the different resin of the resin of stacked film.Particularly, closed to be formed to resin bed progress heat fusion by current-collecting terminals During structure, due to mutually being bonded between metal and resin, thus it is preferable to use the resin with polar group or polarity has been imported The modified resin of group is as the resin between being clamped into resin bed.
[protection element]
As above-mentioned protection element, the increased PTC of resistance when abnormal heat release or super-high-current are flowed through can be enumerated (Positive Temperature Coefficient, positive temperature coefficient), temperature fuse, thermistor, in abnormal heat release When drastically raise to block valve for flowing through electric current in circuit (current blocking valve) etc. by cell internal pressure or internal temperature.On The element that protection element preferably selects idle condition when high current conventional uses is stated, from the angle of height output, It is more preferably made and is also unlikely to be abnormal heat release or the design of thermal runaway even if there be no protection element.
[shell (exterior body)]
The non-aqueous electrolyte secondary battery of the present invention is typically by storages such as above-mentioned nonaqueous electrolytic solution, cathode, anode, partition plates In what is formed in shell.For the shell, there is no limit, can be arbitrary in the range of the effect of the present invention is not destroyed significantly Using well known shell.
Specifically, shell can be arbitrary material, but usually using for example implement the iron of nickel plating, stainless steel, aluminium or Its alloy, nickel, titanium etc..
In addition, the shape of shell is also arbitrary, can be such as cylinder type, square, cascade type, Coin shape, large size In arbitrary shape.
When making to contain the carbonic ester and " mono-fluor phosphate and/or difluorophosphoric acid salt " with halogen atom in nonaqueous electrolytic solution, The non-aqueous electrolyte secondary battery of the nonaqueous electrolytic solution can be made to employ, and preservation characteristics are improved in a high temperauture environment.On The details of this factor is still not clear, but can speculate with following mechanism：It is former with halogen when being existed simultaneously in electrolyte When the carbonic ester and " mono-fluor phosphate and/or difluorophosphoric acid salt " of son, the characteristic of protection envelope can be enable to carry with some form It is high.In addition, by using the carbonic ester with halogen atom as solvent, the oxidative resistance of nonaqueous electrolytic solution can improve, with anode The reaction of active material can be also suppressed, and then be conducive to improve preservation characteristics.
<Nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>
[1. non-aqueous electrolyte for secondary battery 2]
(" the present invention below, is properly termed as the nonaqueous electrolytic solution of the non-aqueous electrolyte secondary battery 2 of the present invention Nonaqueous electrolytic solution 2 ") be mainly by electrolyte and to dissolve the nonaqueous electrolytic solution that forms of nonaqueous solvents of the electrolyte, this is non-aqueous It is liquid that electrolyte, which contains at 25 DEG C, and dielectric constant is more than 5, viscosity is in below 0.6cP, and is contained with being formed The compound of the group (except backbone carbonyl) of heteroatomic skeleton, additionally containing mono-fluor phosphate and/or difluorophosphoric acid salt.
<1-1. electrolyte>
For the electrolyte of nonaqueous electrolytic solution 2 that is used for the present invention, there is no restriction, wherein can arbitrarily use and containing in mesh The well known electrolyte that can be used in mark non-aqueous electrolyte secondary battery as electrolyte.The nonaqueous electrolytic solution 2 of the present invention is used When non-aqueous electrolyte secondary battery, electrolyte is preferably lithium salts.
As the specific example of electrolyte, it can be mentioned, for example：The electrolyte identical in nonaqueous electrolytic solution 1 with being documented in.
Wherein, preferably LiPF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2Or two (oxalate conjunction) boron Sour lithium, particularly preferred LiPF6Or LiBF4。
The ratio of the species of electrolyte during for electrolyte is applied in combination, electrolyte when being applied in combination, it is non-with being documented in Situation in water electrolysis liquid 1 is identical.
In addition, lithium salt, preferred concentration in the final composition of the nonaqueous electrolytic solution 2 of the present invention etc., non-with being documented in Situation in water electrolysis liquid 1 is identical.In addition, the phenomenon that occurring when deviateing numberical range is also with being documented in nonaqueous electrolytic solution 1 Situation it is identical.
Particularly, for nonaqueous electrolytic solution nonaqueous solvents with carbonic acid as alkylene carbonates or dialkyl carbonate Situation based on ester compounds is also identical with situation about being documented in nonaqueous electrolytic solution 1.In addition, it is sent out when deviateing numberical range The phenomenon that raw, is also identical with situation about being documented in nonaqueous electrolytic solution 1.
In addition, when gamma-butyrolacton, gamma-valerolactone containing more than 50 volume % in the nonaqueous solvents in nonaqueous electrolytic solution When cyclic carboxylic acids ester compounds, preferably LiBF4More than 50mol% is accounted in lithium salts total amount.
<1-2. nonaqueous solvents>
The nonaqueous electrolytic solution 2 of the present invention contains following compounds：" be liquid at 25 DEG C, dielectric constant more than 5, it is viscous Property coefficient below 0.6cP, have formed the group (except backbone carbonyl) containing heteroatomic skeleton compound ".
<1-2-1. at 25 DEG C for liquid and dielectric constant more than 5, viscosity below 0.6cP, there is shape Into the compound of the group (except backbone carbonyl) containing heteroatomic skeleton>
The present invention 2 in it is described " at 25 DEG C for liquid, dielectric constant more than 5, viscosity below 0.6cP, With the compound for forming the group (except backbone carbonyl) containing heteroatomic skeleton ", as long as the change in this definition scope It closes object to be then not particularly limited, but considers from the characteristic of nonaqueous electrolytic solution, preferably have the chemical combination of ether skeleton and/or nitrile skeleton Object.That is, the compound of at least one more than ether or cyano as its skeleton part is preferably had.
In addition, from the aspect of its electrochemically reactive is inhibited, the above-mentioned compound with ether skeleton and/or nitrile skeleton into One step preferably has the alkyl optionally with substituent group.Wherein, above-mentioned " alkyl " represents chain-like alkyl or cyclic alkyl.
When above-claimed cpd for compound with ether skeleton when, can be formed optionally has with ether skeleton and alkylidene Combine the saturated cyclic compound as substituent group.I.e., it is possible to it is the ring-type ethers optionally with substituent group.
In addition, the substituent group as " compound with ether skeleton and/or nitrile skeleton ", considers, preferably from its reactivity Halogenic substituent, and/or " the saturated fat hydrocarbon substituent for not having the substituent group in addition to halogen atom ".
In addition, as the substituent group, consider from its reactivity, preferably halogenic substituent, alkoxycarbonyl substituent, alkane Oxygroup carboxyl substituent, alkyl carboxyl substituent group, but due to the raising for worrying viscosity, preferably using fluorine atom as substitution Base.
As described in the present invention 2 " at 25 DEG C for liquid and dielectric constant more than 5, viscosity 0.6cP with Under, have formed the group (except backbone carbonyl) containing heteroatomic skeleton compound " specific example, example can be enumerated Such as：Dimethoxy-ethane, diethoxyethane, ethyoxyl Ethyl Methyl Ether, tetrahydrofuran, oxinane, 1,3- dioxas penta Ring, acetonitrile, propionitrile, fluoride acetonitrile etc..
Described in the present invention 2 " at 25 DEG C for liquid and dielectric constant more than 5, viscosity below 0.6cP, The dielectric constant of compound with group (backbone carbonyl except) of the formation containing heteroatomic skeleton " utilizes Japan Electric chemistry The method described in " Electricity mood Measuring determines マ ニ ュ ア ル real and tramples Knitting " page 13 can be compiled to be measured, will be obtained using the measure Value be defined as the present invention 2 dielectric constant.
In addition, described in the present invention 2 " at 25 DEG C for liquid and dielectric constant more than 5, viscosity 0.6cP with Under, have formed the group (except backbone carbonyl) containing heteroatomic skeleton compound " viscosity utilize oersted Wa Erte (Ostwald) viscosimeter is measured, and the value being obtained using the measure is defined as to the viscosity of the present invention 2.It needs It is noted that " cP " representative " centipoise ".
Dielectric constant is necessary for more than 5, but preferably more than 5.1, more preferably more than 5.2, especially preferably 5.3 with On.Viscosity must be in below 0.6cP, but preferably below 0.5cP.
When use dielectric constant more than 5 and viscosity be below 0.6cP compound when, the ion under low resistance Migration is high, can be made into and (be suitable for being made) the high electrolyte of impregnability, dielectric constant more than 5 and viscosity 0.6cP with Under above-claimed cpd be usually easily occur electrochemical decomposition compound, but can by be applied in combination mono-fluor phosphate and/ Or difluorophosphoric acid salt inhibits the electrochemical decomposition.
<1-2-2. others nonaqueous solvents>
The nonaqueous electrolytic solution 2 of the present invention can be used, can not also used except " at 25 DEG C be liquid and dielectric is normal Number is more than 5, viscosity is below 0.6cP, with group (backbone carbonyl except) of the formation containing heteroatomic skeleton Other nonaqueous solvents beyond compound ", as long as will not be brought when battery is made to battery behavior dysgenic non-aqueous Agent, is used for and its species is not particularly limited.One or more of preferably following nonaqueous solvents enumerated.
As the example of the nonaqueous solvents used, it can be mentioned, for example：Chain or cyclic carbonate, chain or cyclic carboxylic acids Ester, phosphorous organic solvent, sulfur-bearing organic solvent etc..
In addition, for linear carbonate species also there is no limit, be preferably dialkyl carbonate, form dialkyl carbonate The carbon number of the alkyl of ester is respectively preferably 1~5, and especially preferably 1~4.As specific example, it can be mentioned, for example：Carbonic acid Dimethyl ester, methyl ethyl carbonate, diethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, carbonic acid di-n-propyl ester Deng.
In above-mentioned linear carbonate, dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate are due to industrial accessibility And the various characteristics in non-aqueous electrolyte secondary battery are good, therefore preferably.
For the species of cyclic carbonate, there is no restriction, and the carbon number for preferably comprising the alkylidene of cyclic carbonate is 2 ~6, especially preferably 2~4.Specifically, it can be mentioned, for example：Ethylene carbonate, propylene carbonate, butylene carbonate (2- second Base ethylene carbonate, cis and trans 2,3- dimethyl ethylene carbonate) etc..
In above-mentioned cyclic carbonate, ethylene carbonate or propylene carbonate are various in non-aqueous electrolyte secondary battery Characteristic is good, therefore preferably.
In addition, for chain carboxylate species also there is no limit, as specific example, it can be mentioned, for example：Methyl acetate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, propionic acid Ethyl ester, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propanoic acid tert-butyl ester etc..
In above-mentioned chain carboxylate, ethyl acetate, methyl propionate or ethyl propionate are due to industrial accessibility and non- Various characteristics in Water-Electrolyte secondary cell are good, therefore preferably.
In addition, for cyclic carboxylic esters species also there is no limit, can as the example of usually used cyclic carboxylic esters Enumerate gamma-butyrolacton, gamma-valerolactone, δ-valerolactone etc..
In above-mentioned cyclic carboxylic esters, gamma-butyrolacton is due to industrial accessibility and in non-aqueous electrolyte secondary battery Various characteristics it is good, therefore preferably.
In addition, be also not particularly limited for the species of phosphorous organic solvent, as specific example, it can be mentioned, for example：Phosphorus The phosphoric acid esters such as sour trimethyl, triethyl phosphate, triphenyl phosphate；Trimethyl phosphite, triethyl phosphite, phosphorous triphenyl phosphate The phosphorous acid esters such as ester；The phosphinoxides such as trimethyl phosphine oxide, triethyl group phosphine oxide, triphenylphosphine oxide；Etc..
In addition, being also not particularly limited for the species of sulfur-bearing organic solvent, as specific example, it can be mentioned, for example sulfurous Sour glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, ring fourth Alkene sulfone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, a vulcanization tetramethyl autumn Lan Mu, N, N- dimethyl methyls sulfonamide, N, N- diethyl Methanesulfomides etc..
In above-mentioned nonaqueous solvents, chain or cyclic carbonate or chain or cyclic carboxylic esters are secondary in nonaqueous electrolyte Various characteristics in battery are good, therefore preferably, wherein, more preferable ethylene carbonate, propylene carbonate, dimethyl carbonate, carbon Sour methyl ethyl ester, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate or gamma-butyrolacton, further preferred carbonic acid Asia second Ester, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, gamma-butyrolacton.
<It is 1-2-3. other>
" be liquid at 25 DEG C, dielectric constant more than 5, viscosity below 0.6cP, have and formed containing miscellaneous original The compound of the group (except backbone carbonyl) of the skeleton of son " can be used alone, can also with a kind it is listed above it is above-mentioned its Its nonaqueous solvents is applied in combination, but preferred compositions are used including " at 25 DEG C be liquid, dielectric constant is more than 5, viscosity Below 0.6cP, have formed the group (except backbone carbonyl) containing heteroatomic skeleton compound " including 2 kinds with Upper compound.For example, it is preferable to the high dielectric constant solvent of cyclic carbonates and linear carbonate class or chain ester is applied in combination The low viscosity solvents such as class.
For example, it is preferable to be applied in combination cyclic carbonates high dielectric constant solvent and " at 25 DEG C for liquid, dielectric Constant is more than 5, viscosity below 0.6cP, have formed the group containing heteroatomic skeleton (except backbone carbonyl) Compound "；The low viscosity solvents such as the high dielectric constant solvent and linear carbonate class of cyclic carbonates or chain esters, " be liquid at 25 DEG C, dielectric constant more than 5, viscosity below 0.6cP, have and formed containing heteroatomic bone The compound of the group (except backbone carbonyl) of frame ", particularly preferably will " be liquid at 25 DEG C, dielectric constant more than 5, it is viscous Property coefficient below 0.6cP, there is the compound for forming the group (except backbone carbonyl) containing heteroatomic skeleton " and be selected from One or more of cyclic carbonates, 3 class nonaqueous solvents class of linear carbonate class are applied in combination.
Wherein, the total amount of cyclic carbonates and linear carbonate class ratio shared in nonaqueous solvents total amount is usually More than 80 volume %, it is preferably more than 85 volume %, more preferably more than 90 volume %.Also, compared with cyclic carbonates With the total amount of linear carbonate class, the volumes of cyclic carbonates is preferably more than 5 volume %, more preferably 10 volume % with Upper, especially preferably more than 15 volume %, and usually below 50 volume %, preferably below 35 volume %, more preferably 30 Below volume %.When using above-mentioned nonaqueous solvents combination, cycle characteristics and height can be obtained using battery made of the combination Warm preservation characteristics (remaining capacity and high load capacity discharge capacity especially after High temperature storage) it is well balanced, therefore preferably.
Wherein, as above-mentioned cyclic carbonates and the specific example of the preferred compositions of linear carbonate class, example can be enumerated Such as：Ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, carbonic acid Ethyl and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate With diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc..
In the combination of above-mentioned ethylene carbonate and linear carbonate class, combination more preferably, can also enumerate into One step adds the combination of propylene carbonate.When containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is excellent Elect 99 as:1~40:60th, 95 are especially preferably:5~50:50.In addition, working as makes propylene carbonate shared in nonaqueous solvents total amount Ratio for more than 0.1 volume %, be preferably 1 volume %, more preferably more than 2 volume %, and usually below 10 volume %, During preferably below 8 volume %, more preferably below 5 volume %, original ethylene carbonate and linear carbonate can be kept The combined characteristic of class, and superior discharge load characteristic is further obtained, therefore preferably.
In said combination, the combination of further preferably asymmetric linear carbonate class, particularly, ethylene carbonate and carbon Dimethyl phthalate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and carbonic acid diformazan Contain ethylene carbonate and symmetrical linear carbonate class and asymmetric chain as ester and diethyl carbonate and methyl ethyl carbonate The combination of carbonates or the further combination containing propylene carbonate, it is negative with electric discharge that these combinations can obtain cycle characteristics The well balanced of characteristic is carried, therefore preferably.Wherein, preferably asymmetric linear carbonate class is the combination of methyl ethyl carbonate, in addition, The atomic number of alkyl carbon for forming dialkyl carbonate is preferably 1~2.
Other examples of preferred mixed solvent are the mixed solvent containing chain ester.Particularly, putting from raising battery From the point of view of electric loading characteristic, preferably contain chain ester in above-mentioned cyclic carbonates and linear carbonate class in the mixed solvent Mixed solvent, as chain ester, particularly preferred ethyl acetate, methyl propionate.The volume of chain ester is usual in nonaqueous solvents More than 5% is accounted for, more than 8% is preferably accounted for, more preferably accounts for more than 15%, and usually accounts for less than 50%, preferably accounts for less than 35%, is more excellent Choosing accounts for less than 30%, further preferably accounts for less than 25%.
As the example of other preferred nonaqueous solvents, can be account for it is more than 60 volume % of total amount in following solvents 1 kind of organic solvent or the mixed solvent being made of two or more organic solvent in following solvents, the solvent include：Carbon Sour ethyl, propylene carbonate and butylene carbonate, gamma-butyrolacton and gamma-valerolactone.It is preferred that the flash-point of this kind of mixed solvent is 50 DEG C or more, wherein, especially preferably 70 DEG C or more.Even if using the nonaqueous electrolytic solution of the solvent at high temperature using being not easy to Evaporation or the liquid leakage of solvent occurs.Wherein, when using the total amount of the ethylene carbonate and gamma-butyrolacton institute in nonaqueous solvents The ratio accounted for is more than 80 volume %, is preferably more than 90 volume %, and the volume ratio of ethylene carbonate and gamma-butyrolacton is 5: 95~45:During 55 solvent or when the ratio for using the total amount of ethylene carbonate and propylene carbonate shared in nonaqueous solvents Example is more than 80 volume %, is preferably more than 90 volume % and the volume ratio of ethylene carbonate and propylene carbonate is 30:70~ 80:During 20 solvent, the well balanced of cycle characteristics and discharge load characteristic etc. can be usually obtained.
<1-3. mono-fluor phosphates, difluorophosphoric acid salt>
The nonaqueous electrolytic solution 2 of the present invention contains mono-fluor phosphate and/or difluorophosphoric acid salt as essential component.For this hair " mono-fluor phosphate, the difluorophosphoric acid salt " used in bright 2, including their species, content, there are place, analysis method, lifes for it It is identical with situation about being documented in nonaqueous electrolytic solution 1 into process etc..
<1-4. additive>
In the range of significantly the effect of the present invention 2 is not destroyed, it can also contain in nonaqueous electrolytic solution 2 of the invention various Additive.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that Additive can be used alone, can also in any combination and two or more is applied in combination in ratio.
As the example of additive, overcharge preventing agent can be enumerated or keep special for improving the capacity after High temperature storage Auxiliary agent of property or cycle characteristics etc..Wherein, as improving helping for the capacity maintenance characteristics after High temperature storage or cycle characteristics Agent, preferably addition (below, can be also simply referred to as " specific carbonic acid with carbonic ester at least one in unsaturated bond and halogen atom Ester ").Hereinafter, it is divided into specific carbonic ester and other additives illustrates.
<The specific carbonic esters of 1-4-1.>
Specific carbonic ester is the carbonic ester for having at least one of unsaturated bond and halogen atom, and specific carbonic ester can only have There is unsaturated bond, can also only have halogen atom, can also have unsaturated bond and halogen atom simultaneously.
Had no for the molecular weight of specific carbonic ester it is specifically limited, unobvious destroy the present invention 2 effect in the range of Can be arbitrary molecular weight, but usually more than 50, preferably more than 80, and be usually below 250, be preferably less than 150. When molecular weight is excessive, dissolubility of the specific carbonic ester in nonaqueous electrolytic solution reduces, and may cause to be difficult to show sufficient effect Fruit.
In addition, being also not particularly limited for the manufacturing method of specific carbonic ester, well known method can arbitrarily be selected to make It makes.
It, can also be to appoint furthermore, it is possible to individually containing arbitrary a kind of specific carbonic ester in making the nonaqueous electrolytic solution 2 of the present invention Meaning combination and ratio contain two or more simultaneously.
In addition, for specific carbonic ester compared with the present invention nonaqueous electrolytic solution 2 combined amount there is no limit, in unobvious Can be arbitrary combined amount in the range of the effect of the destruction present invention 2, but compared with the nonaqueous electrolytic solution 2 of the present invention, it is contained The ideal concentration of specific carbonic ester is usually more than 0.01 mass %, is preferably more than 0.1 mass %, more preferably 0.3 matter Measure more than %, and usually below 70 mass %, preferably below 50 mass %, more preferably below 40 mass %.
If less than the lower limit of the scope, the nonaqueous electrolytic solution 2 of the present invention is being used for non-aqueous electrolyte secondary battery When, the non-aqueous electrolyte secondary battery may be caused to be difficult to show sufficient cycle characteristics improvement effect.In addition, work as particular carbon When the ratio of acid esters is excessive, when the nonaqueous electrolytic solution 2 of the present invention is used for non-aqueous electrolyte secondary battery, then the nonaqueous electrolyte The High temperature storage characteristic and trickle charge characteristic of secondary cell have the trend of reduction, especially gas generated to increase, and capacity is protected Holdup declines.
<1-4-1-1. unsaturated carbon acid ester>
For the carbonic ester (hereinafter also referred to as " unsaturated carbon acid ester ") with unsaturated bond, with nonaqueous electrolytic solution 1 Situation is identical.
<1-4-1-2. halocarbonate>
On the other hand, in the specific carbonic ester involved by the present invention 2, (below, have as the carbonic ester with halogen atom When be referred to as " halocarbonate "), as long as the carbonic ester with halogen atom then has no other specifically limited, can be used arbitrary Halocarbonate.The carbonic ester identical with " carbonic ester with halogen atom " in nonaqueous electrolytic solution 1 can be used.Wherein, non- In water electrolysis liquid 2, the preferred embodiment as " halocarbonate " is as follows.
As the specific example of halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom can be enumerated.Wherein, preferably fluorine is former Son or chlorine atom, particularly preferred fluorine atom.In addition, the no spy as long as more than 1 of Number of Halogen Atoms possessed by halocarbonate Different limitation, but usually less than 6, preferably less than 4.When halocarbonate has multiple halogen atoms, these halogen atoms can be with It is mutually the same, it can also be different.
As the example of halocarbonate, ethylene carbonate derivative class, dimethyl carbonate derivative species, carbonic acid can be enumerated Methyl ethyl ester derivative species, diethyl carbonate derivative species etc..
As the specific example of ethylene carbonate derivative class, can enumerate：Fluorine ethylene carbonate, vinylene carbonate, 4, 4- difluoros ethylene carbonate, 4,5- difluoros ethylene carbonate, bis- vinylene carbonates of 4,4-, bis- vinylene carbonates of 4,5-, 4- Fluoro- 4- methyl carbonic acids ethyl, the chloro- 4- methyl carbonic acids ethyls of 4-, bis- fluoro- 4- methyl carbonic acids ethyls of 4,5-, 4,5- bis- are chloro- The fluoro- 5- methyl carbonic acids ethyl of 4- methyl carbonic acids ethyl, 4-, the chloro- 5- methyl carbonic acids ethyls of 4-, bis- fluoro- 5- methyl of 4,4- Ethylene carbonate, bis- chloro- 5- methyl carbonic acids ethyls of 4,4-, 4- (methyl fluoride) ethylene carbonate, 4- (chloromethyl) carbonic acid Asia second Ester, 4- (difluoromethyl) ethylene carbonate, 4- (dichloromethyl) ethylene carbonate, 4- (trifluoromethyl) ethylene carbonate, 4- (three Chloromethyl) ethylene carbonate, 4- (methyl fluoride) -4- fluorine ethylene carbonate, 4- (chloromethyl) -4- vinylene carbonates, 4- (fluorine first Base) -5- fluorine ethylene carbonate, 4- (chloromethyl) -5- vinylene carbonates, the fluoro- 4,5- dimethyl ethylene carbonates of 4-, 4- be chloro- 4,5- dimethyl ethylene carbonate, bis- fluoro- 4,5- dimethyl ethylene carbonates of 4,5-, bis- chloro- 4,5- dimethyl carbonic acid of 4,5- are sub- Ethyl ester, bis- fluoro- 5,5- dimethyl ethylene carbonates of 4,4-, bis- chloro- 5,5- dimethyl ethylene carbonates of 4,4- etc..
As the specific example of dimethyl carbonate derivative species, can enumerate：Methyl methyl fluoride ester, methyl difluoro Methyl ester, methyl methyl ester trifluoroacetate, carbonic acid two (methyl fluoride) ester, carbonic acid two (difluoromethyl) ester, two (fluoroform of carbonic acid Base) ester, methyl chloromethane base ester, methyl dichloromethane base ester, methyl trichloromethyl ester, carbonic acid two (chloromethyl) Ester, carbonic acid two (dichloromethyl) ester, carbonic acid two (trichloromethyl) ester etc..
As the specific example of methyl ethyl carbonate derivative species, can enumerate：Methyl 2- fluoro ethyls ester, carbonic acid ethyl fluoride Methyl ester, methyl 2,2- bis-fluoro ethyls ester, carbonic acid methyl fluoride 2- fluoro ethyls ester, carbonic acid ethyl difluoro methyl ester, carbonic acid first Base 2,2,2- trifluoroethyls ester, carbonic acid methyl fluoride 2,2- bis-fluoro ethyls ester, carbonic acid difluoromethyl 2- fluoro ethyls ester, carbonic acid ethyl three Methyl fluoride ester, methyl 2- chloro-ethyl esters, carbonic acid ethyl chloride methyl ester, methyl 2,2- Dichloroethyls ester, carbonic acid chloromethane Base 2- chloro-ethyl esters, carbonic acid ethyl dichloromethane base ester, methyl 2,2,2- trichloroethyls, bis- chloroethenes of carbonic acid chloromethyl 2,2- Base ester, carbonic acid dichloromethyl 2- chloro-ethyl esters, carbonic acid ethyl trichloromethyl ester etc..
As the specific example of diethyl carbonate derivative species, can enumerate：Carbonic acid ethyl (2- fluoro ethyls) ester, carbonic acid ethyl (2,2- bis-fluoro ethyls) ester, carbonic acid two (2- fluoro ethyls) ester, carbonic acid ethyl (2,2,2- trifluoroethyls) ester, carbonic acid 2,2- difluoro second Base -2 '-fluoro ethyl ester, carbonic acid two (2,2- bis-fluoro ethyls) ester, carbonic acid 2,2,2- trifluoroethyls -2 '-fluoro ethyl ester, carbonic acid 2,2, 2- trifluoroethyls -2 ', 2 '-bis-fluoro ethyls ester, carbonic acid two (2,2,2- trifluoroethyls) ester, carbonic acid ethyl (2- chloroethyls) ester, carbon Sour ethyl (2,2- Dichloroethyls) ester, carbonic acid two (2- chloroethyls) ester, carbonic acid ethyl (2,2,2- trichloroethyls) ester, carbonic acid 2,2- Dichloroethyl -2 '-chloro-ethyl ester, carbonic acid two (2,2- Dichloroethyls) ester, carbonic acid 2,2,2- trichloroethyls -2 '-chloro-ethyl ester, carbon Sour 2,2,2- trichloroethyls -2 ', 2 '-Dichloroethyl ester, carbonic acid two (2,2,2- trichloroethyls) ester etc..
In above-mentioned halocarbonate, the carbonic ester of fluorine atom is preferably had, the carbonic acid Asia second more preferably with fluorine atom Ester derivant class, especially since when sub- using fluorine ethylene carbonate, 4- (methyl fluoride) ethylene carbonate, 4,4- difluoros carbonic acid Protection envelope in interface can be formed when ethyl ester, 4,5- difluoro ethylene carbonates, thus is more highly preferred to.
<The halogenated unsaturated carbon acid esters of 1-4-1-3.>
In addition, as specific carbonic ester, it can also use while there is unsaturated bond and the carbonic ester of halogen atom (is fitted When referred to as " halogenated unsaturated carbon acid ester ").It as halogenated unsaturated carbon acid ester, has no specifically limited, is not destroying this significantly Arbitrary halogenated unsaturated carbon acid ester can be used in the range of the effect of invention 2.
As the example of halogenated unsaturated carbon acid ester, vinylene carbonate derivative species can be enumerated, by with aromatic rings or Ethylene carbonate derivative class, the allyl esters etc. of the substituent group substitution of carbon-to-carbon unsaturated bond.
As the specific example of vinylene carbonate derivative species, can enumerate：The fluoro- 5- methyl of fluorine vinylene carbonate, 4- The fluoro- 5- phenyl-carbonic acids vinylene of vinylene carbonate, 4-, 4- (trifluoromethyl) vinylene carbonate, chlorine vinylene carbonate, The chloro- 5- methylvinylene carbonates of 4-, the chloro- 5- phenyl-carbonic acids vinylenes of 4-, 4- (trichloromethyl) vinylene carbonate etc..
As the specific of the ethylene carbonate derivative class substituted by the substituent group with aromatic rings or carbon-to-carbon unsaturated bond Example can be enumerated：The fluoro- 4- vinylethylene carbonates of 4-, the fluoro- 5- vinylethylene carbonates of 4-, bis- fluoro- 5- vinyl of 4,4- Ethylene carbonate, bis- fluoro- 4- vinylethylene carbonates of 4,5-, the chloro- 5- vinylethylene carbonates of 4-, bis- chloro- 5- second of 4,4- Alkenyl ethylene carbonate, bis- chloro- 4- vinylethylene carbonates of 4,5-, the fluoro- 4,5- divinyl ethylene carbonates of 4-, 4,5- bis- Fluoro- 4,5- divinyl ethylene carbonate, the chloro- 4,5- divinyl ethylene carbonates of 4-, bis- chloro- 4,5- divinyl carbon of 4,5- The fluoro- 4- phenyl-carbonic acids ethyl of sour ethyl, 4-, the fluoro- 5- phenyl-carbonic acids ethyls of 4-, bis- fluoro- 5- phenyl-carbonic acids Asia second of 4,4- Ester, bis- fluoro- 4- phenyl-carbonic acids ethyls of 4,5-, the chloro- 4- phenyl-carbonic acids ethyls of 4-, the chloro- 5- phenyl-carbonic acids ethyls of 4-, 4,4- Two chloro- 5- phenyl-carbonic acids ethyls, bis- chloro- 4- phenyl-carbonic acids ethyls of 4,5-, bis- fluoro- 4,5- diphenyl carbonic acid Asia second of 4,5- Ester, bis- chloro- 4,5- diphenyl ethylene carbonates of 4,5- etc..
As the specific example of carbonate esters, can enumerate：Carbonic acid trifluoromethylphenyl ester, carbonic acid 2- fluoro ethyl phenyl Ester, carbonic acid 2,2- bis-fluoro ethyls phenylester, carbonic acid 2,2,2- trifluoroethyls phenylester, carbonic acid chloromethylbenzene base ester, carbonic acid 2- chlorine Ethyl phenyl ester, carbonic acid 2,2- Dichloroethyls phenylester, carbonic acid 2,2,2- trichloroethyl phenylesters etc..
As the specific example of ethylene carbonate esters, can enumerate：Carbonic acid methyl fluoride vinyl esters, carbonic acid 2- fluoro ethyl ethylene Base ester, carbonic acid 2,2- bis-fluoro ethyls vinyl esters, carbonic acid 2,2,2- trifluoroethyls vinyl esters, carbonic acid chloromethyl vinyl base ester, Carbonic acid 2- chloroethyl vinyls base ester, carbonic acid 2,2- Dichloroethyls vinyl esters, carbonic acid 2,2,2- trichloroethyl vinyl esters etc..
As the specific example of allyl esters, can enumerate：Carbonic acid methyl fluoride allyl ester, carbonic acid 2- fluoro ethyl allyls Base ester, carbonic acid 2,2- bis-fluoro ethyls allyl ester, carbonic acid 2,2,2- trifluoroethyls allyl ester, carbonic acid chloromethyl allyl ester, Carbonic acid 2- chloroethyls allyl ester, carbonic acid 2,2- Dichloroethyls allyl ester, carbonic acid 2,2,2- trichloroethyl allyl esters etc..
In the example of above-mentioned halogenated unsaturated carbon acid ester, as specific carbonic ester, particularly preferably using to be selected from individually makes The better vinylene carbonate of effect, vinylethylene carbonate, fluorine ethylene carbonate and the 4,5- difluoro carbonic acid Asia second of used time The compound of one or more of ester and their derivative.
<The other additives of 1-4-2.>
As the additive in addition to specific carbonic ester, overcharge preventing agent can be enumerated, for improving High temperature storage after Capacity maintenance characteristics or cycle characteristics auxiliary agent etc..For " overcharge preventing agent " and " for improving the appearance after High temperature storage Measure the auxiliary agent of retention performance or cycle characteristics ", it is identical with situation about being documented in nonaqueous electrolytic solution 1.
[2. non-aqueous electrolyte secondary battery]
The present invention non-aqueous electrolyte secondary battery 2 have can occlude and release the cathode of ion and anode, Yi Jishang State the nonaqueous electrolytic solution of the present invention.
<2-1. battery structure>
The battery structure of non-aqueous electrolyte secondary battery 2 on the present invention, with being documented in non-aqueous electrolyte secondary battery 1 Partial situation is identical.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution 2 of the invention described above can be used.It should be noted that without departing from In the range of the main points of the present invention 2, other nonaqueous electrolytic solutions can also be mixed into the nonaqueous electrolytic solution 2 of the present invention and are used.
<2-3. cathode>
On the cathode of non-aqueous electrolyte secondary battery 2, with saying for the cathode that is documented in non-aqueous electrolyte secondary battery 1 It is bright identical.
<2-4. anode>
On the anode of non-aqueous electrolyte secondary battery 2, with saying for the anode that is documented in non-aqueous electrolyte secondary battery 1 It is bright identical.
<2-5. partition plate>
As the partition plate of non-aqueous electrolyte secondary battery 2, with saying for the partition plate that is documented in non-aqueous electrolyte secondary battery 1 It is bright identical.
<2-6. battery design>
On the battery design of non-aqueous electrolyte secondary battery 2, with the battery being documented in non-aqueous electrolyte secondary battery 1 The explanation of design is identical.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>
[1. nonaqueous electrolytic solution]
The nonaqueous electrolytic solution 3 of the present invention is mainly made of electrolyte with the nonaqueous solvents for dissolving the electrolyte, the non-water power Solution liquid contains mono-fluor phosphate and/or difluorophosphoric acid salt, also containing " compound, nitrilation selected from above-mentioned general formula (1) expression are closed Object, isocyanate compound, phosphazene compound, disulfonate compound, sulfide compound, disulfide compound, acid anhydrides, α At least one kind of compound in lactone compound with substituent group and the compound with carbon-carbon triple bond ".It hereinafter, will be upper The compound in quotation marks is stated to be referred to as " the compound A of the present invention 3 ".
<1-1. electrolyte>
The nonaqueous electrolytic solution 3 of the present invention is containing electrolyte and dissolves the nonaqueous solvents of the electrolyte.For the non-of the present invention There is no limit can arbitrarily use and electric containing that can be used as in target non-aqueous electrolyte secondary battery the electrolyte of water electrolysis liquid 3 The known electrolytic matter that solution matter uses.When the nonaqueous electrolytic solution 3 of the present invention is used for non-aqueous electrolyte secondary battery, electrolyte is preferred For lithium salts.
The electrolyte of nonaqueous electrolytic solution 3 on the present invention is identical with the explanation for being documented in 1 part of nonaqueous electrolytic solution.
<The compound A of the 1-2. present invention 3>
The nonaqueous electrolytic solution 3 of the present invention contains above-mentioned " the compound A of the present invention 3 "." the compound A of the present invention 3 " is：It is logical The compound of formula (1) expression, nitrile compound, isocyanate compound, phosphazene compound, disulfonate compound, thioether chemical combination Object, disulfide compound, acid anhydrides, the α lactone compounds with substituent group or the compound with carbon-carbon triple bond.Hereinafter, More specifically illustrated for the compound of " the compound A of the present invention 3 " group formed in the present invention 3.
<The compound that 1-2-1. general formulas (5) represent>
[chemical formula 4]
[in general formula (5), R1、R2And R3The carbon number 1 for each independently represent fluorine atom, being optionally replaced by fluorine atoms The alkoxy of~12 alkyl or the carbon number 1~12 being optionally replaced by fluorine atoms.]
It as the alkyl that carbon number is 1~12, has no specifically limited, preferably enumerates carbon number 1~8, especially excellent Select the chain or cyclic alkyl of carbon number 1~6.Wherein, preferred chain-like alkyl.Specific enumerable such as methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, cyclopenta, cyclohexyl etc..
As the alkoxy of carbon number 1~12, specifically limited, but preferably carbon number 1~8, particularly preferred carbon is had no The alkoxy of atomicity 1~6.It is specific enumerable such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, different Butoxy, sec-butoxy, tert-butoxy etc..
It is specific enumerable such as trifluoromethyl, trifluoroethyl, pentafluoroethyl group as the alkyl being replaced by fluorine atoms.
As the alkoxy being replaced by fluorine atoms, specific enumerable such as trifluoromethoxy, trifluoro ethoxy, five fluorine ethoxies Base etc..
As R1、R2And R3It is the specific example of the compound of alkoxy, it can be mentioned, for example：Trimethyl phosphate, phosphoric acid second Base dimethyl esters, phosphoric acid n-propyl dimethyl esters, mixture of n-butyl dimethyl esters, phosphoric acid methyl diethyl ester, phosphoric acid methyl second Base n-propyl ester, phosphoric acid Methylethyl n-butyl, phosphoric acid methyl diη-propyl ester, phosphoric acid methyl n-propyl n-butyl, phosphorus Acid methyl di-n-butyl ester, triethyl phosphate, phosphoric acid n-propyl diethyl ester, mixture of n-butyl diethyl ester, ethyl two N-propyl ester, ethyl n-propyl n-butyl, ethyl di-n-butyl ester, tricresyl phosphate n-propyl, mixture of n-butyl two N-propyl ester, phosphoric acid n-propyl di-n-butyl ester, TRI N BUTYL PHOSPHATE, phosphoric acid cyclopenta dimethyl esters, phosphoric acid cyclopenta diethyl Base ester, phosphoric acid cyclopenta diη-propyl ester, phosphoric acid cyclopenta di-n-butyl ester, phosphoric acid Methylethyl cyclopentyl ester, phosphoric acid methyl Bicyclopentyl ester, phosphoric acid tricyclic pentyl ester, phosphoric acid cyclohexyldimethyl ester, phosphoric acid cyclohexyl diethyl ester, phosphoric acid cyclohexyl two are just Propyl diester, phosphoric acid cyclohexyl di-n-butyl ester, phosphoric acid Methylethyl cyclohexyl ester, phosphoric acid methyldicyclohexyl ester, phosphoric acid tricyclic Own ester, p trifluoromethylbenzoic acid dimethyl esters, p trifluoromethylbenzoic acid diethyl ester, phosphoric acid Methylethyl methyl ester trifluoroacetate, phosphoric acid (2, 2,2- trifluoroethyls) dimethyl esters, phosphoric acid (2,2,2- trifluoroethyls) diethyl ester, phosphoric acid (2,2,2- trifluoroethyls) methyl second Base ester, phosphoric acid (pentafluoroethyl group) dimethyl esters, phosphoric acid (pentafluoroethyl group) diethyl ester, phosphoric acid (pentafluoroethyl group) Methylethyl ester, Phosphoric acid methyl two (trifluoromethyl) ester, tricresyl phosphate (trifluoromethyl) ester, phosphoric acid methyl two (2,2,2- trifluoroethyls) ester, tricresyl phosphate Methyl fluoride two (2,2,2- trifluoroethyls) ester, phosphoric acid methyl two (pentafluoroethyl group) ester, p trifluoromethylbenzoic acid two (pentafluoroethyl group) ester, Ethyl two (trifluoromethyl) ester, phosphoric acid 2,2,2- trifluoroethyls two (trifluoromethyl) ester, two (fluoroform of phosphoric acid pentafluoroethyl group Base) ester, ethyl two (2,2,2- trifluoroethyls) ester, tricresyl phosphate (2,2,2- trifluoroethyls) ester, phosphoric acid pentafluoroethyl group two (2, 2,2- trifluoroethyls) ester, ethyl two (pentafluoroethyl group) ester, phosphoric acid 2,2,2- trifluoroethyls two (pentafluoroethyl group) ester, phosphoric acid Three (pentafluoroethyl group) esters etc..
It is listed above go out phosphate in, preferably：Trimethyl phosphate, ethyl dimethyl esters, phosphoric acid methyl diethyl Base ester, triethyl phosphate, p trifluoromethylbenzoic acid dimethyl esters, p trifluoromethylbenzoic acid diethyl ester, phosphoric acid Methylethyl fluoroform Base ester, phosphoric acid (2,2,2- trifluoroethyls) dimethyl esters, phosphoric acid (2,2,2- trifluoroethyls) diethyl ester, phosphoric acid (2,2,2- tri- Fluoro ethyl) Methylethyl ester, phosphoric acid (pentafluoroethyl group) dimethyl esters, phosphoric acid (pentafluoroethyl group) diethyl ester, phosphoric acid (five fluorine second Base) Methylethyl ester, di(2-ethylhexyl)phosphate (trifluoromethyl) methyl ester, tricresyl phosphate (trifluoromethyl) ester, di(2-ethylhexyl)phosphate (2,2,2- trifluoro second Base) methyl ester, di(2-ethylhexyl)phosphate (2,2,2- trifluoroethyls) methyl ester trifluoroacetate, di(2-ethylhexyl)phosphate (pentafluoroethyl group) methyl ester, phosphoric acid fluoroform Base two (pentafluoroethyl group) ester, ethyl two (trifluoromethyl) ester, phosphoric acid 2,2,2- trifluoroethyls two (trifluoromethyl) ester, phosphoric acid Pentafluoroethyl group two (trifluoromethyl) ester, ethyl two (2,2,2- trifluoroethyls) ester, tricresyl phosphate (2,2,2- trifluoroethyls) ester, Phosphoric acid pentafluoroethyl group two (2,2,2- trifluoroethyls) ester, ethyl two (pentafluoroethyl group) ester, phosphoric acid 2,2,2- trifluoroethyls two (pentafluoroethyl group) ester, tricresyl phosphate (pentafluoroethyl group) ester etc..
As R1、R2And R3In wantonly 1 be alkyl, it is wantonly 2 be alkoxy compound specific example, example can be enumerated Such as：Dimethyl methyl phosphonate, diethyl ethylphosphate, n-propyl phosphonic acids di-n-propyl ester, isopropyl phosphonic acids diisopropyl ester, normal-butyl Phosphonic acids di-n-butyl, isobutyl group phosphonic acids diisobutyl ester, tert-butylphosphonic acid di tert butyl carbonate, two ring pentyl ester of cyclopenta phosphonic acids, hexamethylene Base phosphonic acids dicyclohexyl maleate, methylphosphonic acid diethylester, methylphosphonic acid di-n-propyl ester, methylphosphonic acid di-n-butyl, two ring of methylphosphonic acid Pentyl ester, methylphosphonic acid dicyclohexyl maleate, ethylphosphonic acid dimethyl ester, ethylphosphonic acid di-n-propyl ester, ethylphosphonic acid di-n-butyl, ethyl phosphine Sour two ring pentyl esters, ethylphosphonic acid dicyclohexyl maleate, n-propyl phosphine dimethyl phthalate, n-propyl phosphine diethyl phthalate, normal-butyl phosphonic acids diformazan Ester, normal-butyl diethyl phosphonate, cyclohexyl dimethyl phosphonate, cyclohexyl diethyl phosphonate, methylphosphonic acid Methylethyl ester, methyl Phosphonomethyl n-propyl ester, methylphosphonic acid methyl n-butyl, methylphosphonic acid methylcyclopentyl ester, methylphosphonic acid methylcyclohexyl Ester, methylphosphonic acid ethyl n-propyl ester, methylphosphonic acid cyclohexyl base ester, ethylphosphonic acid Methylethyl ester, ethylphosphonic acid methyl N-propyl ester, ethylphosphonic acid methyl n-butyl, ethylphosphonic acid methylcyclopentyl ester, ethylphosphonic acid methyl cyclohexane base ester, ethyl Phosphonic-ethyl n-propyl ester, ethylphosphonic acid cyclohexyl base ester, n-propyl phosphine acid methyl ethyl ester, n-propyl phosphine acid methyl positive third Base ester, n-propyl phosphine acid methyl n-butyl, n-propyl phosphine acid methyl cyclopentyl ester, n-propyl phosphine acid methyl cyclohexyl ester, just Propyl phosphonous acid ethyl n-propyl ester, n-propyl phosphonic acids ethylcyclohexyl ester, normal-butyl phosphonomethyl ethyl ester, normal-butyl phosphonic acids first Base n-propyl ester, normal-butyl phosphonomethyl n-butyl, normal-butyl phosphonomethyl cyclopentyl ester, normal-butyl phosphonomethyl cyclohexyl Ester, normal-butyl phosphonic-ethyl n-propyl ester, normal-butyl phosphonic-ethyl cyclohexyl ester,
Cyclohexyl phosphonomethyl ethyl ester, cyclohexyl phosphonomethyl n-propyl ester, cyclohexyl phosphonomethyl n-butyl, ring Hexyl phosphonomethyl cyclopentyl ester, cyclohexyl phosphonomethyl cyclohexyl ester, cyclohexyl phosphonic-ethyl n-propyl ester, cyclohexyl phosphonic acids Cyclohexyl base ester, two perfluoro-methyl ester of methylphosphonic acid, methylphosphonic acid two (2,2,2- trifluoroethyls) ester, two perfluor of methylphosphonic acid Ethyl ester, methylphosphonic acid two (2- fluorine cyclohexyl) ester, methylphosphonic acid two (3- fluorine cyclohexyl) ester, (the 4- fluorine hexamethylenes of methylphosphonic acid two Base) ester, two perfluoro-methyl ester of ethylphosphonic acid, ethylphosphonic acid two (2,2,2- trifluoroethyls) ester, two perfluoro-ethyl ester of ethylphosphonic acid, Ethylphosphonic acid two (2- fluorine cyclohexyl) ester, ethylphosphonic acid two (3- fluorine cyclohexyl) ester, ethylphosphonic acid two (4- fluorine cyclohexyl) ester, just Propyl phosphonous acid two (2,2,2- trifluoroethyls) ester, two perfluoro-ethyl ester of n-propyl phosphonic acids, (the 2,2,2- trifluoro second of normal-butyl phosphonic acids two Base) ester, two perfluoro-ethyl ester of normal-butyl phosphonic acids, cyclohexyl phosphonic acids two (2,2,2- trifluoroethyls) ester, two perfluor of cyclohexyl phosphonic acids Ethyl ester,
Methylphosphonic acid methyl perfluoro methyl ester, methylphosphonic acid methyl (2,2,2- trifluoroethyls) ester, methylphosphonic acid methyl are complete Fluoro ethyl ester, methylphosphonic acid methyl (2- fluorine cyclohexyl) ester, methylphosphonic acid methyl (3- fluorine cyclohexyl) ester, methylphosphonic acid methyl (4- fluorine cyclohexyl) ester, methylphosphonic acid ethylperfluoro ethyl ester, methylphosphonic acid cyclohexyl (2,2,2- trifluoroethyls) ester, methylphosphine Sour cyclohexyl perfluoro-ethyl ester, methylphosphonic acid perfluoro-ethyl (2,2,2- trifluoroethyls) ester, ethylphosphonic acid ethyl (2,2,2- trifluoros Ethyl) ester, ethylphosphonic acid ethylperfluoro ethyl ester, ethylphosphonic acid cyclohexyl (2,2,2- trifluoroethyls) ester, ethylphosphonic acid hexamethylene Base perfluoro-ethyl ester, ethylphosphonic acid perfluoro-ethyl (2,2,2- trifluoroethyls) ester, ethylphosphonic acid (2- fluorine cyclohexyl) (2,2,2- tri- Fluoro ethyl) ester, n-propyl phosphonic-ethyl (2,2,2- trifluoroethyls) ester, n-propyl phosphonic acids ethylperfluoro ethyl ester, n-propyl phosphine Sour cyclohexyl (2,2,2- trifluoroethyls) ester, n-propyl phosphonic acids cyclohexyl perfluoro-ethyl ester, n-propyl phosphonic acids perfluoro-ethyl (2,2, 2- trifluoroethyls) ester, n-propyl phosphonic acids (2- fluorine cyclohexyl) (2,2,2- trifluoroethyls) ester, normal-butyl phosphonic-ethyl (2,2,2- Trifluoroethyl) ester, normal-butyl phosphonic-ethyl perfluoro-ethyl ester, normal-butyl phosphonic acids cyclohexyl (2,2,2- trifluoroethyls) ester, positive fourth Base phosphonic acids cyclohexyl perfluoro-ethyl ester, normal-butyl phosphonic acids perfluoro-ethyl (2,2,2- trifluoroethyls) ester, normal-butyl phosphonic acids (2- fluorine rings Hexyl) (2,2,2- trifluoroethyls) ester,
Cyclohexyl phosphonic-ethyl (2,2,2- trifluoroethyls) ester, cyclohexyl phosphonic-ethyl perfluoro-ethyl ester, cyclohexyl phosphonic acids Cyclohexyl (2,2,2- trifluoroethyls) ester, cyclohexyl phosphonic acids cyclohexyl perfluoro-ethyl ester, cyclohexyl phosphonic acids perfluoro-ethyl (2,2,2- Trifluoroethyl) ester, cyclohexyl phosphonic acids (2- fluorine cyclohexyl) (2,2,2- trifluoroethyls) ester, two perfluoro-methyl of perfluoro-methyl phosphonic acids Ester, (2,2,2- trifluoroethyls) phosphonic acids two (2,2,2- trifluoroethyls) ester, two perfluoro-ethyl ester of perfluoro-ethyl phosphonic acids, (2- fluorine rings Hexyl) phosphonic acids two (2- fluorine cyclohexyl) ester, (3- fluorine cyclohexyl) phosphonic acids two (3- fluorine cyclohexyl) ester, (4- fluorine cyclohexyl) phosphonic acids two (4- fluorine cyclohexyl) ester,
(2,2,2- trifluoroethyls) dimethyl phosphonate, (2,2,2- trifluoroethyls) diethyl phosphonate, (2,2,2- trifluoro second Base) phosphonic acids di-n-butyl, (2,2,2- trifluoroethyls) phosphonic acids dicyclohexyl maleate, two perfluor ethyl ester of (2,2,2- trifluoroethyls) phosphonic acids, (2,2,2- trifluoroethyls) phosphonic acids two (2- fluorine cyclohexyl) ester, (2,2,2- trifluoroethyls) phosphonomethyl ethyl ester, (2,2,2- tri- Fluoro ethyl) phosphonomethyl n-butyl, (2,2,2- trifluoroethyls) phosphonomethyl cyclohexyl ester, (2,2,2- trifluoroethyls) phosphonic acids Methyl (2,2,2- trifluoroethyls) ester, (2,2,2- trifluoroethyls) phosphonomethyl perfluoro-ethyl ester, (2,2,2- trifluoroethyls) phosphine Acid methyl (2- fluorine cyclohexyl) ester, (2,2,2- trifluoroethyls) phosphonic-ethyl cyclohexyl ester, (2,2,2- trifluoroethyls) phosphonic acids second Base (2,2,2- trifluoroethyls) ester, (2,2,2- trifluoroethyls) phosphonic acids cyclohexyl (2,2,2- trifluoroethyls) ester, (2- fluorine hexamethylenes Base) dimethyl phosphonate, (2- fluorine cyclohexyl) diethyl phosphonate, (2- fluorine cyclohexyl) phosphonic acids dicyclohexyl maleate, (2- fluorine cyclohexyl) phosphine Sour two (2,2,2- trifluoroethyls) esters, (2- fluorine cyclohexyl) phosphonomethyl ethyl ester, (2- fluorine cyclohexyl) phosphonomethyl cyclohexyl Ester, (2- fluorine cyclohexyl) phosphonomethyl (2,2,2- trifluoroethyls) ester etc..
It is listed above go out phosphonate ester in, preferably：Dimethyl methyl phosphonate, diethyl ethylphosphate, n-propyl phosphonic acids Di-n-propyl ester, normal-butyl phosphonic acids di-n-butyl, isobutyl group phosphonic acids diisobutyl ester, methylphosphonic acid diethylester, two positive fourth of methylphosphonic acid Ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid di-n-propyl ester, n-propyl phosphine dimethyl phthalate, n-propyl phosphine diethyl phthalate, methylphosphonic acid Two (2,2,2- trifluoroethyls) esters, ethylphosphonic acid two (2,2,2- trifluoroethyls) ester, two perfluor methyl esters of perfluoro-methyl phosphonic acids, (2, 2,2- trifluoroethyls) phosphonic acids two (2,2,2- trifluoroethyls) ester, two perfluor ethyl ester of perfluoro-ethyl phosphonic acids, (2,2,2- trifluoroethyls) Dimethyl phosphonate, (2,2,2- trifluoroethyls) diethyl phosphonate etc..
As R1、R2And R3In wantonly 2 be alkyl, it is wantonly 1 be alkoxy compound specific example, example can be enumerated Such as：Dimethylphosphinic acid methyl esters, diethyl phosphinicacid ethyl ester, diη-propyl phosphinic acids n-propyl, diisopropyl phosphinic acids isopropyl Ester, di-n-butyl phosphinic acids N-butyl, diisobutylphosphinicacid acid isobutyl ester, di-t-butyl phosphinic acid tert-butyl ester, bicyclopentyl time Phosphonic acid cyclic pentyl ester, dicyclohexyl phosphinic acids cyclohexyl, diethyl phosphinic acid methyl ester, diη-propyl phosphinic acid methyl ester, diisopropyl Phosphinic acid methyl ester, di-n-butyl phosphinic acid methyl ester, diisobutylphosphinicacid acid methyl esters, di-t-butyl phosphinic acid methyl ester, bicyclopentyl Phosphinic acid methyl ester, dicyclohexyl phosphinic acid methyl ester, dimethylphosphinic acid ethyl ester, diη-propyl phosphinicacid ethyl ester, diisopropyl time Phosphinic acid ethyl ester, di-n-butyl phosphinicacid ethyl ester, diisobutylphosphinicacid acid ethyl ester, di-t-butyl phosphinicacid ethyl ester, bicyclopentyl time Phosphinic acid ethyl ester, dicyclohexyl phosphinicacid ethyl ester, dimethylphosphinic acid n-propyl, diethyl phosphinic acids n-propyl, diisopropyl time Phosphonic acids n-propyl, di-n-butyl phosphinic acids n-propyl, diisobutylphosphinicacid acid n-propyl, di-t-butyl phosphinic acids n-propyl, two Cyclopenta phosphinic acids n-propyl, dicyclohexyl phosphinic acids n-propyl, dimethylphosphinic acid N-butyl, the positive fourth of diethyl phosphinic acids Ester, dicyclohexyl phosphinic acids N-butyl, dimethylphosphinic acid cyclohexyl, diethyl phosphinic acids cyclohexyl, diη-propyl phosphinic acids Cyclohexyl, di-n-butyl phosphinic acids cyclohexyl, Methylethyl phosphinic acid methyl ester, methyl-n-propylphosphinic acid methyl esters, the positive fourth of methyl Base phosphinic acid methyl ester, methylcyclohexyl phosphinic acid methyl ester, ethyl n-propyl phosphinic acid methyl ester, ethyl normal-butyl phosphinic acid methyl ester, Ethylcyclohexyl phosphinic acid methyl ester, n-propyl cyclohexyl phosphinic acid methyl ester, normal-butyl cyclohexyl phosphinic acid methyl ester, Methylethyl time Phosphinic acid ethyl ester, methyl-n-propylphosphinic acid ethyl ester, methyl normal-butyl phosphinicacid ethyl ester, methylcyclohexyl phosphinicacid ethyl ester, ethyl Normal-butyl phosphinicacid ethyl ester, ethylcyclohexyl phosphinicacid ethyl ester, normal-butyl cyclohexyl phosphinicacid ethyl ester, Methylethyl phosphinic acids are just Butyl ester, methyl normal-butyl phosphinic acids N-butyl, methylcyclohexyl phosphinic acids N-butyl, methylphenylphosphinic acid N-butyl, ethyl Normal-butyl phosphinic acids N-butyl, ethylcyclohexyl phosphinic acids N-butyl, ethylphenyl phosphinic acids N-butyl, normal-butyl cyclohexyl Phosphonic acids N-butyl, cyclohexylvinyl phosphinic acids N-butyl, Methylethyl phosphinic acids cyclohexyl, methyl normal-butyl phosphinic acids hexamethylene Ester, methylcyclohexyl phosphinic acids cyclohexyl, ethyl normal-butyl phosphinic acids cyclohexyl, ethylcyclohexyl phosphinic acids cyclohexyl, positive fourth Butylcyclohexyl phosphinic acids cyclohexyl, two perfluoro-methyl phosphinic acids perfluor methyl esters, two (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- Trifluoroethyl) ester, two perfluoro-ethyl phosphinic acids perfluor ethyl esters, two (2- fluorine cyclohexyl) phosphinic acids (2- fluorine cyclohexyl) esters, two (3- Fluorine cyclohexyl) phosphinic acids (3- fluorine cyclohexyl) ester, two (4- fluorine cyclohexyl) phosphinic acids (4- fluorine cyclohexyl) esters, two perfluoro-methyls time Methyl-phosphonate, two (2,2,2- trifluoroethyls) phosphinic acid methyl esters, two perfluoro-ethyl phosphinic acid methyl esters, two (2- fluorine cyclohexyl) secondary phosphines Sour methyl esters, two (3- fluorine cyclohexyl) phosphinic acid methyl esters, two (4- fluorine cyclohexyl) phosphinic acid methyl esters, two perfluoro-methyl phosphinic acids second Ester, two (2,2,2- trifluoroethyls) phosphinicacid ethyl esters, two perfluoro-ethyl phosphinicacid ethyl esters, two (2- fluorine cyclohexyl) phosphinic acids second Ester, two (3- fluorine cyclohexyl) phosphinicacid ethyl esters, two (4- fluorine cyclohexyl) phosphinicacid ethyl esters, two (2,2,2- trifluoroethyls) phosphinic acids N-butyl, two (2,2,2- trifluoroethyls) phosphinic acids cyclohexyls, dimethylphosphinic acid (2,2,2- trifluoroethyls) ester, diethyl time Phosphonic acids (2,2,2- trifluoroethyls) ester, di-n-butyl phosphinic acids (2,2,2- trifluoroethyls) ester, dicyclohexyl phosphinic acids (2,2,2- Trifluoroethyl) ester, methyl (2,2,2- trifluoroethyls) phosphinicacid ethyl ester, methyl (2- fluorophenyls) phosphinicacid ethyl ester, ethyl (2,2, 2- trifluoroethyls) phosphinicacid ethyl ester, normal-butyl (2,2,2- trifluoroethyls) phosphinicacid ethyl ester, cyclohexyl (2,2,2- trifluoroethyls) Phosphinicacid ethyl ester, methyl (2,2,2- trifluoroethyls) phosphinic acids N-butyl, ethyl (2,2,2- trifluoroethyls) phosphinic acids N-butyl, Normal-butyl (2,2,2- trifluoroethyls) phosphinic acids N-butyl, cyclohexyl (2,2,2- trifluoroethyls) phosphinic acids N-butyl, methyl (2, 2,2- trifluoroethyls) phosphinic acids cyclohexyl, ethyl (2,2,2- trifluoroethyls) phosphinic acids cyclohexyl, normal-butyl (2,2,2- trifluoros Ethyl) phosphinic acids cyclohexyl, cyclohexyl (2,2,2- trifluoroethyls) phosphinic acids cyclohexyl, Methylethyl phosphinic acids (2,2,2- tri- Fluoro ethyl) ester, methyl normal-butyl phosphinic acids (2,2,2- trifluoroethyls) ester, methylcyclohexyl phosphinic acids (2,2,2- trifluoroethyls) Ester, methyl (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- trifluoroethyls) ester, ethyl normal-butyl phosphinic acids (2,2,2- trifluoro second Base) ester, ethylcyclohexyl phosphinic acids (2,2,2- trifluoroethyls) ester, ethyl (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- tri- Fluoro ethyl) ester, normal-butyl cyclohexyl phosphinic acids (2,2,2- trifluoroethyls) ester, normal-butyl (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- trifluoroethyls) ester, cyclohexyl (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- trifluoroethyls) ester, (2,2,2- trifluoros Ethyl) phenyl phosphinic acid (2,2,2- trifluoroethyls) ester etc..
It is listed above go out phosphinate in, preferably：Dimethylphosphinic acid methyl esters, diethyl phosphinicacid ethyl ester, two are just Propylphosphinic acid n-propyl, di-n-butyl phosphinic acids N-butyl, diethyl phosphinic acid methyl ester, dimethylphosphinic acid ethyl ester, two are entirely Methyl fluoride phosphinic acids perfluor methyl esters, two (2,2,2- trifluoroethyls) phosphinic acids (2,2,2- trifluoroethyls) esters, two perfluoro-ethyls time Phosphonic acids perfluor ethyl ester, two perfluoro-methyl phosphinic acid methyl esters, two (2,2,2- trifluoroethyls) phosphinic acid methyl esters, two perfluoro-ethyls time phosphine Sour methyl esters, two perfluoro-methyl phosphinicacid ethyl esters, two (2,2,2- trifluoroethyls) phosphinicacid ethyl esters, two perfluoro-ethyl phosphinic acids second Ester, dimethylphosphinic acid (2,2,2- trifluoroethyls) ester, diethyl phosphinic acids (2,2,2- trifluoroethyls) ester etc..
As R1、R2And R3It is the specific example of the compound of alkyl, it can be mentioned, for example：Trimethyl phosphine oxide, triethyl group Phosphine oxide, three n-propyl phosphine oxides, triisopropyl phosphine oxide, three normal-butyl phosphine oxides, triisobutyl phosphine oxide, tri-tert oxygen Change phosphine, three cyclopenta phosphine oxides, tricyclohexylphosphine oxide, ethyl dimethyl phosphine, n-propyl dimethyl phosphine, isopropyl Dimethyl phosphine, normal-butyl dimethyl phosphine, isobutyl group dimethyl phosphine, fert-butyidimethylsilyl phosphine oxide, cyclopenta Dimethyl phosphine, cyclohexyldimethyl phosphine oxide, methyl diethyl phosphine oxide, n-propyl diethyl phosphine oxide, normal-butyl two Ethyl phosphine oxide, cyclohexyl diethyl phosphine oxide, methyl diη-propyl phosphine oxide, ethyl diη-propyl phosphine oxide, cyclohexyl two N-propyl phosphine oxide, methyl di-n-butyl phosphine oxide, ethyl di-n-butyl phosphine oxide, cyclohexyl di-n-butyl phosphine oxide, methyl Dicyclohexyl phosphine oxide, ethyl dicyclohexyl phosphine oxide, n-propyl dicyclohexyl phosphine oxide, normal-butyl dicyclohexyl phosphine oxide, Methylethyl n-propyl phosphine oxide, Methylethyl isopropyl phosphine oxide, Methylethyl normal-butyl phosphine oxide, Methylethyl isobutyl group Phosphine oxide, Methylethyl tertiary butyl phosphine oxide, Methylethyl cyclopenta phosphine oxide, Methylethyl cyclohexyl phosphine oxide, methyl are just Propyl normal-butyl phosphine oxide, methyl normal-butyl cyclohexyl phosphine oxide, methylcyclohexyl (2,2,2- trifluoroethyls) phosphine oxide, three are entirely Methyl fluoride phosphine oxide, three (2,2,2- trifluoroethyls) phosphine oxides, three perfluoro-ethyl phosphine oxides, three (2- fluorine cyclohexyl) phosphine oxides, Three (3- fluorine cyclohexyl) phosphine oxides, three (4- fluorine cyclohexyl) phosphine oxides, perfluoro-methyl dimethyl phosphine, (2,2,2- trifluoro second Base) dimethyl phosphine, perfluoro-ethyl dimethyl phosphine, (2- fluorine cyclohexyl) dimethyl phosphine, (3- fluorine cyclohexyl) two Methyl oxidation phosphine, (4- fluorine cyclohexyl) dimethyl phosphine, (2,2,2- trifluoroethyls) diethyl phosphine oxide, (2,2,2- trifluoros Ethyl) di-n-butyl phosphine oxide, (2,2,2- trifluoroethyls) dicyclohexyl phosphine oxide, methyl two (2,2,2- trifluoroethyls) oxidation Phosphine, ethyl two (2,2,2- trifluoroethyls) phosphine oxide, normal-butyl two (2,2,2- trifluoroethyls) phosphine oxide, cyclohexyl two (2,2, 2- trifluoroethyls) phosphine oxide, Methylethyl perfluoro-methyl phosphine oxide, Methylethyl (2,2,2- trifluoroethyls) phosphine oxide, methyl Ethylperfluoro ethyl phosphine oxide, Methylethyl (2- fluorine cyclohexyl) phosphine oxide, Methylethyl (3- fluorine cyclohexyl) phosphine oxide, methyl Ethyl (4- fluorine cyclohexyl) phosphine oxide, methyl normal-butyl (2,2,2- trifluoroethyls) phosphine oxide, the oxidation of ethyl n-propyl normal-butyl Phosphine, ethyl normal-butyl cyclohexyl phosphine oxide, ethyl normal-butyl (2,2,2- trifluoroethyls) phosphine oxide, ethylcyclohexyl (2,2,2- Trifluoroethyl) phosphine oxide, normal-butyl cyclohexyl (2,2,2- trifluoroethyls) phosphine oxide etc..
It is listed above go out phosphine oxide in, preferably：Trimethyl phosphine oxide, triethyl group phosphine oxide, three n-propyl phosphine oxides, Three normal-butyl phosphine oxides, ethyl dimethyl phosphine, methyl diethyl phosphine oxide, three perfluoro-methyl phosphine oxides, three (2,2,2- tri- Fluoro ethyl) phosphine oxide, three perfluoro-ethyl phosphine oxides etc..
As R1、R2And R3In any one for fluorine atom compound specific example, it can be mentioned, for example：Fluorophosphoric acid two Methyl esters, fluorophosphoric acid Methylethyl ester, fluorophosphoric acid methyl n-propyl ester, fluorophosphoric acid methyl n-butyl, diethyl phthalate, fluorine phosphorus Sour ethyl n-propyl ester, fluorophosphoric acid ethyl n-butyl, fluorophosphoric acid di-n-propyl ester, fluorophosphoric acid n-propyl n-butyl, fluorophosphoric acid Di-n-butyl, fluorophosphoric acid methylcyclopentyl ester, fluorophosphoric acid ethylcyclopentyl ester, fluorophosphoric acid n-propyl cyclopentyl ester, fluorophosphoric acid are just Butyl cyclopentyl ester, two ring pentyl ester of fluorophosphoric acid, fluorophosphoric acid methyl cyclohexane base ester, fluorophosphoric acid cyclohexyl base ester, fluorophosphoric acid positive third Cyclohexyl acetate, fluorophosphoric acid normal-butyl cyclohexyl ester, fluorophosphoric acid dicyclohexyl maleate, fluorophosphoric acid two (trifluoromethyl) ester, fluorophosphoric acid first Base (trifluoromethyl) ester, fluorophosphoric acid ethyl (trifluoromethyl) ester, fluorophosphoric acid n-propyl (trifluoromethyl) ester, fluorophosphoric acid two (2,2, 2- trifluoroethyls) ester, fluorophosphoric acid methyl (2,2,2- trifluoroethyls) ester, fluorophosphoric acid ethyl (2,2,2- trifluoroethyls) ester, fluorine phosphorus Sour n-propyl (2,2,2- trifluoroethyls) ester, fluorophosphoric acid (2,2,2- trifluoroethyls) (trifluoromethyl) ester, (the five fluorine second of fluorophosphoric acid two Base) ester, fluorophosphoric acid methyl (pentafluoroethyl group) ester, fluorophosphoric acid ethyl (pentafluoroethyl group) ester, fluorophosphoric acid n-propyl (pentafluoroethyl group) ester, Fluorophosphoric acid (pentafluoroethyl group) (trifluoromethyl) ester, fluorophosphoric acid (pentafluoroethyl group) (2,2,2- trifluoroethyls) ester etc..
It is listed above go out single fluorophosphoric acid ester in, preferably：Fluorophosphoric acid dimethyl ester, fluorophosphoric acid Methylethyl ester, fluorophosphoric acid Methyl n-propyl ester, diethyl phthalate, fluorophosphoric acid ethyl n-propyl ester, fluorophosphoric acid di-n-propyl ester, two (fluoroform of fluorophosphoric acid Base) ester, fluorophosphoric acid methyl (trifluoromethyl) ester, fluorophosphoric acid ethyl (trifluoromethyl) ester, fluorophosphoric acid n-propyl (trifluoromethyl) ester, Fluorophosphoric acid two (2,2,2- trifluoroethyls) ester, fluorophosphoric acid methyl (2,2,2- trifluoroethyls) ester, fluorophosphoric acid ethyl (2,2,2- trifluoros Ethyl) ester, fluorophosphoric acid n-propyl (2,2,2- trifluoroethyls) ester, fluorophosphoric acid two (pentafluoroethyl group) ester, fluorophosphoric acid methyl (five fluorine second Base) ester, fluorophosphoric acid ethyl (pentafluoroethyl group) ester, fluorophosphoric acid n-propyl (pentafluoroethyl group) etc..
As R1、R2And R3In wantonly 2 for fluorine atom compound specific example, can enumerate：Difluorophosphoric acid methyl esters, Difluorophosphoric acid ethyl ester, difluorophosphoric acid n-propyl, difluorophosphoric acid N-butyl, difluorophosphoric acid ring pentyl ester, difluorophosphoric acid cyclohexyl, difluoro Phosphoric acid (trifluoromethyl) ester, difluorophosphoric acid (2,2,2- trifluoroethyls) ester, difluorophosphoric acid (pentafluoroethyl group) etc..
<1-2-2. nitrile compound>
As nitrile compound, as long as intramolecular has the compound of cyano, its species is not particularly limited.Separately Outside, can also be has the compound of multiple cyano in every 1 molecule.As the specific example of nitrile compound, it can be mentioned, for example：Second Nitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isobutyl cyanide, 2- methylbutyronitriles, trimethylacetonitrile, own nitrile, ring valeronitrile, cyclohexanenitrile, propylene Nitrile, methacrylonitrile, butene nitrile, 3- methyl butenes nitrile, 2- methyl-2-butenes nitrile, 2- allyl acetonitriles, 2- methyl -2- allyl acetonitriles, 3- Methyl -2- allyl acetonitriles, 2- hexenes nitrile, fluoride acetonitrile, two fluoride acetonitriles, trifluoro acetonitrile, 2- fluorine propionitrile, 3- fluorine propionitrile, 2,2- difluoros third The mononitriles chemical combination such as nitrile, 2,3- difluoros propionitrile, 3,3- difluoros propionitrile, 2,2,3- trifluoros propionitrile, 3,3,3- trifluoros propionitrile, five fluorine propionitrile Object；
Malononitrile, succinonitrile, 2- methyl succinonitrile, tetramethyl succinonitrile, glutaronitrile, 2- methyl cellosolve acetate glutaronitriles, adiponitrile, richness The dinitrile compounds such as horse nitrile, 2- methylene glutaronitriles；
Four nitrile compound such as tetracyanoethylene；Deng.
In above-mentioned nitrile compound, preferably acetonitrile, propionitrile, butyronitrile, valeronitrile, butene nitrile, 3- methyl butenes nitrile, malononitrile, Succinonitrile, glutaronitrile, adiponitrile, flumaronitrile etc..
<1-2-3. isocyanate compound>
As isocyanate compound, as long as intramolecular has the compound of isocyanate groups, to its species It is not particularly limited.Alternatively, it is also possible to be in 1 molecule have multiple isocyanate groups compound.As isocyanic acid The specific example of ester compounds, it can be mentioned, for example：Methyl isocyanate, ethyl isocyanate, propyl isocyanate, isocyanic acid isopropyl Ester, n-butyl isocyanate, tert-butyl isocyanate, cyclic isocyanate pentyl ester, NSC 87419, phenyl isocyanate, isocyanic acid ethylene The monoisocyanate compounds such as ester, allyl isocyanate；
Methane diisocyanate, 1,2- ethane diisocyanate, 1,3- propane diisocyanate, 1,4- butane diisocyanates The diisocyanate cpds such as ester；
Isocyanate group methyl formate (メ チ Le イ ソ シ ア ネ ー ト ホ ル メ ー ト), isocyanate group Ethyl formate, Isocyanates acetic acid methyl ester, isocyanates ethyl, isocyanate group n-propyl acetate, 3- isocyanate group propionic acid first Ester, 3- isocyanate group ethyl propionate, 3- isocyanate group n propyl propionate, 2- isocyanate group methyl propionate, 2- isocyanic acids The isocyanate compounds containing ester group such as ester group ethyl propionate, 2- isocyanate group n propyl propionates；
Isocyanate group trimethyl silane, isocyanate group triethylsilane, three n-propyl silane of isocyanate group, isocyanide Perester radical trimethoxy silane, isocyanate group triethoxysilane, three positive propoxy silane of isocyanate group, isocyanate group Methyltrimethylsilane, isocyanatomethyl triethylsilane, 2- isocyanatoethyls trimethyl silane, 2- isocyanates Base ethyl triethylsilane, 3- isocyanate group oxypropyl trimethyls silane, 3- isocyanate group propyl-triethylsilicanes alkane, isocyanic acid Ester group methyltrimethoxysilane, isocyanatomethyl triethoxysilane, 2- isocyanatoethyls trimethoxy silane, 2- isocyanatoethyls triethoxysilane, 3- isocyanate group propyl trimethoxy silicane, 3- isocyanate group propyl three The siliceous isocyanate compound such as Ethoxysilane；
Phosphoric acid isocyanate group dimethyl esters, phosphoric acid isocyanatoethyl methyl ester, phosphoric acid isocyanatomethyl are just Propyl diester, phosphoric acid isocyanate group normal-butyl methyl ester, phosphoric acid isocyanate group diethyl ester, phosphoric acid isocyanatoethyl are just Propyl diester, phosphoric acid isocyanate group normal-butyl ethyl ester, phosphoric acid isocyanate group diη-propyl ester, the positive fourth of phosphoric acid isocyanate group The phosphorous isocyanate compounds such as base n-propyl ester, phosphoric acid isocyanate group di-n-butyl methyl ester.
Wherein, preferably methyl isocyanate, ethyl isocyanate, propyl isocyanate, n-butyl isocyanate, methane diisocyanate Ester, 1,2- ethane diisocyanate, 1,3- propane diisocyanate, 1,4- butane diisocyanates, isocyanate group formic acid first Ester, isocyanate group Ethyl formate, isocyanates acetic acid methyl ester, isocyanates ethyl, isocyanate group trimethyl Silane, isocyanate group triethylsilane, isocyanate group tripropyl silane, isocyanate group trimethoxy silane, isocyanic acid Ester group triethoxysilane, three positive propoxy silane of isocyanate group, phosphoric acid isocyanate group dimethyl esters, phosphoric acid isocyanates Base ethyl-methyl ester, phosphoric acid isocyanate group diethyl ester etc..
<1-2-4. phosphazene compound>
In the present invention 3, so-called " phosphazene compound " refers to use-PXaXbThe compound for the structural unit that=N- is represented (wherein, Xa、XbEach independently represent 1 valency substituent group).According to the number and its bond styles of said structure unit, the present invention In phosphonitrile can be divided into：Single phosphonitrile, the multiple structural units being only made of the structural unit are formed with reference to cyclization Cyclic phosphazene, multiple structural units polyphosphazene for being combined into chain and being formed etc..The species of phosphazene compound is not special Limitation, can use be equivalent in above-mentioned classification any phosphonitrile, wherein, it is preferable to use represented by the following general formula (6) Chain phosphonitrile represented by cyclic phosphazene, and/or the following general formula (7).
[chemical formula 5]
[in general formula (6), X11、X12Separately represent the substituent group of 1 valency.]
[chemical formula 6]
` [in general formula (7), X21、X22、X23、X24、X25、X26、X27Each independently represent 1 valency substituent group.]
It should be noted that in the following description, if not distinguishing ground especially refers to X11、X12、X21、X22、X23、X24、 X25、X26、X27When, then it is represented with X.
As the substituent group of 1 valency, without special limitation as long as the purport of the present invention 3 is not damaged, halogen original can be enumerated The group (R represents alkyl or aryl) that son, alkyl, aryl, acyl group, carboxyl, R-O- are represented (below, is suitably abbreviated as sometimes " RO groups ") etc..Wherein, from the viewpoint of electrochemical stability, preferably halogen atom or RO groups.
As halogen atom, preferably fluorine atom, chlorine atom, bromine atoms, particularly preferred fluorine atom.On the other hand, as RO bases Group, when R is alkyl, the preferred alkyl of carbon number 1~6.As the specific example of preferred alkyl R, methyl, second can be enumerated Base, n-propyl, isopropyl etc., but particularly preferably methyl or ethyl.On the other hand, when R is aryl, preferably phenyl, tolyl, naphthalene Base etc., particularly preferred phenyl.In addition, hydrogen atom can be substituted by halogen atom possessed by alkyl or aryl R.Particularly, pass through Substituted by fluorine, electrochemical stability can be improved, therefore preferably.Upper note X can be entirely same kind of substituent group, but preferably Combine two or more different types of substituent group.
In above-mentioned general formula (6), n usually represents more than 3, less than 10, preferably less than 5 integer.In addition, in general formula (7) In, m usually represents more than 0, and usually less than 10, is preferably less than 3 integer.When N or m is more than 10, electrolyte contains During these compounds, viscosity can increase, and cause the reduction of the battery performances such as load characteristic due to the reduction of conductivity sometimes.
The molecular weight of the compound of above-mentioned general formula (6) and above-mentioned general formula (7) is usually all more than 200, and less than 2000, preferably Scope below 1000.When molecular weight is excessively high, it some times happens that solubilizing poorly, alternatively, since high viscosity causes load special Property deteriorate.
<1-2-5. disulfonate compounds>
As disulfonate compound, as long as intramolecular has the compound of 2 sulfonic acid ester structures, species does not have There is special restriction.As the specific example of chain disulfonate, such as can enumerate：
Glycol dinitrate sulphonic acid ester, two esilate of ethylene glycol, ethylene glycol dipropyl sulphonic acid ester, two fourth sulphonic acid ester of ethylene glycol, Ethylene glycol two (triflate), ethylene glycol two (five fluorine esilates), ethylene glycol two (seven fluorine propane sulfonic acid esters), ethylene glycol two (perfluor butanesulfonate), ethylene glycol two (penta sulphonic acid ester of perfluor), ethylene glycol two (the own sulphonic acid ester of perfluor), (perfluor is pungent for ethylene glycol two Sulphonic acid ester), ethylene glycol two (perfluor 1- methyl esilate), ethylene glycol two (perfluor 1,1- dimethyl esilate), ethylene glycol Two (perfluor 3- methyl fourths sulphonic acid esters), ethylene glycol two (fluorine methanesulfonates), ethylene glycol two (Difluore methane-sulfonic acid ester), ethylene glycol two (2- fluorine esilate), ethylene glycol two (1,1- difluoros esilate), ethylene glycol two (1,2- difluoros esilate), ethylene glycol two (2,2- difluoros esilate), ethylene glycol two (1,1,2- trifluoros esilate), ethylene glycol two (1,2,2- trifluoros esilate), Ethylene glycol two (2,2,2- trifluoros esilate), ethylene glycol two (1,1,2,2- tetrafluoros esilate), two (1,2,2,2- of ethylene glycol Tetrafluoro esilate), ethylene glycol two (the fluoro- 1- methyl esilates of 1-), (the tetra- fluoro- 1- methyl second sulphurs of 1,2,2,2- of ethylene glycol two Acid esters), ethylene glycol two (bis- fluoro- 2- methyl propane sulfonic acids esters of 1,1-), (1,2,2,3,3,3- hexafluoro -1- methyl-prop sulphurs of ethylene glycol two Acid esters), ethylene glycol two (the fluoro- 1- methyl fluorides esilates of 2-), (the tri- fluoro- 1- trifluoromethyls ethanesulfonic acids of 2,2,2- of ethylene glycol two Ester), ethylene glycol two (1- trifluoromethyls esilate), ethylene glycol two (1- methyl-1s-trifluoromethyl esilate), ethylene glycol two Ethylene glycol disulfonic acid esters such as (the own sulphonic acid esters of 1- trifluoromethyls)；
1,2- propylene glycol bis-mesylate, two esilate of 1,2- propylene glycol, 1,2- propylene glycol dipropyls sulphonic acid ester, 1,2- third Two fourth sulphonic acid ester of glycol, 1,2- propylene glycol two (triflate), 1,2- propylene glycol two (five fluorine esilates), 1,2- the third two Alcohol two (seven fluorine propane sulfonic acid esters), 1,2- propylene glycol two (perfluor butanesulfonate), 1,2- propylene glycol two (penta sulphonic acid ester of perfluor), 1,2- Propylene glycol two (the own sulphonic acid ester of perfluor), 1,2- propylene glycol two (perfluorooctane sulfonate ester), (the perfluor 1- methyl second sulphurs of 1,2- propylene glycol two Acid esters), 1,2- propylene glycol two (perfluor 1,1- dimethyl esilate), 1,2- propylene glycol two (perfluor 3- methyl fourths sulphonic acid ester), 1,2- propylene glycol two (fluorine methanesulfonates), 1,2- propylene glycol two (Difluore methane-sulfonic acid ester), (the 2- fluorine ethanesulfonic acids of 1,2- propylene glycol two Ester), 1,2- propylene glycol two (1,1- difluoros esilate), 1,2- propylene glycol two (1,2- difluoros esilate), 1,2- propylene glycol Two (2,2- difluoros esilates), 1,2- propylene glycol two (1,1,2- trifluoros esilate), (the 1,2,2- trifluoros of 1,2- propylene glycol two Esilate), 1,2- propylene glycol two (2,2,2- trifluoros esilate), (the 1,1,2,2- tetrafluoro ethanesulfonic acids of 1,2- propylene glycol two Ester), 1,2- propylene glycol two (1,2,2,2- tetrafluoros esilate), 1,2- propylene glycol two (the fluoro- 1- methyl esilates of 1-), 1,2- Propylene glycol two (tetra- fluoro- 1- methyl esilates of 1,2,2,2-), 1,2- propylene glycol two (bis- fluoro- 2- methyl propane sulfonic acids esters of 1,1-), 1,2- propylene glycol two (1,2,2,3,3,3- hexafluoro -1- methyl propane sulfonic acids ester), (the fluoro- 1- methyl fluorides second sulphurs of 2- of 1,2- propylene glycol two Acid esters), 1,2- propylene glycol two (tri- fluoro- 1- trifluoromethyls esilates of 2,2,2-), (the 1- trifluoromethyl second sulphurs of 1,2- propylene glycol two Acid esters), 1,2- propylene glycol two (1- methyl-1s-trifluoromethyl esilate), (the own sulfonic acid of 1- trifluoromethyls of 1,2- propylene glycol two Ester) etc. 1,2- propylene glycol disulfonic acid esters；
1,3- propylene glycol bis-mesylate, two esilate of 1,3- propylene glycol, 1,3- propylene glycol dipropyls sulphonic acid ester, 1,3- third Two fourth sulphonic acid ester of glycol, 1,3- propylene glycol two (triflate), 1,3- propylene glycol two (five fluorine esilates), 1,3- the third two Alcohol two (seven fluorine propane sulfonic acid esters), 1,3- propylene glycol two (perfluor butanesulfonate), 1,3- propylene glycol two (penta sulphonic acid ester of perfluor), 1,3- Propylene glycol two (the own sulphonic acid ester of perfluor), 1,3- propylene glycol two (perfluorooctane sulfonate ester), (the perfluor 1- methyl second sulphurs of 1,3- propylene glycol two Acid esters), 1,3- propylene glycol two (perfluor 1,1- dimethyl esilate), 1,3- propylene glycol two (perfluor 3- methyl fourths sulphonic acid ester), 1,3- propylene glycol two (fluorine methanesulfonates), 1,3- propylene glycol two (Difluore methane-sulfonic acid ester), (the 2- fluorine ethanesulfonic acids of 1,3- propylene glycol two Ester), 1,3- propylene glycol two (1,1- difluoros esilate), 1,3- propylene glycol two (1,2- difluoros esilate), 1,3- propylene glycol Two (2,2- difluoros esilates), 1,3- propylene glycol two (1,1,2- trifluoros esilate), (the 1,2,2- trifluoros of 1,3- propylene glycol two Esilate), 1,3- propylene glycol two (2,2,2- trifluoros esilate), (the 1,1,2,2- tetrafluoro ethanesulfonic acids of 1,3- propylene glycol two Ester), 1,3- propylene glycol two (1,2,2,2- tetrafluoros esilate), 1,3- propylene glycol two (the fluoro- 1- methyl esilates of 1-), 1,3- Propylene glycol two (tetra- fluoro- 1- methyl esilates of 1,2,2,2-), 1,3- propylene glycol two (bis- fluoro- 2- methyl propane sulfonic acids esters of 1,1-), 1,3- propylene glycol two (1,2,2,3,3,3- hexafluoro -1- methyl propane sulfonic acids ester), (the fluoro- 1- methyl fluorides second sulphurs of 2- of 1,3- propylene glycol two Acid esters), 1,3- propylene glycol two (tri- fluoro- 1- trifluoromethyls esilates of 2,2,2-), (the 1- trifluoromethyl second sulphurs of 1,3- propylene glycol two Acid esters), 1,3- propylene glycol two (1- methyl-1s-trifluoromethyl esilate), (the own sulfonic acid of 1- trifluoromethyls of 1,3- propylene glycol two Ester) etc. 1,3- propylene glycol disulfonic acid esters；
1,2- butanediols bis-mesylate, two esilate of 1,2- butanediols, 1,2- butanediols two (triflate), 1,2- butanediols two (five fluorine esilates), 1,2- butanediols two (seven fluorine propane sulfonic acid esters), (the perfluor fourth sulfonic acid of 1,2- butanediols two Ester), 1,2- butanediols two (perfluor 1- methyl esilate), 1,2- butanediols two (perfluor 1,1- dimethyl esilate), 1, 2- butanediols two (fluorine methanesulfonates), 1,2- butanediols two (Difluore methane-sulfonic acid ester), 1,2- butanediols two (2- fluorine esilate), 1,2- butanediols two (2,2- difluoros esilate), 1,2- butanediols two (2,2,2- trifluoros esilate), 1,2- butanediols two (the fluoro- 1- methyl esilates of 1-), 1,2- butanediols two (the fluoro- 1- methyl fluorides esilates of 2-), two (2,2,2- of 1,2- butanediols Three fluoro- 1- trifluoromethyls esilates), 1,2- butanediols two (1- trifluoromethyls esilate), (the 1- first of 1,2- butanediols two Base -1- trifluoromethyls esilate), the 1,2- butanediol disulfonates such as 1,2- butanediols two (the own sulphonic acid ester of 1- trifluoromethyls) Class；
1,3 butylene glycol bis-mesylate, two esilate of 1,3 butylene glycol, 1,3 butylene glycol two (triflate), 1,3 butylene glycol two (five fluorine esilates), 1,3 butylene glycol two (seven fluorine propane sulfonic acid esters), (the perfluor fourth sulfonic acid of 1,3 butylene glycol two Ester), 1,3 butylene glycol two (perfluor 1- methyl esilate), 1,3 butylene glycol two (perfluor 1,1- dimethyl esilate), 1, 3- butanediols two (fluorine methanesulfonates), 1,3 butylene glycol two (Difluore methane-sulfonic acid ester), 1,3 butylene glycol two (2- fluorine esilate), 1,3 butylene glycol two (2,2- difluoros esilate), 1,3 butylene glycol two (2,2,2- trifluoros esilate), 1,3 butylene glycol two (the fluoro- 1- methyl esilates of 1-), 1,3 butylene glycol two (the fluoro- 1- methyl fluorides esilates of 2-), two (2,2,2- of 1,3 butylene glycol Three fluoro- 1- trifluoromethyls esilates), 1,3 butylene glycol two [(1- trifluoromethyls) esilate], (the 1- first of 1,3 butylene glycol two Base -1- trifluoromethyls esilate), the 1,3 butylene glycols disulfonate such as 1,3 butylene glycol two (the own sulphonic acid ester of 1- trifluoromethyls) Class；
1,4- butanediols bis-mesylate, two esilate of 1,4- butanediols, 1,4- butanediol dipropyls sulphonic acid ester, 1,4- fourths Two fourth sulphonic acid ester of glycol, 1,4- butanediols two (triflate), 1,4- butanediols two (five fluorine esilates), 1,4- fourths two Alcohol two (seven fluorine propane sulfonic acid esters), 1,4- butanediols two (perfluor butanesulfonate), 1,4- butanediols two (penta sulphonic acid ester of perfluor), 1,4- Butanediol two (the own sulphonic acid ester of perfluor), 1,4- butanediols two (perfluorooctane sulfonate ester), (the perfluor 1- methyl second sulphurs of 1,4- butanediols two Acid esters), 1,4- butanediols two (perfluor 1,1- dimethyl esilate), 1,4- butanediols two (perfluor 3- methyl fourths sulphonic acid ester), 1,4- butanediols two (fluorine methanesulfonates), 1,4- butanediols two (Difluore methane-sulfonic acid ester), (the 2- fluorine ethanesulfonic acids of 1,4- butanediols two Ester), 1,4- butanediols two (1,1- difluoros esilate), 1,4- butanediols two (1,2- difluoros esilate), 1,4- butanediols Two (2,2- difluoros esilates), 1,4- butanediols two (1,1,2- trifluoros esilate), (the 1,2,2- trifluoros of 1,4- butanediols two Esilate), 1,4- butanediols two (2,2,2- trifluoros esilate), (the 1,1,2,2- tetrafluoro ethanesulfonic acids of 1,4- butanediols two Ester), 1,4- butanediols two (1,2,2,2- tetrafluoros esilate), 1,4- butanediols two (the fluoro- 1- methyl esilates of 1-), 1,4- Butanediol two (tetra- fluoro- 1- methyl esilates of 1,2,2,2-), 1,4- butanediols two (bis- fluoro- 2- methyl propane sulfonic acids esters of 1,1-), 1,4- butanediols two (1,2,2,3,3,3- hexafluoro -1- methyl propane sulfonic acids ester), (the fluoro- 1- methyl fluorides second sulphurs of 2- of 1,4- butanediols two Acid esters), 1,4- butanediols two (tri- fluoro- 1- trifluoromethyls esilates of 2,2,2-), (the 1- trifluoromethyl second sulphurs of 1,4- butanediols two Acid esters), 1,4- butanediols two (1- methyl-1s-trifluoromethyl esilate), (the own sulfonic acid of 1- trifluoromethyls of 1,4- butanediols two Ester) etc. 1,4- butanediol disulfonic acid esters；
Hydroquinone bis-mesylate, two esilate of hydroquinone, hydroquinone two (triflate), to benzene two Phenol two (five fluorine esilates), hydroquinone two (seven fluorine propane sulfonic acid esters), hydroquinone two (perfluor butanesulfonate), hydroquinone Two (perfluor 1- methyl esilates), hydroquinone two (perfluor 1,1- dimethyl esilate), (the fluorine methanesulfonic acid of hydroquinone two Ester), hydroquinone two (2- fluorine esilate), hydroquinone two (2,2- difluoros esilate), (2,2,2- tri- of hydroquinone two Fluorine esilate), hydroquinone two (the fluoro- 1- methyl esilates of 1-), (the fluoro- 1- methyl fluorides ethanesulfonic acids of 2- of hydroquinone two Ester), hydroquinone two (tri- fluoro- 1- trifluoromethyls esilates of 2,2,2-), hydroquinone two (1- trifluoromethyls esilate), Hydroquinone two (1- methyl-1s-trifluoromethyl esilate), hydroquinone two (the own sulphonic acid ester of 1- trifluoromethyls) etc. are to benzene two Pbenoldisulfonic Acid esters etc..
Among these, preferably：
Glycol dinitrate sulphonic acid ester, two esilate of ethylene glycol, ethylene glycol two (triflate), ethylene glycol two (five Fluorine esilate), ethylene glycol two (fluorine methanesulfonates), ethylene glycol two (Difluore methane-sulfonic acid ester), (the 2- fluorine ethanesulfonic acids of ethylene glycol two Ester), ethylene glycol two (2,2- difluoros esilate), the ethylene glycol disulfonate such as ethylene glycol two (2,2,2- trifluoros esilate) Class；
1,2- propylene glycol bis-mesylate, two esilate of 1,2- propylene glycol, 1,2- propylene glycol two (triflate), 1,2- propylene glycol two (five fluorine esilates), 1,2- propylene glycol two (fluorine methanesulfonates), two (Difluore methane-sulfonic acid of 1,2- propylene glycol Ester), 1,2- propylene glycol two (2- fluorine esilate), 1,2- propylene glycol two (2,2- difluoros esilate), 1,2- propylene glycol two (2, 2,2- trifluoros esilate) etc. 1,2- propylene glycol disulfonic acid esters；
1,3- propylene glycol bis-mesylate, two esilate of 1,3- propylene glycol, 1,3- propylene glycol two (triflate), 1,3- propylene glycol two (five fluorine esilates), 1,3- propylene glycol two (fluorine methanesulfonates), two (Difluore methane-sulfonic acid of 1,3- propylene glycol Ester), 1,3- propylene glycol two (2- fluorine esilate), 1,3- propylene glycol two (2,2- difluoros esilate), 1,3- propylene glycol two (2, 2,2- trifluoros esilate) etc. 1,3- propylene glycol disulfonic acid esters；
1,2- butanediols bis-mesylate, two esilate of 1,2- butanediols, 1,2- butanediols two (triflate), 1,2- butanediols two (five fluorine esilates), 1,2- butanediols two (fluorine methanesulfonates), two (Difluore methane-sulfonic acid of 1,2- butanediols Ester), 1,2- butanediols two (2- fluorine esilate), 1,2- butanediols two (2,2- difluoros esilate), 1,2- butanediols two (2, 2,2- trifluoros esilate) etc. 1,2- butanediol disulfonic acid esters；
1,3 butylene glycol bis-mesylate, two esilate of 1,3 butylene glycol, 1,3 butylene glycol two (triflate), 1,3 butylene glycol two (five fluorine esilates), 1,3 butylene glycol two (fluorine methanesulfonates), two (Difluore methane-sulfonic acid of 1,3 butylene glycol Ester), 1,3 butylene glycol two (2- fluorine esilate), 1,3 butylene glycol two (2,2- difluoros esilate), 1,3 butylene glycol two (2, 2,2- trifluoros esilate) etc. 1,3 butylene glycols disulfonic acid esters；
1,4- butanediols bis-mesylate, two esilate of 1,4- butanediols, 1,4- butanediols two (triflate), 1,4- butanediols two (five fluorine esilates), 1,4- butanediols two (fluorine methanesulfonates), two (Difluore methane-sulfonic acid of 1,4- butanediols Ester), 1,4- butanediols two (2- fluorine esilate), 1,4- butanediols two (2,2- difluoros esilate), 1,4- butanediols two (2, 2,2- trifluoros esilate) etc. 1,4- butanediol disulfonic acid esters etc..
In these compounds, it is more highly preferred to：
Ethylene glycol two (triflate), ethylene glycol two (five fluorine esilates), ethylene glycol two (fluorine methanesulfonates), second The ethylene glycol disulfonic acid esters such as glycol two (2- fluorine esilate), ethylene glycol two (2,2,2- trifluoros esilate)；
1,2- propylene glycol two (triflate), 1,2- propylene glycol two (five fluorine esilates), two (fluorine of 1,2- propylene glycol Methanesulfonates), 1,2- propylene glycol two (2- fluorine esilate), the 1,2- third such as 1,2- propylene glycol two (2,2,2- trifluoros esilate) Glycol disulfonic acid esters；
1,3- propylene glycol two (triflate), 1,3- propylene glycol two (five fluorine esilates), two (2- of 1,3- propylene glycol Fluorine esilate), the 1,3- propylene glycol disulfonic acid esters such as 1,3- propylene glycol two (2,2,2- trifluoros esilate)；
1,2- butanediols two (triflate), 1,2- butanediols two (five fluorine esilates), two (fluorine of 1,2- butanediols Methanesulfonates), 1,2- butanediols two (2- fluorine esilate), the 1,2- fourths such as 1,2- butanediols two (2,2,2- trifluoros esilate) Glycol disulfonic acid esters；
1,3 butylene glycol two (triflate), 1,3 butylene glycol two (five fluorine esilates), two (fluorine of 1,3 butylene glycol Methanesulfonates), 1,3 butylene glycol two (2- fluorine esilate), the 1,3- fourths such as 1,3 butylene glycol two (2,2,2- trifluoros esilate) Glycol disulfonic acid esters；
1,4- butanediols two (triflate), 1,4- butanediols two (five fluorine esilates), two (fluorine of 1,4- butanediols Methanesulfonates), 1,4- butanediols two (2- fluorine esilate), the 1,4- fourths such as 1,4- butanediols two (2,2,2- trifluoros esilate) Glycol disulfonic acid esters etc..
As the specific example of cyclic disulfonic acid ester, can enumerate, such as：
1,5,2,4- dioxas dithian (dioxadithiane) -2,2,4,4- tetroxides, 1,5,2,4- bis- Oxa- dithian -3- methyl -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithian -3,3- diformazans Base -2,2,4,4- tetroxides, the fluoro- 2,2,4,4- tetroxides of 1,5,2,4- dioxa dithians -3-, 1,5,2,4- Two fluoro- 2,2,4,4- tetroxides of dioxa dithian -3,3-, 1,5,2,4- dioxa dithian -6- first Base -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithian -6,6- dimethyl -2,2,4,4- tetroxides, 1, The fluoro- 2,2,4,4- tetroxides of 5,2,4- dioxa dithians -6-, 1,5,2,4- dioxas dithian -6, Bis- fluoro- 2,2,4,4- tetroxides of 6-, 1,5,2,4- dioxa dithian -3,6- dimethyl -2,2,4,4- four are aoxidized Object, two fluoro- 2,2,4,4- tetroxides of 1,5,2,4- dioxa dithians -3,6-, 1,5,2,4- dioxa dithias Hexamethylene -3,3,6,6- tetramethyl -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithians -3,3,6,6- four Fluoro- 2,2,4,4- tetroxides,
1,4,2,5- dioxa dithian -2,2,5,5- tetroxides, 1,4,2,5- dioxa dithia hexamethylenes Alkane -3- methyl -2,2,5,5- tetroxides, four oxygen of 1,4,2,5- dioxa dithian -3,3- dimethyl -2,2,5,5- Compound, the fluoro- 2,2,5,5- tetroxides of 1,4,2,5- dioxa dithians -3-, 1,4,2,5- dioxa dithia rings Two fluoro- 2,2,5,5- tetroxides of hexane -3,3-, 1,4,2,5- dioxa dithian -3,6- dimethyl -2,2,5,5- Tetroxide, two fluoro- 2,2,5,5- tetroxides of 1,4,2,5- dioxa dithians -3,6-, 1,4,2,5- dioxas Dithian -3,3,6,6- tetramethyl -2,2,5,5- tetroxides, 1,4,2,5- dioxas dithian -3,3, Tetra- fluoro- 2,2,5,5- tetroxides of 6,6-,
1,5,2,4- dioxa dithian -6- ketone -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithias Hexamethylene -3- methyl -6- ketone -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithian -3,3- dimethyl -6- Ketone -2,2,4,4- tetroxides, the fluoro- 6- ketone -2,2,4,4- tetroxides of 1,5,2,4- dioxa dithians -3-, 1, Two fluoro- 6- ketone -2,2,4,4- tetroxides of 5,2,4- dioxa dithians -3,3-,
1,5,2,4- dioxa dithia cycloheptane (ジ オ キ サ ジ チ エ パ Application, dioxadithiepane) -2,2,4, 4- tetroxides, 1,5,2,4- dioxa dithia cycloheptane -3- methyl -2,2,4,4- tetroxides, 1,5,2,4- dioxas Dithia cycloheptane -3,3- dimethyl -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithia cycloheptane -3- fluoro- 2,2, 4,4- tetroxides, two fluoro- 2,2,4,4- tetroxides of 1,5,2,4- dioxa dithia cycloheptane -3,3-, 1,5,2,4- bis- Oxa- dithia cycloheptane -6- methyl -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithia cycloheptane -6,7- diformazans Base -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithia cyclooctane (ジ オ キ サ ジ チ オ カ Application, Dioxadithiocane) -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithias cyclononane (ジ オ キ サ ジ チ オ Na Application, dioxadithionane) -2,2,4,4- tetroxides etc..
It is preferred that the following compound with 6 Yuans ring structures：
1,5,2,4- dioxa dithian -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithia hexamethylenes Alkane -3- methyl -2,2,4,4- tetroxides, four oxygen of 1,5,2,4- dioxa dithian -3,3- dimethyl -2,2,4,4- Compound, the fluoro- 2,2,4,4- tetroxides of 1,5,2,4- dioxa dithians -3-, 1,5,2,4- dioxa dithia rings Two fluoro- 2,2,4,4- tetroxides of hexane -3,3-, four oxygen of 1,5,2,4- dioxa dithian -6- methyl -2,2,4,4- Compound, 1,5,2,4- dioxa dithian -6,6- dimethyl -2,2,4,4- tetroxides, 1,5,2,4- dioxas two The fluoro- 2,2,4,4- tetroxides of thia hexamethylene -6-, two fluoro- 2,2,4,4- of 1,5,2,4- dioxa dithians -6,6- Tetroxide, 1,5,2,4- dioxa dithian -3,6- dimethyl -2,2,4,4- tetroxides, 1,5,2,4- dioxies Miscellaneous two fluoro- 2,2,4,4- tetroxides of dithian -3,6-, 1,5,2,4- dioxa dithians -3,3,6,6- Tetramethyl -2,2,4,4- tetroxides, four fluoro- tetra- oxygen of 2,2,4,4- of 1,5,2,4- dioxa dithians -3,3,6,6- Compound,
1,4,2,5- dioxa dithian -2,2,5,5- tetroxides, 1,4,2,5- dioxa dithia hexamethylenes Alkane -3- methyl -2,2,5,5- tetroxides, four oxygen of 1,4,2,5- dioxa dithian -3,3- dimethyl -2,2,5,5- Compound, the fluoro- 2,2,5,5- tetroxides of 1,4,2,5- dioxa dithians -3-, 1,4,2,5- dioxa dithia rings Two fluoro- 2,2,5,5- tetroxides of hexane -3,3-, 1,4,2,5- dioxa dithian -3,6- dimethyl -2,2,5,5- Tetroxide, two fluoro- 2,2,5,5- tetroxides of 1,4,2,5- dioxa dithians -3,6-, 1,4,2,5- dioxas Dithian -3,3,6,6- tetramethyl -2,2,5,5- tetroxides, 1,4,2,5- dioxas dithian -3,3, Tetra- fluoro- 2,2,5,5- tetroxides of 6,6-,
1,5,2,4- dioxa dithian -6- ketone -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithias Hexamethylene -3- methyl -6- ketone -2,2,4,4- tetroxides, 1,5,2,4- dioxa dithian -3,3- dimethyl -6- Ketone -2,2,4,4- tetroxides, the fluoro- 6- ketone -2,2,4,4- tetroxides of 1,5,2,4- dioxa dithians -3-, 1, Two fluoro- 6- ketone -2,2,4,4- tetroxides of 5,2,4- dioxa dithians -3,3- etc..
<1-2-6. sulfide compound>
As sulfide compound, as long as intramolecular has the compound of sulfide based structural, species is not special Limitation.As the specific example of sulfide compound, can enumerate, such as：
Dimethyl sulfide, diethyl thioether, diη-propyl thioether, diisopropyl thioether, di-n-butyl thioether, diisobutyl Thioether, di-t-butyl thioether, bicyclopentyl thioether, dicyclohexylsulfide,
Ethyl methyl sulfide, methyl-propyl thioether, isopropyl methyl thioether, methyl n-butyl sulfide, methyl-isobutyl sulphur Ether, methyl tertbutyl thioether, methylcyclopentyl thioether, methylcyclohexyl thioether, ethyl propyl thioether, ethylisopropyl base thioether, Ethyl n-butyl sulfide, ethyl isobutyl base thioether, ethyl tert-butyl thioether, ethylcyclopentyl thioether, ethylcyclohexyl thioether,
Diphenylsulfide, two (2- toluyls) thioethers, two (3- toluyls) thioethers, two (4- toluyls) thioethers, Vinyl thioether, allyl sulfide, dibenzyl sulfide,
Aminomethyl phenyl thioether, methyl (2- toluyls) thioether, methyl (3- toluyls) thioether, methyl (4- toluoyls Base) thioether, methyl vinyl sulfide, methyl allyl sufide, methylbenzyl thioether, ethylphenyl thioether, ethyl (2- toluoyls Base) thioether, ethyl (3- toluyls) thioether, ethyl (4- toluyls) thioether, ethyl vinyl thioether, allyl ethyl sulphur Ether, Ethylbenzyl thioether,
Phenyl propyl thioether, propyloxy phenyl base thioether, phenyl n-butyl sulfide, phenyl isobutyl base thioether, phenyl t-butyl Thioether, phenylcyclopentyl thioether, phenylcyclohexyl thioether, phenyl (2- toluyls) thioether, phenyl (3- toluyls) thioether, Phenyl (4- toluyls) thioether, phenyl vinyl sulfide, phenyl allyl thioether, phenylbenzyl thioether,
Two (methyl fluoride) thioethers, two (difluoromethyl) thioethers, two (trifluoromethyl) thioethers, two (1- fluoro ethyls) thioethers, two (2- fluoro ethyls) thioether, two (2,2,2- trifluoroethyls) thioethers, two (perfluoro-ethyl) thioethers, two (3,3,3- trifluoros n-propyl) sulphur Ether, two (five fluorine n-propyls of 2,2,3,3,3-) thioethers, two (perfluor n-propyl) thioethers, two (2- fluorine isopropyl) thioethers, two (2,2, 2,2 ', 2 ', 2 '-hexafluoro isopropyl) thioether, two (perfluoro-n-butyl group) thioethers, two (2- fluorine tertiary butyl) thioethers, two (the tertiary fourths of perfluor Base) thioether, two (2- fluorine cyclohexyl) thioethers, two (3- fluorine cyclohexyl) thioethers, two (4- fluorine cyclohexyl) thioethers, two (perfluor hexamethylenes Base) thioether, methyl (methyl fluoride) thioether,
Methyl (difluoromethyl) thioether, methyl (trifluoromethyl) thioether, methyl (1- fluoro ethyls) thioether, methyl (2- fluorine second Base) thioether, methyl (2,2,2- trifluoroethyls) thioether, methyl (perfluoro-ethyl) thioether, methyl (3,3,3- trifluoros n-propyl) sulphur Ether, methyl (five fluorine n-propyls of 2,2,3,3,3-) thioether, methyl (perfluor n-propyl) thioether, methyl (2- fluorine isopropyl) thioether, Methyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) thioether, methyl (perfluoro-n-butyl group) thioether, methyl (2- fluorine tertiary butyl) sulphur Ether, methyl (perfluoro-t-butyl) thioether, methyl (2- fluorine cyclohexyl) thioether, methyl (3- fluorine cyclohexyl) thioether, methyl (4- fluorine rings Hexyl) thioether, methyl (perfluorocyclohexyl) thioether,
Ethyl (methyl fluoride) thioether, ethyl (difluoromethyl) thioether, ethyl (trifluoromethyl) thioether, ethyl (1- fluoro ethyls) Thioether,
Ethyl (2- fluoro ethyls) thioether, ethyl (2,2,2- trifluoroethyls) thioether, ethyl (perfluoro-ethyl) thioether, ethyl (3,3,3- trifluoros n-propyl) thioether, ethyl (five fluorine n-propyls of 2,2,3,3,3-) thioether, ethyl (perfluor n-propyl) thioether, second Base (2- fluorine isopropyl) thioether, ethyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) thioether, ethyl (perfluoro-n-butyl group) thioether, Ethyl (2- fluorine tertiary butyl) thioether, ethyl (perfluoro-t-butyl) thioether, ethyl (2- fluorine cyclohexyl) thioether, ethyl (3- fluorine hexamethylenes Base) thioether, ethyl (4- fluorine cyclohexyl) thioether, ethyl (perfluorocyclohexyl) thioether,
(2,2,2- trifluoroethyls) (methyl fluoride) thioether, (2,2,2- trifluoroethyls) (difluoromethyl) thioether, (2,2,2- tri- Fluoro ethyl) (trifluoromethyl) thioether, (2,2,2- trifluoroethyls) (1- fluoro ethyls) thioether, (2,2,2- trifluoroethyls) (2- fluorine second Base) thioether, (2,2,2- trifluoroethyls) (perfluoro-ethyl) thioether, (2,2,2- trifluoroethyls) (3,3,3- trifluoros n-propyl) sulphur Ether, (2,2,2- trifluoroethyls) (five fluorine n-propyls of 2,2,3,3,3-) thioether, (2,2,2- trifluoroethyls) (perfluor n-propyl) sulphur Ether, (2,2,2- trifluoroethyls) (2- fluorine isopropyl) thioether, (2,2,2- trifluoroethyls) (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl Base) thioether, (2,2,2- trifluoroethyls) (perfluoro-n-butyl group) thioether, (2,2,2- trifluoroethyls) (2- fluorine tertiary butyl) thioether, (2, 2,2- trifluoroethyls) (perfluoro-t-butyl) thioether, (2,2,2- trifluoroethyls) (2- fluorine cyclohexyl) thioether, (2,2,2- trifluoro second Base) (3- fluorine cyclohexyl) thioether, (2,2,2- trifluoroethyls) (4- fluorine cyclohexyl) thioether, (2,2,2- trifluoroethyls) (perfluor ring Hexyl) thioether,
Two (2- fluorophenyls) thioethers, two (3- fluorophenyls) thioethers, two (4- fluorophenyls) thioethers, two (2,3- difluorophenyls) sulphur Ether, two (2,4 difluorobenzene base) thioethers, two (3,5- difluorophenyls) thioethers, two (2,4,6- trifluorophenyls) thioethers, two (perfluor benzene Base) thioether, two (1- is fluoride-based) thioethers, two (2- is fluoride-based) thioethers, two (perfluorovinyl sulfide) thioethers, two [(2- fluorobenzene Base) methyl] thioether, two [(3- fluorophenyls) methyl] thioethers, two [(4- fluorophenyls) methyl] thioethers, two [(perfluorophenyl) methyl] Thioether,
Methyl (2- fluorophenyls) thioether, methyl (3- fluorophenyls) thioether, methyl (4- fluorophenyls) thioether, methyl (2,3- bis- Fluorophenyl) thioether, methyl (2,4 difluorobenzene base) thioether, methyl (3,5- difluorophenyls) thioether, methyl (2,4,6- trifluoro-benzenes Base) thioether, methyl (perfluorophenyl) thioether, methyl (1- is fluoride-based) thioether, methyl (2- is fluoride-based) thioether, methyl be (complete It is fluoride-based) thioether, methyl [(2- fluorophenyls) methyl] thioether, methyl [(3- fluorophenyls) methyl] thioether, methyl [(4- fluorobenzene Base) methyl] thioether, methyl [(perfluorophenyl) methyl] thioether,
Ethyl (2- fluorophenyls) thioether, ethyl (3- fluorophenyls) thioether, ethyl (4- fluorophenyls) thioether, ethyl (2,3- bis- Fluorophenyl) thioether, ethyl (2,4 difluorobenzene base) thioether, ethyl (3,5- difluorophenyls) thioether, ethyl (2,4,6- trifluoro-benzenes Base) thioether, ethyl (perfluorophenyl) thioether, ethyl (1- is fluoride-based) thioether, ethyl (2- is fluoride-based) thioether, ethyl be (complete It is fluoride-based) thioether, ethyl [(2- fluorophenyls) ethyl] thioether, ethyl [(3- fluorophenyls) methyl] thioether, ethyl [(4- fluorobenzene Base) methyl] thioether, ethyl [(perfluorophenyl) methyl] thioether,
Phenyl (methyl fluoride) thioether, phenyl (difluoromethyl) thioether, phenyl (trifluoromethyl) thioether, phenyl (1- fluoro ethyls) Thioether, phenyl (2- fluoro ethyls) thioether, phenyl (2,2,2- trifluoroethyls) thioether, phenyl (perfluoro-ethyl) thioether, phenyl (3,3, 3- trifluoros n-propyl) thioether, phenyl (five fluorine n-propyls of 2,2,3,3,3-) thioether, phenyl (perfluor n-propyl) thioether, phenyl (2- Fluorine isopropyl) thioether, phenyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) thioether, phenyl (perfluoro-n-butyl group) thioether, phenyl (2- fluorine tertiary butyl) thioether, phenyl (perfluoro-t-butyl) thioether, phenyl (2- fluorine cyclohexyl) thioether, phenyl (3- fluorine cyclohexyl) sulphur Ether, phenyl (4- fluorine cyclohexyl) thioether, phenyl (perfluorocyclohexyl) thioether, phenyl (2- fluorophenyls) thioether, phenyl (3- fluorobenzene Base) thioether, phenyl (4- fluorophenyls) thioether, phenyl (2,3- difluorophenyls) thioether, phenyl (2,4 difluorobenzene base) thioether, phenyl (3,5- difluorophenyls) thioether, phenyl (2,4,6- trifluorophenyls) thioether, phenyl (perfluorophenyl) thioether, phenyl (1- vinyl fluoride Base) thioether, phenyl (2- is fluoride-based) thioether, phenyl (perfluorovinyl sulfide) thioether, phenyl [(2- fluorophenyls) methyl] thioether, benzene Base [(3- fluorophenyls) methyl] thioether, phenyl [(4- fluorophenyls) methyl] thioether, phenyl [(perfluorophenyl) methyl] thioether,
(2,2,2- trifluoroethyls) (2- fluorophenyls) thioether, (2,2,2- trifluoroethyls) (3- fluorophenyls) thioether, (2,2,2- Trifluoroethyl) (4- fluorophenyls) thioether, (2,2,2- trifluoroethyls) (2,3- difluorophenyls) thioether, (2,2,2- trifluoroethyls) (2,4 difluorobenzene base) thioether, (2,2,2- trifluoroethyls) (3,5- difluorophenyls) thioether, (2,2,2- trifluoroethyls) (2,4,6- Trifluorophenyl) thioether, (2,2,2- trifluoroethyls) (perfluorophenyl) thioether, (2,2,2- trifluoroethyls) (1- is fluoride-based) sulphur Ether, (2,2,2- trifluoroethyls) (2- is fluoride-based) thioether, (2,2,2- trifluoroethyls) (perfluorovinyl sulfide) thioether, (2,2,2- Trifluoroethyl) [(2- fluorophenyls) methyl] thioether, (2,2,2- trifluoroethyls) [(3- fluorophenyls) methyl] thioether, (2,2,2- tri- Fluoro ethyl) [(4- fluorophenyls) methyl] thioether, (2,2,2- trifluoroethyls) [(perfluorophenyl) methyl] thioether etc..
<1-2-7. disulfide compound>
As disulfide compound, as long as intramolecular has the compound of disulfide structure, species is without spy Other restriction.As the specific example of disulfide compound, can enumerate, such as：
Dimethyl disulfide, diethyl disulphide, diη-propyl disulfide, diisopropyl disulfide ether, two sulphur of di-n-butyl Ether, diisobutyl disulfide, di-tert-butyl disulfide, bicyclopentyl disulfide, dicyclohexyldisulfide,
Ethyl-methyl disulfide, methyl propyl disulfide, isopropyl methyl disulfide, methyl normal-butyl disulfide, methyl Isobutyl group disulfide, methyl tertbutyl disulfide, methylcyclopentyl disulfide, methylcyclohexyl disulfide, two sulphur of ethyl propyl Ether, ethylisopropyl base disulfide, ethyl normal-butyl disulfide, ethyl isobutyl base disulfide, ethyl tert-butyl disulfide, ethyl ring Diamyl disulfide ether, ethylcyclohexyl disulfide,
Diphenyl disulfide ether, two (2- toluyls) disulfides, two (3- toluyls) disulfides, two (4- toluyls) Disulfide, divinyl disulfide, diallyl disulphide, benzyldithio toluene,
Aminomethyl phenyl disulfide, methyl (2- toluyls) disulfide, methyl (3- toluyls) disulfide, methyl (4- Toluyl) disulfide, methyl ethylene disulfide, methacrylic disulfide, methylbenzyl disulfide, two sulphur of ethylphenyl Ether, ethyl (2- toluyls) disulfide, ethyl (3- toluyls) disulfide, ethyl (4- toluyls) disulfide, ethyl Vinyl disulfide, allyl ethyl disulfide, Ethylbenzyl disulfide,
Phenyl propyl disulfide, propyloxy phenyl base disulfide, phenyl normal-butyl disulfide, phenyl isobutyl base disulfide, benzene Base butyl disulphide, phenylcyclopentyl disulfide, phenylcyclohexyl disulfide, phenyl (2- toluyls) disulfide, phenyl (3- toluyls) disulfide, phenyl (4- toluyls) disulfide, phenyl vinyl disulfide, phenyl allyl disulfide, Phenylbenzyl disulfide,
Two (methyl fluoride) disulfides, two (difluoromethyl) disulfides, two (trifluoromethyl) disulfides, two (1- fluoro ethyls) two Thioether, two (2- fluoro ethyls) disulfides, two (2,2,2- trifluoroethyls) disulfides, two (perfluoro-ethyl) disulfides, two (3,3,3- Trifluoro n-propyl) disulfide, two (five fluorine n-propyls of 2,2,3,3,3-) disulfides, two (perfluor n-propyl) disulfides, two (2- fluorine Isopropyl) disulfide, two (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) disulfides, two (perfluoro-n-butyl group) disulfides, two (2- Fluorine tertiary butyl) disulfide, two (perfluoro-t-butyl) disulfides, two (2- fluorine cyclohexyl) disulfides, two (3- fluorine cyclohexyl) two sulphur Ether, two (4- fluorine cyclohexyl) disulfides, two (perfluorocyclohexyl) disulfides,
Methyl (methyl fluoride) disulfide, methyl (difluoromethyl) disulfide, methyl (trifluoromethyl) disulfide, methyl (1- Fluoro ethyl) disulfide, methyl (2- fluoro ethyls) disulfide, methyl (2,2,2- trifluoroethyls) disulfide, methyl (perfluoro-ethyl) Disulfide, methyl (3,3,3- trifluoros n-propyl) disulfide, methyl (five fluorine n-propyls of 2,2,3,3,3-) disulfide, methyl are (complete Fluorine n-propyl) disulfide, methyl (2- fluorine isopropyl) disulfide, methyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) disulfide, Methyl (perfluoro-n-butyl group) disulfide, methyl (the fluoro- tertiary butyls of 2-) disulfide, methyl (perfluoro-t-butyl) disulfide, methyl (2- Fluorine cyclohexyl) disulfide, methyl (3- fluorine cyclohexyl) disulfide, methyl (4- fluorine cyclohexyl) disulfide, methyl (perfluor hexamethylene Base) disulfide,
Ethyl (methyl fluoride) disulfide, ethyl (difluoromethyl) disulfide, ethyl (trifluoromethyl) disulfide, ethyl (1- Fluoro ethyl) disulfide, ethyl (2- fluoro ethyls) disulfide, ethyl (2,2,2- trifluoroethyls) disulfide, ethyl (perfluoro-ethyl) Disulfide, ethyl (3,3,3- trifluoros n-propyl) disulfide, ethyl (five fluorine n-propyls of 2,2,3,3,3-) disulfide, ethyl are (complete Fluorine n-propyl) disulfide, ethyl (2- fluorine isopropyl) disulfide, ethyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) disulfide, Ethyl (perfluoro-n-butyl group) disulfide, ethyl (2- fluorine tertiary butyl) disulfide, ethyl (perfluoro-t-butyl) disulfide, ethyl (2- Fluorine cyclohexyl) disulfide, ethyl (3- fluorine cyclohexyl) disulfide, ethyl (4- fluorine cyclohexyl) disulfide, ethyl (perfluor hexamethylene Base) disulfide,
(2,2,2- trifluoroethyls) (methyl fluoride) disulfide, (2,2,2- trifluoroethyls) (difluoromethyl) disulfide, (2,2, 2- trifluoroethyls) (trifluoromethyl) disulfide, (2,2,2- trifluoroethyls) (1- fluoro ethyls) disulfide, (2,2,2- trifluoroethyls) (2- fluoro ethyls) disulfide, (2,2,2- trifluoroethyls) (perfluoro-ethyl) disulfide, (2,2,2- trifluoroethyls) (3,3,3- trifluoros N-propyl) disulfide, (2,2,2- trifluoroethyls) (five fluoro- n-propyls of 2,2,3,3,3-) disulfide, (2,2,2- trifluoroethyls) (perfluor n-propyl) disulfide, (2,2,2- trifluoroethyls) (2- fluorine isopropyl) disulfide, (2,2,2- trifluoroethyls) (2,2,2, 2 ', 2 ', 2 '-hexafluoro isopropyl) disulfide, (2,2,2- trifluoroethyls) (perfluoro-n-butyl group) disulfide, (2,2,2- trifluoro second Base) (2- fluorine tertiary butyl) disulfide, (2,2,2- trifluoroethyls) (perfluoro-t-butyl) disulfide, (2,2,2- trifluoroethyls) (2- Fluorine cyclohexyl) disulfide, (2,2,2- trifluoroethyls) (3- fluorine cyclohexyl) disulfide, (2,2,2- trifluoroethyls) (4- fluorine hexamethylenes Base) disulfide, (2,2,2- trifluoroethyls) (perfluorocyclohexyl) disulfide,
Two (2- fluorophenyls) disulfides, two (3- fluorophenyls) disulfides, two (4- fluorophenyls) disulfides, two (2,3- difluoros Phenyl) disulfide, two (2,4 difluorobenzene base) disulfides, two (3,5- difluorophenyls) disulfides, two (2,4,6- trifluorophenyls) Disulfide, two (perfluorophenyl) disulfides, two (1- is fluoride-based) disulfides, two (2- is fluoride-based) disulfides, two (perfluor second Alkenyl) disulfide, two [(2- fluorophenyls) methyl] disulfides, two [(3- fluorophenyls) methyl] disulfides, two [(4- fluorophenyls) first Base] disulfide, two [(perfluorophenyl) methyl] disulfides,
Methyl (2- fluorophenyls) disulfide, methyl (3- fluorophenyls) disulfide, methyl (4- fluorophenyls) disulfide, methyl (2,3- difluorophenyls) disulfide, methyl (2,4 difluorobenzene base) disulfide, methyl (3,5- difluorophenyls) disulfide, methyl (2,4,6- trifluorophenyls) disulfide, methyl (perfluorophenyl) disulfide, methyl (1- is fluoride-based) disulfide, methyl (2- fluorine Vinyl) disulfide, methyl (perfluorovinyl sulfide) disulfide, methyl [(2- fluorophenyls) methyl] disulfide, methyl [(3- fluorobenzene Base) methyl] disulfide, methyl [(4- fluorophenyls) methyl] disulfide, methyl [(perfluorophenyl) methyl] disulfide,
Ethyl (2- fluorophenyls) disulfide, ethyl (3- fluorophenyls) disulfide, ethyl (4- fluorophenyls) disulfide, ethyl (2,3- difluorophenyls) disulfide, ethyl (2,4 difluorobenzene base) disulfide, ethyl (3,5- difluorophenyls) disulfide, ethyl (2,4,6- trifluorophenyls) disulfide, ethyl (perfluorophenyl) disulfide, ethyl (1- is fluoride-based) disulfide, ethyl (2- fluorine Vinyl) disulfide, ethyl (perfluorovinyl sulfide) disulfide, ethyl [(2- fluorophenyls) ethyl] disulfide, ethyl [(3- fluorobenzene Base) methyl] disulfide, ethyl [(4- fluorophenyls) methyl] disulfide, ethyl [(perfluorophenyl) methyl] disulfide,
Phenyl (methyl fluoride) disulfide, phenyl (difluoromethyl) disulfide, phenyl (trifluoromethyl) disulfide, phenyl (1- Fluoro ethyl) disulfide, phenyl (2- fluoro ethyls) disulfide, phenyl (2,2,2- trifluoroethyls) disulfide, phenyl (perfluoro-ethyl) Disulfide, phenyl (3,3,3- trifluoros n-propyl) disulfide, phenyl (five fluorine n-propyls of 2,2,3,3,3-) disulfide, phenyl are (complete Fluorine n-propyl) disulfide, phenyl (2- fluorine isopropyl) disulfide, phenyl (2,2,2,2 ', 2 ', 2 '-hexafluoro isopropyl) disulfide, Phenyl (perfluoro-n-butyl group) disulfide, phenyl (the fluoro- tertiary butyls of 2-) disulfide, phenyl (perfluoro-t-butyl) disulfide, phenyl (2- Fluorine cyclohexyl) disulfide, phenyl (3- fluorine cyclohexyl) disulfide, phenyl (4- fluorine cyclohexyl) disulfide, phenyl (perfluor hexamethylene Base) disulfide, phenyl (2- fluorophenyls) disulfide, phenyl (3- fluorophenyls) disulfide, phenyl (4- fluorophenyls) disulfide, phenyl (2,3- difluorophenyls) disulfide, phenyl (2,4 difluorobenzene base) disulfide, phenyl (3,5- difluorophenyls) disulfide, phenyl (2,4,6- trifluorophenyls) disulfide, phenyl (perfluorophenyl) disulfide, phenyl (1- is fluoride-based) disulfide, phenyl (2- fluorine Vinyl) disulfide, phenyl (perfluorovinyl sulfide) disulfide, phenyl [(2- fluorophenyls) methyl] disulfide, phenyl [(3- fluorobenzene Base) methyl] disulfide, phenyl [(4- fluorophenyls) methyl] disulfide, phenyl [(perfluorophenyl) methyl] disulfide,
(2,2,2- trifluoroethyls) (2- fluorophenyls) disulfide, (2,2,2- trifluoroethyls) (3- fluorophenyls) disulfide, (2, 2,2- trifluoroethyls) (4- fluorophenyls) disulfide, (2,2,2- trifluoroethyls) (2,3- difluorophenyls) disulfide, (2,2,2- tri- Fluoro ethyl) (2,4 difluorobenzene base) disulfide, (2,2,2- trifluoroethyls) (3,5- difluorophenyls) disulfide, (2,2,2- trifluoros Ethyl) (2,4,6- trifluorophenyls) disulfide, (2,2,2- trifluoroethyls) (perfluorophenyl) disulfide, (2,2,2- trifluoroethyls) (1- is fluoride-based) disulfide, (2,2,2- trifluoroethyls) (2- is fluoride-based) disulfide, (2,2,2- trifluoroethyls) (perfluor second Alkenyl) disulfide, (2,2,2- trifluoroethyls) [(2- fluorophenyls) methyl] disulfide, (2,2,2- trifluoroethyls) [(3- fluorobenzene Base) methyl] disulfide, (2,2,2- trifluoroethyls) [(4- fluorophenyls) methyl] disulfide, (2,2,2- trifluoroethyls) [(perfluor Phenyl) methyl] disulfide.
<1-2-8. acid anhydrides>
The species of acid anhydrides is not particularly limited.As long as in addition, there is the compound of multiple acid anhydride structures in a molecule .It as the acid anhydrides that the present invention 3 uses, can enumerate, the acid that the acid anhydrides of carboxylic acid, the acid anhydrides of sulfonic acid, carboxylic acid and sulfonic acid are formed Acid anhydride.
As the specific example of carboxylic acid anhydrides, can enumerate：
Acetic anhydride, propionic andydride, butyric anhydride, crotonic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride, succinic anhydride, glutaric acid Acid anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, anhydride diethylene glycol, cyclohexane cyclohexanedimethanodibasic acid anhydride, pentamethylene tetramethyl Acid dianhydride, 4- cyclohexene -1,2- dicarboxylic acid anhydrides, 3,4,5,6- tetrabydrophthalic anhydrides, 5- norbornene -2,3- dioctyl phthalate Acid anhydride, phenylsuccinic acid acid anhydride, 2- phenyl glutaric anhydride, phthalic anhydride, pyromellitic dianhydride, fluoro succinic anhydride, tetrafluoro amber Amber acid anhydrides etc..
Wherein, preferably：Succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, anhydride diethylene glycol, ring Hexane dicarboxylic acid acid anhydride, fluoro succinic anhydride, tetrafluoro succinic anhydride etc..
As the specific example of sulphonic acid anhydride, can enumerate,
Methanesulfonic acid acid anhydride, ethanesulfonic acid acid anhydride, propane sulfonic acid acid anhydride, fourth sulphonic acid anhydride, penta sulphonic acid anhydride, own sulphonic acid anhydride, vinyl sulfonic acid acid anhydride, benzene The third two sulphur of sulphonic acid anhydride, trifluoromethanesulfanhydride anhydride, 2,2,2- trifluoro ethanesulfonic acids acid anhydride, five fluorine ethanesulfonic acid acid anhydrides, 1,2- ethionic anhydrides, 1,3- Acid anhydrides, 1,4- fourth disulfonic acid acid anhydride, 1,2- benzenedisulfonic acids acid anhydride, four fluoro- 1,2- ethionic anhydrides, the third disulfonic acid of hexafluoro -1,3- acid anhydride, eight Fluoro- 1,4- fourths disulfonic acid acid anhydride, the fluoro- 1,2- benzenedisulfonic acids acid anhydrides of 3-, the fluoro- 1,2- benzenedisulfonic acids acid anhydrides of 4-, tetra- fluoro- 1,2- benzene of 3,4,5,6- Disulfonic acid acid anhydride etc..
Wherein, preferably：
Methanesulfonic acid acid anhydride, ethanesulfonic acid acid anhydride, propane sulfonic acid acid anhydride, fourth sulphonic acid anhydride, vinyl sulfonic acid acid anhydride, benzene sulfonic acid acid anhydride, trifluoromethanesulfonic acid Acid anhydride, 2,2,2- trifluoro ethanesulfonic acids acid anhydride, five fluorine ethanesulfonic acid acid anhydrides, 1,2- ethionic anhydrides, the third disulfonic acid of 1,3- acid anhydride, 1,2- benzenedisulfonic acids Acid anhydride etc..
As the specific example for the acid anhydrides that carboxylic acid and sulfonic acid are formed, can enumerate：
Acetic acid methanesulfonic acid acid anhydride, acetic acid ethanesulfonic acid acid anhydride, acetic acid propane sulfonic acid acid anhydride, propionic acid methanesulfonic acid acid anhydride, propionic acid ethanesulfonic acid acid anhydride, propionic acid Propane sulfonic acid acid anhydride, trifluoroacetic acid methanesulfonic acid acid anhydride, trifluoroacetic acid ethanesulfonic acid acid anhydride, trifluoroacetic acid propane sulfonic acid acid anhydride, acetic acid trifluoromethanesulfanhydride anhydride, Acetic acid 2,2,2- trifluoro ethanesulfonic acids acid anhydride, five fluorine ethanesulfonic acid acid anhydride of acetic acid, trifluoroacetic acid trifluoromethanesulfanhydride anhydride, trifluoroacetic acid 2,2,2- tri- Fluorine ethanesulfonic acid acid anhydride, five fluorine ethanesulfonic acid acid anhydride of trifluoroacetic acid, 3- Sulfo propionic acids acid anhydride, 2- methyl -3- Sulfo propionic acids acid anhydride, 2,2- dimethyl - 3- Sulfo propionic acids acid anhydride, 2- ethyl -3- Sulfo propionic acids acid anhydride, 2,2- diethyl -3- Sulfo propionic acids acid anhydride, the fluoro- 3- Sulfo propionic acids acid anhydrides of 2-, 2, Bis- fluoro- 3- Sulfo propionic acids acid anhydrides of 2-, tetra- fluoro- 3- Sulfo propionic acids acid anhydrides of 2,2,3,3-, 2- sulfosalicylic acids acid anhydride, the fluoro- 2- sulphophenyls first of 3- The fluoro- 2- sulfosalicylic acids acid anhydride of acid anhydrides, 4-, the fluoro- 2- sulfosalicylic acids acid anhydrides of 5-, the fluoro- 2- sulfosalicylic acids acid anhydrides of 6-, bis- fluoro- 2- of 3,6- Sulfosalicylic acid acid anhydride, tetra- fluoro- 2- sulfosalicylic acids acid anhydrides of 3,4,5,6-, 3- trifluoromethyl -2- sulfosalicylic acids acid anhydride, 4- fluoroforms Base -2- sulfosalicylic acids acid anhydride, 5- trifluoromethyl -2- sulfosalicylic acids acid anhydride, 6- trifluoromethyl -2- sulfosalicylic acid acid anhydrides etc..
Wherein, preferably：
Acetic acid methanesulfonic acid acid anhydride, acetic acid ethanesulfonic acid acid anhydride, acetic acid propane sulfonic acid acid anhydride, propionic acid methanesulfonic acid acid anhydride, propionic acid ethanesulfonic acid acid anhydride, propionic acid Propane sulfonic acid acid anhydride, trifluoroacetic acid methanesulfonic acid acid anhydride, trifluoroacetic acid ethanesulfonic acid acid anhydride, trifluoroacetic acid propane sulfonic acid acid anhydride, acetic acid trifluoromethanesulfanhydride anhydride, Acetic acid 2,2,2- trifluoro ethanesulfonic acids acid anhydride, five fluorine ethanesulfonic acid acid anhydride of acetic acid, trifluoroacetic acid trifluoromethanesulfanhydride anhydride, trifluoroacetic acid 2,2,2- tri- Fluorine ethanesulfonic acid acid anhydride, five fluorine ethanesulfonic acid acid anhydride of trifluoroacetic acid, 2- sulfosalicylic acids acid anhydride, the fluoro- 2- sulfosalicylic acids acid anhydrides of 3-, the fluoro- 2- sulphurs of 4- The fluoro- 2- sulfosalicylic acids acid anhydride of yl benzoic acid acid anhydride, 5-, the fluoro- 2- sulfosalicylic acids acid anhydrides of 6- etc..
<α lactone compounds with substituent group of 1-2-9.>
The α lactone compounds with substituent group are not particularly limited, and can be enumerated：
Alpha-Methyl-beta-propiolactone, α-ethyl-beta-propiolactone, α-propyl-beta-propiolactone, α-vinyl-beta-propiolactone, α- Pi-allyl-beta-propiolactone, α-phenyl-beta-propiolactone, α-tolyl-beta-propiolactone, Alpha-Naphthyl-beta-propiolactone, in α-fluoro-beta-the third Ester, alpha, alpha-dimethyl-beta-propiolactone, α, α-diethyl-beta-propiolactone, α-ethyl-alpha-methyl-beta-propiolactone, Alpha-Methyl-α-benzene Base-beta-propiolactone, α, α-diphenyl-beta-propiolactone, α, alpha, alpha-dimethyl phenyl-beta-propiolactone, α, α-bis- (3,5-dimethylphenyls)-β-the third Lactone, α, α-dinaphthyl-beta-propiolactone, α, α-divinyl-beta-propiolactone, α, α-diallyl-beta-propiolactone, α, α-dibenzyl Base-beta-propiolactone, α, the beta-propiolactones derivatives such as α-diphenylethyllene-beta-propiolactone, the fluoro- beta-propiolactone of α, α-two；
Alpha-Methyl-beta-butyrolactone, α-ethyl-beta-butyrolactone, α-propyl-beta-butyrolactone, α-vinyl-beta-butyrolactone, α- Pi-allyl-beta-butyrolactone, α-phenyl-beta-butyrolactone, α-tolyl-beta-butyrolactone, Alpha-Naphthyl-beta-butyrolactone, α-fluoro-beta-Ding Nei Ester, alpha, alpha-dimethyl-beta-butyrolactone, α, α-diethyl-beta-butyrolactone, α-ethyl-alpha-methyl-beta-butyrolactone, Alpha-Methyl-α-benzene Base-beta-butyrolactone, α, α-diphenyl-beta-butyrolactone, α, alpha, alpha-dimethyl phenyl-beta-butyrolactone, α, α-bis- (3,5-dimethylphenyls)-β-fourth Lactone, α, α-dinaphthyl-beta-butyrolactone, α, α-divinyl-beta-butyrolactone, α, α-diallyl-beta-butyrolactone, α, α-dibenzyl Base-beta-butyrolactone, α, the beta-butyrolactones derivatives such as α-diphenylethyllene-beta-butyrolactone, the fluoro- beta-butyrolactone of α, α-two；
Alpha-Methyl-gamma-butyrolacton, α-ethyl-gamma-butyrolacton, α-propyl-gamma-butyrolacton, α-vinyl-γ-Ding Nei Ester, α-pi-allyl-gamma-butyrolacton, α-phenyl-gamma-butyrolacton, α-tolyl-gamma-butyrolacton, Alpha-Naphthyl-gamma-butyrolacton, α- Fluoro- gamma-butyrolacton, alpha, alpha-dimethyl-gamma-butyrolacton, α, α-diethyl-gamma-butyrolacton, α-ethyl-alpha-methyl-γ-Ding Nei Ester, Alpha-Methyl-α-phenyl-gamma-butyrolacton, α, α-diphenyl-gamma-butyrolacton, α, alpha, alpha-dimethyl phenyl-gamma-butyrolacton, α, α-bis- (3,5-dimethylphenyl)-gamma-butyrolacton, α, α-dinaphthyl-gamma-butyrolacton, α, α-divinyl-gamma-butyrolacton, α, α-two allyl Base-gamma-butyrolacton, α, α-dibenzyl-gamma-butyrolacton, α, α-diphenylethyllene-gamma-butyrolacton, the fluoro- gamma-butyrolacton of α, α-two Wait gamma-butyrolactone derivatives；
Alpha-Methyl-gamma-valerolactone, α-ethyl-gamma-valerolactone, α-propyl-gamma-valerolactone, in α-vinyl-γ-penta Ester, α-pi-allyl-gamma-valerolactone, α-phenyl-gamma-valerolactone, α-tolyl-gamma-valerolactone, Alpha-Naphthyl-gamma-valerolactone, α- Fluoro- gamma-valerolactone, alpha, alpha-dimethyl-gamma-valerolactone, α, in α-diethyl-gamma-valerolactone, α-ethyl-alpha-methyl-γ-penta Ester, Alpha-Methyl-α-phenyl-gamma-valerolactone, α, α-diphenyl-gamma-valerolactone, α, alpha, alpha-dimethyl phenyl-gamma-valerolactone, α, α-bis- (3,5-dimethylphenyl)-gamma-valerolactone, α, α-dinaphthyl-gamma-valerolactone, α, α-divinyl-gamma-valerolactone, α, α-two allyl Base-gamma-valerolactone, α, α-dibenzyl-gamma-valerolactone, α, α-diphenylethyllene-gamma-valerolactone, the fluoro- gamma-valerolactone of α, α-two Wait gamma-valerolactones derivative；
Alpha-Methyl-δ-valerolactone, α-ethyl-δ-valerolactone, α-propyl-δ-valerolactone, α-vinyl-δ-valerolactone, α- Pi-allyl-δ-valerolactone, α-phenyl-δ-valerolactone, α-tolyl-δ-valerolactone, Alpha-Naphthyl-δ-valerolactone, in α-fluoro- δ-penta Ester, alpha, alpha-dimethyl-δ-valerolactone, α, α-diethyl-δ-valerolactone, α-ethyl-alpha-methyl-δ-valerolactone, Alpha-Methyl-α-benzene Base-δ-valerolactone, α, α-diphenyl-δ-valerolactone, α, alpha, alpha-dimethyl phenyl-δ-valerolactone, α, α-bis- (3,5-dimethylphenyls)-δ-penta Lactone, α, α-dinaphthyl-δ-valerolactone, α, α-divinyl-δ-valerolactone, α, α-diallyl-δ-valerolactone, α, α-dibenzyl Base-δ-valerolactone, α, the δ-valerolactones derivatives such as α-diphenylethyllene-δ-valerolactone, the fluoro- δ-valerolactone of α, α-two；
Alpha-Methyl-γ-hexalactone, α-ethyl-γ-hexalactone, α-propyl-γ-hexalactone, α-vinyl-γ-oneself in Ester, α-pi-allyl-γ-hexalactone, α-phenyl-γ-hexalactone, α-tolyl-γ-hexalactone, Alpha-Naphthyl-γ-hexalactone, α- Fluoro- γ-hexalactone, alpha, alpha-dimethyl-γ-hexalactone, α, α-diethyl-γ-hexalactone, α-ethyl-alpha-methyl-γ-oneself in Ester, Alpha-Methyl-α-phenyl-γ-hexalactone, α, α-diphenyl-γ-hexalactone, α, alpha, alpha-dimethyl phenyl-γ-hexalactone, α, α-bis- (3,5-dimethylphenyl)-γ-hexalactone, α, α-dinaphthyl-γ-hexalactone, α, α-divinyl-γ-hexalactone, α, α-two allyl Base-γ-hexalactone, α, α-dibenzyl-γ-hexalactone, α, α-diphenylethyllene-γ-hexalactone, the fluoro- γ-hexalactone of α, α-two Wait γ-hexalactones derivative；
Alpha-Methyl-δ-caprolactone, α-ethyl-δ-caprolactone, α-propyl-δ-caprolactone, α-vinyl-δ-caprolactone, α- Pi-allyl-δ-caprolactone, α-phenyl-δ-caprolactone, α-tolyl-δ-caprolactone, Alpha-Naphthyl-δ-caprolactone, α-fluoro- δ-oneself in Ester, alpha, alpha-dimethyl-δ-caprolactone, α, α-diethyl-δ-caprolactone, α-ethyl-alpha-methyl-δ-caprolactone, Alpha-Methyl-α-benzene Base-δ-caprolactone, α, α-diphenyl-δ-caprolactone, α, alpha, alpha-dimethyl phenyl-δ-caprolactone, α, α-bis- (3,5-dimethylphenyls)-δ-oneself Lactone, α, α-dinaphthyl-δ-caprolactone, α, α-divinyl-δ-caprolactone, α, α-diallyl-δ-caprolactone, α, α-dibenzyl Base-δ-caprolactone, α, the δ-caprolactone derivatives such as α-diphenylethyllene-δ-caprolactone, the fluoro- δ-caprolactone of α, α-two；
Alpha-Methyl -6-caprolactone, α-ethyl-s-caprolactone, α-propyl -6-caprolactone, α-vinyl -6-caprolactone, α - Pi-allyl -6-caprolactone, α-phenyl -6-caprolactone, α-tolyl -6-caprolactone, Alpha-Naphthyl -6-caprolactone, α-fluoro- ε-oneself in Ester, alpha, alpha-dimethyl -6-caprolactone, α, α-diethyl -6-caprolactone, α-ethyl-alpha-methyl -6-caprolactone, Alpha-Methyl-α-benzene Base -6-caprolactone, α, α-diphenyl -6-caprolactone, α, alpha, alpha-dimethyl phenyl -6-caprolactone, α, α-bis- (3,5-dimethylphenyls)-ε-oneself Lactone, α, α-dinaphthyl -6-caprolactone, α, α-divinyl -6-caprolactone, α, α-diallyl -6-caprolactone, α, α-dibenzyl Base -6-caprolactone, α, the epsilon-caprolactone derivatives such as α-diphenylethyllene -6-caprolactone, the fluoro- 6-caprolactone of α, α-two etc..
In these compounds, preferably：
The α such as Alpha-Methyl-gamma-butyrolacton, Alpha-Methyl-gamma-valerolactone, Alpha-Methyl-δ-valerolactone, Alpha-Methyl-δ-caprolactone- Methyl substitutes lactone；
The α such as α-phenyl-gamma-butyrolacton, α-phenyl-gamma-valerolactone, α-phenyl-δ-valerolactone, α-phenyl-δ-caprolactone- Phenyl substitutes lactone；
Alpha, alpha-dimethyl-gamma-butyrolacton, alpha, alpha-dimethyl-gamma-valerolactone, alpha, alpha-dimethyl-δ-valerolactone, α, α-two The alpha, alpha-dimethyls such as methyl-γ-hexalactone, alpha, alpha-dimethyl-δ-caprolactone substitute lactone；
α, α-diphenyl-gamma-butyrolacton, α, α-diphenyl-gamma-valerolactone, α, α-diphenyl-δ-valerolactone, α, α-two The α, α such as phenyl-γ-hexalactone, α, α-diphenyl-δ-caprolactone-diphenyl substitution lactone etc..
Among these, more preferably：Alpha-Methyl-gamma-butyrolacton, α-phenyl-gamma-butyrolacton, alpha, alpha-dimethyl-γ-Ding Nei Ester, α, α-diphenyl-gamma-butyrolacton etc..
<1-2-10. the compound with carbon-carbon triple bond>
As the compound with carbon-carbon triple bond, as long as intramolecular has the compound of carbon-carbon triple bond, kind Class is not particularly limited.
As the specific example of the compound with carbon-carbon triple bond, can enumerate, such as：
Methyl 2-propynyl ester, carbonic acid ethyl 2-propynyl ester, carbonic acid propyl 2-propynyl ester, carbonic acid butyl 2- third Alkynyl ester, carbonic acid cyclohexyl 2-propynyl ester, carbonate 2-propynyl ester, carbonic acid two (2-propynyl) ester, methyl 2- Butine base ester, carbonic acid ethyl 2- butine base ester, carbonic acid propyl 2- butine base ester, carbonic acid butyl 2- butine base ester, carbonic acid cyclohexyl 2- butine base ester, carbonate 2- butine base ester, carbonic acid two (2- butine base ester), methyl 3- butine base ester, carbonic acid ethyl 3- butine base ester, methyl valerylene base ester, methyl 1- methyl -2- butine base ester, carbonic acid 2- butine -1,4- glycol two Methyl ester, carbovinate 2- butine -1,4- diol esters (2-butyne-1,4-diol diethyl carbonate), dipropyl Base carbonic acid 2- butine -1,4- diol esters (2-butyne-1,4-diol dipropyl carbonate), dicyclohexyl carbonic acid 2- Butine -1,4- diol esters (2-butyne-1,4-diol dicyclohexyl carbonate), diphenyl carbonic acid 2- butine -1, The carbonate products such as 4- diol esters (2-butyne-1,4-diol diphenyl carbonate)；
Acetic acid 2- propynyl esters, propionic acid 2- propynyl esters, butyric acid 2- propynyl esters, naphthenic acid 2- propynyl esters, benzoic acid 2- third Alkynes ester, acetic acid 2- butine ester, propionic acid 2- butine ester, butyric acid 2- butine ester, naphthenic acid 2- butine ester, benzoic acid 2- butine Ester, acetic acid 3- butine ester, propionic acid 3- butine ester, butyric acid 3- butine ester, naphthenic acid 3- butine ester, benzoic acid 3- butine ester, Acetic acid valerylene ester, acetic acid 1- methyl -2- butine ester, 2- butine -1,4- glycol diacetates, 2- butine -1,4- glycol dipropyls The carboxylate compounds such as acid esters, 2- butine -1,4- glycol bicyclohexane formic acid esters, two alcohol benzoic ethers of 2- butine -1,4-；
Methanesulfonic acid 2- propynyl esters, ethanesulfonic acid 2- propynyl esters, propane sulfonic acid 2- propynyl esters, hexamic acid 2- propynyl esters, benzene sulfonic acid 2- propynyl esters, methanesulfonic acid 2- butine ester, ethanesulfonic acid 2- butine ester, propane sulfonic acid 2- butine ester, hexamic acid 2- butine ester, benzene sulfonic acid 2- butine ester, methanesulfonic acid 3- butine ester, ethanesulfonic acid 3- butine ester, propane sulfonic acid 3- butine ester, hexamic acid 3- butine ester, benzene sulfonic acid 3- butine ester, methanesulfonic acid valerylene ester, methanesulfonic acid 1- methyl -2- butine ester, trifluoromethanesulfonic acid 2- propynyl esters, five fluorine ethanesulfonic acid 2- Propynyl ester, 2- butine -1,4- glycol bis-mesylate, 2- butine -1,4- glycol dipropyls sulphonic acid ester, 2- butine -1,4- glycol two Sulfonate compounds such as hexamic acid ester, 2- butine -1,4- glycol diphenyl sulfonic acid esters etc..
<1-2-11. content, technical scope etc.>
These " compound A of the present invention 3 ", i.e., compound, nitrile compound selected from general formula (1) expression, isocyanation esterification Close object, phosphazene compound, disulfonate compound, sulfide compound, disulfide compound, acid anhydrides, α it is interior with substituent group Ester compounds and with carbon-carbon triple bond compound at least one kind of compound, can be used alone, can also use Compound of more than two kinds is applied in combination in arbitrary combination and ratio.In addition, in " the compound A of the present invention 3 ", even belonging to Compound in every one kind, can also be used alone a kind or chemical combination of more than two kinds is applied in combination with ratio in any combination Object.
The content ratio of these " the compound A of the present invention 3 " in nonaqueous electrolytic solution is not particularly limited, in general, phase For nonaqueous electrolytic solution total amount, the total amount of " the compound A of the present invention 3 " is more than 0.001 mass %, is more preferably 0.01 matter Measure more than %, further preferably more than 0.1 mass %, the upper limit of the total amount of " present invention 3 compound A " for 50 mass % with Under, more preferably below 25 mass %, further preferably below 10 mass %, particularly preferably below 5 mass %." this hair When the concentration of bright 3 compound A " is too low, it is difficult to obtain the improvement of trickle charge characteristic sometimes, and during excessive concentration, have When efficiency for charge-discharge is caused to reduce.
<1-3. nonaqueous solvents>
As long as the nonaqueous solvents contained by the nonaqueous electrolytic solution 3 of the present invention will not be to battery behavior band when battery is made Carry out dysgenic nonaqueous solvents, application method and its species are not particularly limited.It can enumerate above-mentioned non-aqueous Agent, but one or more of nonaqueous solvents used in the nonaqueous electrolytic solution being preferably exemplified below.
As the example for the nonaqueous solvents that can be used, it can be mentioned, for example：Chain or cyclic carbonate, chain or annular carboxylic Acid esters, chain or cyclic ether, sulfur-bearing organic solvent etc..
In addition, also there is no limit for the species of linear carbonate, but preferred dialkyl carbonate, form dialkyl carbonate The carbon number of alkyl is preferably respectively 1~5, particularly preferably 1~4.As specific example, can enumerate：Dimethyl carbonate, Methyl ethyl carbonate, diethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, carbonic acid di-n-propyl ester etc..
Wherein, come from the good viewpoint of various characteristics being industrially readily available and in non-aqueous electrolyte secondary battery It sees, preferably dimethyl carbonate, methyl ethyl carbonate or diethyl carbonate.
Also there is no particular limitation for the species of cyclic carbonate, preferably comprises the carbon number of the alkylidene of cyclic carbonate For 2~6, particularly preferably 2~4.Specifically, it can be mentioned, for example：Ethylene carbonate, propylene carbonate, butylene carbonate (2- second Base ethylene carbonate, cis and trans 2,3- dimethyl ethylene carbonate) etc..
Among these, from the perspective of various characteristics from non-aqueous electrolyte secondary battery are excellent, preferably carbonic acid is sub- Ethyl ester or propylene carbonate.
In addition, the species of chain carboxylate is also not particularly limited, as specific example, it can be mentioned, for example：Acetic acid first Ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, Ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propanoic acid tert-butyl ester etc..
Among these, from the angle being industrially readily available and various characteristics in non-aqueous electrolyte secondary battery are excellent From the point of view of, ethyl acetate, methyl propionate or ethyl propionate.
In addition, also there is no limit as the example that can usually use, can enumerate the species of cyclic carboxylic esters：γ-fourth Lactone, gamma-valerolactone, δ-valerolactone etc..
Among these, from the angle being industrially readily available and various characteristics in non-aqueous electrolyte secondary battery are excellent From the point of view of, preferred gamma-butyrolacton.
In addition, the species of chain ether is also without any restrictions, as specific example, it can be mentioned, for example：Dimethoxymethane, Dimethoxy-ethane, diethoxymethane, diethoxyethane, (ethoxymethyl) oxygroup methane, ethyoxyl Ethyl Methyl Ether etc..
Among these, from the angle being industrially readily available and various characteristics in non-aqueous electrolyte secondary battery are excellent From the point of view of, preferably dimethoxy-ethane, diethoxyethane.
In addition, the species of cyclic ether is not particularly limited, as specific example, can enumerate：Tetrahydrofuran, 2- methyl Tetrahydrofuran, oxinane etc..
In addition, the species of sulfur-bearing organic solvent is also not particularly limited, as specific example, can enumerate：Sulfurous acid Glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, sulfolane, cyclobufene sultone etc..
Among these, from the perspective of various characteristics from non-aqueous electrolyte secondary battery are good, preferably chain or Cyclic carbonate or chain or cyclic carboxylic esters, wherein, more preferred ethylene carbonate, propylene carbonate, carbonic acid diformazan Ester, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate or gamma-butyrolacton, particularly preferred carbonic acid Ethyl, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate or γ-Ding Nei Ester.
These solvents may be used alone, two or more kinds can also be used in combination, but preferably two or more compound combination makes With.For example, the particularly preferably high solvent of cyclic carbonates dielectric constants and the low viscosities such as linear carbonate class or chain esters Solvent combination uses.
One of preferred compositions of nonaqueous solvents are the combinations based on cyclic carbonates and linear carbonate class.Wherein, ring The total amount of shape carbonic ester and linear carbonate ratio shared in whole nonaqueous solvents is usually more than 80 volume %, is preferably More than 85 volume %, more preferably more than 90 volume %.In addition, the volume of cyclic carbonates is compared with cyclic carbonate and chain The total amount of shape carbonates is preferably more than 5 volume %, more preferably more than 10 volume %, particularly preferably 15 volume % with On, and usually below 50 volume %, preferably below 35 volume %, particularly preferably below 30 volume %.It is non-using these It is (particularly residual after High temperature storage using the cycle characteristics and High temperature storage characteristic of the battery of its making during the combination of aqueous solvent Retention capacity and high load discharge capacity) balance it is excellent, therefore preferably.
In addition, as above-mentioned cyclic carbonates and the specific example of the preferred compositions of linear carbonate class, can enumerate： Ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, carbonic acid Asia second Ester and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and carbon Diethyl phthalate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc..
Group obtained from further adding in propylene carbonate in the combination of these ethylene carbonates and linear carbonate class It is also preferred combination to close.During containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is preferably 99:1~ 40:60, particularly preferably 95:5~50:50.In addition, the amount of propylene carbonate account for nonaqueous solvents total amount for more than 0.1 volume %, Preferably more than 1 volume %, more preferably more than 2 volume %, and usually below 10 volume %, be preferably below 8 volume %, More preferably below 5 volume %, can so keep the characteristic of the combination of ethylene carbonate and linear carbonate class, and discharge Load is good.
Among these, from the perspective of cycle characteristics and discharge load balance are good, more preferably containing asymmetric chain The combination of shape carbonates, particularly preferably：Contain ethylene carbonate and symmetrical linear carbonate class and asymmetric linear carbonate The combination of class, for example, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and carbonic acid Methyl ethyl ester, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate；Alternatively, further contain polypropylene carbonate The combination of ester.Wherein, preferably asymmetric linear carbonate class is methyl ethyl carbonate, in addition, forming the alkyl of dialkyl carbonate Carbon number preferably 1~2.
The other examples of preferred mixed solvent are to include the solvent of chain ester.From the viewpoint for the discharge load for improving battery From the point of view of, particularly preferably contain chain ester in the in the mixed solvent of above-mentioned cyclic carbonates and linear carbonate class, as chain Ester, particularly preferred methyl acetate, ethyl acetate or methyl propionate.The volume of chain ester ratio shared in whole nonaqueous solvents Usually more than 5%, be preferably more than 8%, be more preferably more than 15%, and usually less than 50%, be preferably 35% with Under, be more preferably less than 30%, particularly preferably less than 25%.
As the example of other preferably nonaqueous solvents, more than the 60 volume % of nonaqueous solvents total amount are selected from carbonic acid Asia second 1 kind of organic solvent in ester, propylene carbonate, butylene carbonate, gamma-butyrolacton and gamma-valerolactone or selected from above-mentioned organic molten The mixed solvent of two or more organic solvent in agent.This kind of preferred flash-point of mixed solvent at 50 DEG C or more, wherein, particularly preferably At 70 DEG C or more.The evaporation and liquid for being not easy to occur solvent at high temperature using the nonaqueous electrolytic solution 3 of the solvent when being used are let out Leakage.Wherein, when the ratio for using the total amount of ethylene carbonate and gamma-butyrolacton shared in nonaqueous solvents total amount is 80 volume % Above, it is preferably more than 90 volume %, and the volume ratio of ethylene carbonate and gamma-butyrolacton is 5:95~45:During 55 solvent, Or be more than 80 volume %, be preferably more than 90 volume % when using ethylene carbonate and propylene carbonate total amount, and carbonic acid The volume ratio of ethyl and propylene carbonate is 30:70~80:During 20 solvent, in general, cycle characteristics can be obtained and discharged negative Carry the well balanced of characteristic etc..
<1-4. mono-fluor phosphates, difluorophosphoric acid salt>
The nonaqueous electrolytic solution 3 of the present invention contains mono-fluor phosphate and/or difluorophosphoric acid salt as required ingredient.With regard to the present invention For " mono-fluor phosphate, the difluorophosphoric acid salt " that is used in 3, species, content, there are place, analysis method, generating process for it Deng identical described in nonaqueous electrolytic solution 1.
<1-5. additive>
In the range of the effect of the unobvious damage present invention 3, nonaqueous electrolytic solution 3 of the invention can also contain various add Add agent.When additional additive carries out preparing processing, known additive can be arbitrarily used.In addition, additive can be single Solely using one kind, can also two or more be applied in combination with ratio in any combination.
It as the example of additive, can enumerate, overcharge preventing agent keeps special for improving the capacity after High temperature storage The auxiliary agent etc. of property, cycle characteristics.In these additives, as special for improving the capacity maintenance characteristics after High temperature storage, cycle Property auxiliary agent, preferably addition at least one of unsaturated bond and halogen atom carbonic ester (it is following, be abbreviated as sometimes " special Determine carbonic ester ").In the following, specific carbonic ester and other additives are illustrated respectively.
<The specific carbonic esters of 1-5-1.>
Specific carbonic ester refers to the carbonic ester at least one of unsaturated bond and halogen atom, and specific carbonic ester can be with Only contain unsaturated bond, can also only contain halogen atom, both unsaturated bond and halogen atom can also be contained.
As long as not damaging the effect of the present invention 3, the molecular weight of specific carbonic ester is not particularly limited, and can be arbitrary point Son amount, but usually more than 50, be preferably more than 80, in addition, usually less than 250, be preferably less than 150.Molecular weight is excessive When, dissolubility of the specific carbonic ester in nonaqueous electrolytic solution 3 reduces, and is difficult to fully show technique effect sometimes.
In addition, the manufacturing method of specific carbonic ester is not particularly limited, well known method system can be arbitrarily selected It makes.
In addition, the present invention nonaqueous electrolytic solution 3 in, can individually contain arbitrary a kind of specific carbonic ester, can also with times The combination of meaning and ratio contain specific carbonic ester of more than two kinds simultaneously.
In addition, additive amount of the specific carbonic ester in the nonaqueous electrolytic solution 3 of the present invention there is no limit as long as damage by unobvious The effect of the present invention 3, then can be any amount.But it is usually 0.01 mass % compared with the nonaqueous electrolytic solution 3 of the present invention Above, it is preferably more than 0.1 mass %, is more preferably more than 0.3 mass %, in addition, usually below 70 mass %, preferably For the concentration of below 50 mass %, more preferably below 40 mass %.In particular it is preferred that the carbonic ester phase with unsaturated bond Content for nonaqueous electrolytic solution 3 is below 10 mass %.
If less than the lower limit of above range, the nonaqueous electrolytic solution 3 of the present invention is used for non-aqueous electrolyte secondary battery When, the non-aqueous electrolyte secondary battery is difficult to show sufficiently to cycle specific improvement effect sometimes.In addition, if specific carbonic acid The ratio of ester is excessive, then when the nonaqueous electrolytic solution 3 of the present invention being used for non-aqueous electrolyte secondary battery, the nonaqueous electrolyte is secondary The High temperature storage characteristic and trickle charge characteristic of battery have the tendency of reduction, and particularly, gas generated increase sometimes, capacity is protected Holdup reduces.
<1-5-1-1. unsaturated carbon acid ester>
As the carbonic ester with unsaturated bond in the specific carbonic ester of the present invention 3 (" insatiable hunger below, is abbreviated as sometimes And carbonic ester "), as long as the carbonic ester with carbon-to-carbon double bond, without other limitations, can use arbitrary unsaturated Carbonic ester.It should be noted that also include the carbonic ester with aromatic rings in the carbonic ester with unsaturated bond.
As the example of unsaturated carbon acid ester, can enumerate, vinylene carbonate derivative species, by with aromatic rings or The ethylene carbonate derivative class of the substituent group substitution of carbon-to-carbon unsaturated bond, carbonic acid phenyl ester, ethylene carbonate esters, allyl Esters etc..
As the specific example of vinylene carbonate derivative species, can enumerate：Vinylene carbonate, methyl carbonic acid Asia second Enester, 4,5- dimethyl vinylene carbonate, phenyl-carbonic acid vinylene, 4,5- diphenyl vinylene carbonate, carbonic acid catechu Phenolic ester.
Tool as the ethylene carbonate derivative class substituted by the substituent group with aromatic rings or carbon-to-carbon unsaturated bond Body example can be enumerated：Vinylethylene carbonate, 4,5- divinyl ethylene carbonate, phenyl-carbonic acid ethyl, 4,5- bis- Phenyl-carbonic acid ethyl.
As the specific example of carbonic acid phenyl ester class, can enumerate：Diphenyl carbonate, carbonic acid ethyl phenyl ester, methyl Phenylester, carbonic acid tert-butyl benzene base ester etc..
As the specific example of ethylene carbonate esters, can enumerate：Divinyl carbonate, methyl vinyl esters etc..
As the specific example of allyl esters, can enumerate：Diallyl carbonate, methyl allyl ester etc..
In these unsaturated carbon acid esters, as specific carbonic ester, preferably vinylene carbonate derivative species, by with virtue The ethylene derivative species that the substituent group of fragrant ring or carbon-to-carbon unsaturated bond is substituted, particularly vinylene carbonate, 4,5- diphenyl Vinylene carbonate, 4,5- dimethyl vinylene carbonate or vinylethylene carbonate, since stable interface can be formed Protective film, therefore more preferably use.
<1-5-1-2. halocarbonate>
On the other hand, (below, write a Chinese character in simplified form sometimes as the carbonic ester with halogen atom in the specific carbonic ester of the present invention 3 For " halocarbonate "), as long as the carbonic ester with halogen atom, without other limitations, can use arbitrary halogen For carbonic ester.
As the specific example of halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atoms, iodine atom.Wherein, preferred fluorine Atom or chlorine atom, particularly preferred fluorine atom.In addition, as long as the number more than 1 of halogen atom possessed by halocarbonate is i.e. Can, it is not particularly limited, is usually less than 6, be preferably less than 4.When halocarbonate has multiple halogen atoms, these halogen are former Son may be the same or different.
As the example of halocarbonate, can enumerate：Ethylene carbonate derivative class, dimethyl carbonate derivative species, Methyl ethyl carbonate derivative species, diethyl carbonate derivative species.
As the specific example of ethylene carbonate derivative class, can enumerate, for example,
Fluorine ethylene carbonate, vinylene carbonate, 4,4- difluoros ethylene carbonate, 4,5- difluoros ethylene carbonate, 4,4- Two vinylene carbonates, bis- vinylene carbonates of 4,5-, the fluoro- 4- methyl carbonic acids ethyls of 4-, the chloro- 4- methyl carbonic acids Asia second of 4- Ester, bis- fluoro- 4- methyl carbonic acids ethyls of 4,5-, bis- chloro- 4- methyl carbonic acids ethyls of 4,5-, the fluoro- 5- methyl carbonic acids ethyls of 4-, The chloro- 5- methyl carbonic acids ethyls of 4-, bis- fluoro- 5- methyl carbonic acids ethyls of 4,4-, bis- chloro- 5- methyl carbonic acids ethyls of 4,4-, 4- (methyl fluoride)-ethylene carbonate, 4- (chloromethyl) ethylene carbonate, 4- (difluoromethyl) ethylene carbonate, 4- (dichloromethyl) Ethylene carbonate, 4- (trifluoromethyl) ethylene carbonate, 4- (trichloromethyl) ethylene carbonate, 4- (methyl fluoride) -4- fluorine carbonic acid Ethyl, 4- (chloromethyl) -4- vinylene carbonates, 4- (methyl fluoride) -5- fluorine ethylene carbonate, 4- (chloromethyl) -5- chlorine carbon The fluoro- 4,5- dimethyl ethylene carbonate of sour ethyl, 4-, the chloro- 4,5- dimethyl ethylene carbonates of 4-, bis- fluoro- 4,5- bis- of 4,5- Methyl carbonic acid ethyl, bis- chloro- 4,5- dimethyl ethylene carbonates of 4,5-, bis- fluoro- 5,5- dimethyl ethylene carbonates of 4,4-, 4, Bis- chloro- 5,5- dimethyl ethylene carbonates of 4- etc..
As the specific example of dimethyl carbonate derivative species, it can be mentioned, for example：Methyl methyl fluoride ester, methyl Difluoromethyl ester, methyl methyl ester trifluoroacetate, carbonic acid two (methyl fluoride) ester, carbonic acid two (difluoromethyl) ester, two (trifluoro of carbonic acid Methyl) ester, methyl chloromethane base ester, methyl dichloromethane base ester, methyl trichloromethyl ester, carbonic acid two (chloromethyl) Ester, carbonic acid two (dichloromethyl) ester, carbonic acid two (trichloromethyl) ester etc..
As the specific example of methyl ethyl carbonate derivative species, it can be mentioned, for example：
Methyl 2- fluoro ethyls ester, carbonic acid ethyl fluoride methyl ester, methyl 2,2- bis-fluoro ethyls ester, carbonic acid methyl fluoride 2- fluoro ethyls ester, carbonic acid ethyl difluoro methyl ester, methyl 2,2,2- trifluoroethyls ester, carbonic acid methyl fluoride 2,2- bis-fluoro ethyls Ester, carbonic acid 2- fluoro ethyl difluoromethyls ester, carbonic acid ethyl methyl ester trifluoroacetate, methyl 2- chloro-ethyl esters, carbonic acid ethyl chloromethane Base ester, methyl 2,2- Dichloroethyls ester, carbonic acid 2- chloroethyl chloromethanes base ester, carbonic acid ethyl dichloromethane base ester, methyl 2,2,2- trichloroethyls, carbonic acid 2,2- Dichloroethyl chloromethanes base ester, carbonic acid 2- chloroethyl dichloromethanes base ester, carbonic acid ethyl trichlorine Methyl ester etc..
As the specific example of diethyl carbonate derivative species, it can be mentioned, for example：
Carbonic acid ethyl (2- fluoro ethyls) ester, carbonic acid ethyl (2,2- bis-fluoro ethyls) ester, carbonic acid two (2- fluoro ethyls) ester, carbonic acid Ethyl (2,2,2- trifluoroethyls) ester, carbonic acid 2,2- bis-fluoro ethyls -2 '-fluoro ethyl ester, carbonic acid two (2,2- bis-fluoro ethyls) ester, carbon Sour 2,2,2- trifluoroethyls -2 '-fluoro ethyl ester, carbonic acid 2,2,2- trifluoroethyls -2 ', 2 '-bis-fluoro ethyls ester, carbonic acid two (2,2, 2- trifluoroethyls) ester, carbonic acid ethyl (2- chloroethyls) ester, carbonic acid ethyl (2,2- Dichloroethyls) ester, carbonic acid two (2- chloroethyls) Ester, carbonic acid ethyl (2,2,2- trichloroethyls) ester, carbonic acid 2,2- Dichloroethyls -2 '-chloro-ethyl ester, (bis- chloroethenes of 2,2- of carbonic acid two Base) ester, carbonic acid 2,2,2- trichloroethyls -2 '-chloro-ethyl ester, carbonic acid 2,2,2- trichloroethyls -2 ', 2 '-Dichloroethyl ester, carbonic acid Two (2,2,2- trichloroethyls) esters etc..
In these halocarbonates, the carbonic ester of fluorine atom is preferably had, more preferably the carbonic ester with fluorine atom derives Species, particularly fluorine ethylene carbonate, 4- (methyl fluoride) ethylene carbonate, 4,4- difluoros ethylene carbonate, 4,5- difluoro carbonic acid Ethyl can form interface protective film, therefore particularly preferably use.
<The halogenated unsaturated carbon acid esters of 1-5-1-3.>
In addition, as specific carbonic ester, the carbonic ester that there is unsaturated bond and halogen atom simultaneously can be used (to be abbreviated as " halogenated unsaturated carbon acid ester ").It as halogenated unsaturated carbon acid ester, is not particularly limited, as long as not damaging the effect of the present invention 3 Fruit can then use arbitrary halogenated unsaturated carbon acid ester.
As the example of halogenated unsaturated carbon acid ester, can enumerate：Vinylene carbonate derivative species, by with aromatic rings Or ethylene carbonate derivative class, the allyl esters etc. that the substituent group of carbon-to-carbon unsaturated bond is substituted.Nonaqueous electrolytic solution " halogenated unsaturated carbon acid ester " in 3 is identical described in nonaqueous electrolytic solution 2.
<Other additives of 1-5-2.>
Hereinafter, the additive beyond specific carbonic ester is illustrated.It, can be with as the additive beyond specific carbonic ester It enumerates, overcharge preventing agent, for improving auxiliary agent of the capacity maintenance characteristics after High temperature storage or cycle characteristics etc..
<1-5-2-1. overcharge preventing agent>
The specific example of overcharge preventing agent, content, the specific example when compound of different classifications is applied in combination contained Effect of charging preventing agent etc. is identical described in nonaqueous electrolytic solution 1.
<Other additives of 1-4-2.>
As the additive beyond specific carbonic ester, can enumerate：Overcharge preventing agent, for improving High temperature storage after Auxiliary agent of capacity maintenance characteristics or cycle characteristics etc..It " overcharge preventing agent " and " is kept for improving the capacity after High temperature storage The auxiliary agent of characteristic or cycle characteristics " is identical described in nonaqueous electrolytic solution 1.But above-mentioned " the compound A of the present invention 3 " is no Included in other additives.
<1-5-2-2. auxiliary agent>
As for improving the specific example of the auxiliary agent of the capacity maintenance characteristics after High temperature storage or cycle characteristics, can enumerate Such as：
Carbonate products beyond the specific carbonic esters such as carbonic acid erythrite ester, carbonic acid spiral shell-bis--dimethylene ester；
Sulfurous acid glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, sulfolane, cyclobutane Sulfone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, tetramethylthiuram monosulfide, N, N- dimethyl methyls sulfonamide, N, N- bis- The sulfur-containing compounds such as ethyl Methanesulfomide；
1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2-Oxazolidone, 1,3- dimethyl -2- imidazoles The nitrogenous compounds such as alkanone, N- methyl succimides；
Hydrocarbon compounds such as heptane, octane, cycloheptane etc..
[2. non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery 3 of the present invention has and can occlude and release the cathode of ion and anode and above-mentioned The nonaqueous electrolytic solution 3 of the present invention.
<2-1. battery structure>
The battery structure of the non-aqueous electrolyte secondary battery 3 of the present invention in 1 part of non-aqueous electrolyte secondary battery with being remembered The structure of load is identical.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution 3 of the invention described above is used.As long as in addition, the present invention 3 is not being departed from Purport in the range of, can also the present invention nonaqueous electrolytic solution 3 in mix other nonaqueous electrolytic solutions use.
<2-3. cathode>
The cathode of non-aqueous electrolyte secondary battery 3 is identical described in the cathode of non-aqueous electrolyte secondary battery 1.
<2-4. anode>
The anode of non-aqueous electrolyte secondary battery 3 is identical described in the anode of non-aqueous electrolyte secondary battery 1.
<2-5. partition plate>
The partition plate of non-aqueous electrolyte secondary battery 3 is identical described in the partition plate in non-aqueous electrolyte secondary battery 1.
<2-6. battery design>
Described in battery design in the battery design of non-aqueous electrolyte secondary battery 3 and non-aqueous electrolyte secondary battery 1 It is identical.
<1. nonaqueous electrolytic solution 4>
The nonaqueous electrolytic solution 4 of the present invention is identical with common nonaqueous electrolytic solution, is electrolysed containing electrolyte and for dissolving The nonaqueous electrolytic solution of the nonaqueous solvents of matter, in general, using electrolyte and nonaqueous solvents as main component.
<1-1. electrolyte>
As the electrolyte of the present invention 4, lithium salts can be usually used.As lithium salts, as long as known be used for the purposes Lithium salts, without special limitation, arbitrary lithium salts can be used, also, with the record of the electrolyte in nonaqueous electrolytic solution 1 It is identical.Specifically, following preferred lithium salts can be enumerated：
For example, LiPF6、LiBF4Wait inorganic lithium salts；
LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2, ring-type 1,2- hexafluoroethane di-sulfonyl imides lithium, ring-type 1,3- perfluoropropane di-sulfonyl imides lithium, LiN (CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、LiPF4(CF3)2、LiPF4 (C2F5)2、LiPF4(CF3SO2)2、LiPF4(C2F5SO2)2、LiBF2(CF3)2、LiBF2(C2F5)2、LiBF2(CF3SO)2、LiBF2 (C2F5SO2)2Etc. fluorine-containing organic lithium salt；
Two (oxalate conjunction) lithium borates etc..
Among these, from the viewpoint of battery performance is improved, preferably LiPF6、LiBF4、LiCF3SO3、LiN (CF3SO2)2、LiN(C2F5SO2)2, particularly preferred LiPF6、LiBF4.These lithium salts can be used alone, can also combine 2 kinds with Upper use.Combine two or more using when one of preferred example be LiPF6And LiBF4Be applied in combination, the combination have improve The effect of cycle characteristics.At this point, LiBF4Shared ratio is preferably more than 0.01 mass %, particularly preferably in the two total amount For more than 0.1 mass %, and preferably below 20 mass %, particularly preferably below 5 mass %.During less than the lower limit, have When cannot get desired effect, during more than the upper limit, the battery behavior after High temperature storage has the tendency of reduction.
In addition, another example is being applied in combination for inorganic lithium salt and fluorine-containing organic lithium salt, at this point, inorganic lithium salt is in the two total amount In shared ratio be preferably the mass % of 70 mass %~99.As fluorine-containing organic lithium salt, preferably LiN (CF3SO2)2、LiN (C2F5SO2)2, ring-type 1,2- hexafluoroethane di-sulfonyl imides lithium, appointing in ring-type 1,3- perfluoropropane di-sulfonyl imides lithiums What is a kind of.Both lithium salts are applied in combination, can achieve the effect that inhibit to deteriorate caused by High temperature storage.
The concentration of these electrolyte in nonaqueous electrolytic solution 4 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 3mol/L, is preferably 2mol/ Below L, more preferably below 1.8mol, particularly preferably below 1.5mol/L.When the concentration of electrolyte is too low, electrolyte is led Electric rate is sometimes insufficient, on the other hand, during the excessive concentration of electrolyte, and sometimes due to concentration rises and conductivity is caused to reduce, Sometimes battery performance reduces.
Nonaqueous solvents of the nonaqueous electrolytic solution 4 of the present invention containing electrolyte and dissolving electrolyte.Also, the nonaqueous electrolytic solution 4 at least containing cyclic sulfones, " viscosity at 25 DEG C is in the compound of below 1.5mPas " and " selected from tool There is at least one kind of chemical combination in the carbonic ester of unsaturated bond, the carbonic ester with halogen atom, mono-fluor phosphate and difluorophosphoric acid salt Object ".
<1-2. cyclic sulfones>
As " cyclic sulfones ", as long as the cyclic compound that annular position is made of methylene and sulfo group, It is not particularly limited, arbitrary cyclic sulfones can be used, wherein, the ring-type position is preferably by the methylene of 3 or more Base and the sulfo group of 1 or more are formed, also, the cyclic sulfones that preferred molecular weight is less than 500.
As the example of cyclic sulfones, can enumerate：Single sulphones, such as trimethylene sulfone class, tetramethylene Sulfone class, hexa-methylene sulfone class；Two sulphones, for example, two sulfone class of trimethylene, two sulfone class of tetramethylene, two sulfone of hexa-methylene Class etc., wherein, from the viewpoint of dielectric constant and viscosity, preferably tetramethylene sulfone class, two sulfone class of tetramethylene, hexa-methylene Sulfone class, two sulfone class of hexa-methylene, particularly preferred tetramethylene sulfone class (sulfolane class).
As cyclic sulfones, from the viewpoint of the said effect with the present invention, preferably sulfolane and/or ring fourth Sulfone derivative class (is referred to as " sulfolane class ") including sulfolane sometimes below.As such sulfolane analog derivative, 1 or more the ring for being substituted and formed by halogen atom being particularly preferably bonded in the hydrogen atom on the carbon atom for forming sulfolane ring Fourth sulfone derivative.In addition, as sulfolane derivative, in the degree of effect for not damaging the present invention, alkyl is preferably had, more 1 or more in the hydrogen atom being preferably bonded on the carbon atom for forming the alkyl is added to be substituted by halogen atom.
As the specific example of halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atoms or iodine atom.Wherein, preferably Fluorine atom or chlorine atom, particularly preferred fluorine atom.Above-mentioned (special) preferred halogen atom forms sulfolane ring for being bonded in Any one of halogen atom on carbon atom and the halogen atom that is bonded on the alkyl being connected on sulfolane ring halogen atom For, all it is that (special) is preferred.
As the sulfolane derivative containing alkyl substituent, can enumerate：
2- methyl sulfolanes, 3- methyl sulfolanes, 2,2- dimethylsulfolanes, 3,3- dimethylsulfolanes, 2,3- diformazans Base sulfolane, 2,4- dimethylsulfolanes, 2,5- dimethylsulfolanes, 2,2,3- trimethyls sulfolane, 2,2,4- front three basic rings Fourth sulfone, 2,2,5- trimethyls sulfolane, 2,3,3- trimethyls sulfolane, 3,3,4- trimethyls sulfolane, 3,3,5- front three basic rings Fourth sulfone, 2,3,4- trimethyls sulfolane, 2,3,5- trimethyls sulfolane, 2,2,3,3- tetramethyls sulfolane, 2,2,3,4- tetramethyls Base sulfolane, 2,2,3,5- tetramethyls sulfolane, 2,2,4,4- tetramethyls sulfolane, 2,2,4,5- tetramethyls sulfolane, 2,2, 5,5- tetramethyls sulfolane, 2,3,3,4- tetramethyls sulfolane, 2,3,3,5- tetramethyls sulfolane, 2,3,4,4- tetramethyl-ring fourths Sulfone, 2,3,4,5- tetramethyls sulfolane, 3,3,4,4- tetramethyls sulfolane, 2,2,3,3,4- pentamethyls sulfolane, 2,2,3,3, 5- pentamethyls sulfolane, 2,2,3,4,4- pentamethyls sulfolane, 2,2,3,4,5- pentamethyls sulfolane, 2,3,3,4,4- pentamethyls Sulfolane, 2,3,3,4,5- pentamethyls sulfolane, 2,2,3,3,4,4- hexamethyls sulfolane, 2,2,3,3,4,5- pregnancy basic ring fourths Sulfone, 2,2,3,3,5,5- hexamethyls sulfolane, 2,2,3,4,5,5- hexamethyls sulfolane, seven methyl ring fourths of 2,2,3,3,4,4,5- Sulfone, seven methyl sulfolanes of 2,2,3,3,4,5,5-, prestox sulfolane etc..
As the sulfolane derivative without substituent group, but containing fluorine atom, it can be mentioned, for example：
2- fluorine sulfolane, 3- fluorine sulfolane, 2,2- difluoros sulfolane, 2,3- difluoros sulfolane, 2,4- difluoros sulfolane, 2, 5- difluoros sulfolane, 3,4- difluoros sulfolane, 2,2,3- trifluoros sulfolane, 2,3,3- trifluoros sulfolane, 2,2,4- trifluoro ring fourths Sulfone, 2,2,5- trifluoros sulfolane, 2,3,4- trifluoros sulfolane, 2,3,5- trifluoros sulfolane, 2,4,4- trifluoros sulfolane, 2,2,3, 3- tetrafluoros sulfolane, 2,2,3,4- tetrafluoros sulfolane, 2,2,4,4- tetrafluoros sulfolane, 2,2,5,5- tetrafluoros sulfolane, 2,3,3, 4- tetrafluoros sulfolane, 2,3,3,5- tetrafluoros sulfolane, 2,3,4,4- tetrafluoros sulfolane, 2,3,4,5- tetrafluoros sulfolane, 2,2,3, Five fluorine sulfolane of 3,4-, five fluorine sulfolane of 2,2,3,3,5-, five fluorine sulfolane of 2,2,3,4,4-, five fluorine ring fourths of 2,2,3,4,5- Sulfone, five fluorine sulfolane of 2,3,3,4,4-, five fluorine sulfolane of 2,3,3,4,5-, 2,2,3,3,4,4- hexafluoros sulfolane, 2,2,3,3, 4,5- hexafluoros sulfolane, 2,2,3,3,5,5- hexafluoros sulfolane, 2,2,3,4,5,5- hexafluoros sulfolane, 2,2,3,3,4,4,5- seven Fluorine sulfolane, seven fluorine sulfolane of 2,2,3,3,4,5,5-, octafluoro sulfolane etc..
As the sulfolane derivative with alkyl substituent and fluorine atom, it can be mentioned, for example：
The fluoro- 3- methyl sulfolanes of 2-, the fluoro- 2- methyl sulfolanes of 2-, the fluoro- 3- methyl sulfolanes of 3-, the fluoro- 2- methyl ring fourths of 3- The fluoro- 3- methyl sulfolanes of sulfone, 4-, the fluoro- 2- methyl sulfolanes of 4-, the fluoro- 3- methyl sulfolanes of 5-, the fluoro- 2- methyl sulfolanes of 5-, 2- The fluoro- 2,4- dimethylsulfolanes of fluoro- 2,4- dimethylsulfolanes, 4-, the fluoro- 2,4- dimethylsulfolanes of 5-, bis- fluoro- 3- first of 2,2- Base sulfolane, bis- fluoro- 3- methyl sulfolanes of 2,3-, bis- fluoro- 3- methyl sulfolanes of 2,4-, bis- fluoro- 3- methyl sulfolanes of 2,5-, 3, Bis- fluoro- 3- methyl sulfolanes of 4-, bis- fluoro- 3- methyl sulfolanes of 3,5-, bis- fluoro- 3- methyl sulfolanes of 4,4-, bis- fluoro- 3- first of 4,5- Base sulfolane, bis- fluoro- 3- methyl sulfolanes of 5,5-, tri- fluoro- 3- methyl sulfolanes of 2,2,3-, tri- fluoro- 3- methyl ring fourths of 2,2,4- Sulfone, tri- fluoro- 3- methyl sulfolanes of 2,2,5-, tri- fluoro- 3- methyl sulfolanes of 2,3,4-, tri- fluoro- 3- methyl sulfolanes of 2,3,5-, 2, Tri- fluoro- 3- methyl sulfolanes of 4,4-, tri- fluoro- 3- methyl sulfolanes of 2,4,5-, tri- fluoro- 3- methyl sulfolanes of 2,5,5-, 3,4,4- Three fluoro- 3- methyl sulfolanes, tri- fluoro- 3 methyl sulfolanes of 3,4,5-, tri- fluoro- 3- methyl sulfolanes of 4,4,5-, 4,5,5- tri- are fluoro- 3- methyl sulfolanes, tetra- fluoro- 3 methyl sulfolanes of 2,2,3,4-, tetra- fluoro- 3- methyl sulfolanes of 2,2,3,5-, 2,2,4,4- tetra- are fluoro- 3- methyl sulfolanes, tetra- fluoro- 3- methyl sulfolanes of 2,2,4,5-, tetra- fluoro- 3- methyl sulfolanes of 2,2,5,5-, 2,3,4,4- tetra- Fluoro- 3- methyl sulfolanes, tetra- fluoro- 3- methyl sulfolanes of 2,3,4,5-, tetra- fluoro- 3- methyl sulfolanes of 2,3,5,5-, 3,4,4,5- Four fluoro- 3- methyl sulfolanes, tetra- fluoro- 3- methyl sulfolanes of 3,4,5,5-, tetra- fluoro- 3- methyl sulfolanes of 4,4,5,5-, 2,2,3, Five fluoro- 3- methyl sulfolanes of 4,4-, five fluoro- 3- methyl sulfolanes of 2,2,3,4,5-, five fluoro- 3- methyl ring fourths of 2,2,3,5,5- Sulfone, five fluoro- 3- methyl sulfolanes of 2,3,4,4,5-, five fluoro- 3- methyl sulfolanes of 2,3,4,5,5-, 2,2,3,4,4,5- hexafluoros- 3- methyl sulfolanes, 2,2,3,4,5,5- hexafluoro -3- methyl sulfolanes, 2,3,4,4,5,5- hexafluoro -3- methyl sulfolanes, seven Fluoro- 3- methyl sulfolanes etc..
As the sulfolane derivative with Monofluoroalkyl substituent group and fluorine atom, it can be mentioned, for example：
2- fluoro- 3- (methyl fluoride) sulfolane, 3- fluoro- 3- (methyl fluoride) sulfolane, 4- fluoro- 3- (methyl fluoride) sulfolane, 5- Fluoro- 3- (methyl fluoride) sulfolane, 2,2- bis- fluoro- 3- (methyl fluoride) sulfolane, 2,3- bis- fluoro- 3- (methyl fluoride) sulfolane, 2,4- Two fluoro- 3- (methyl fluoride) sulfolane, 2,5- bis- fluoro- 3- (methyl fluoride) sulfolane, 3,4- bis- fluoro- 3- (methyl fluoride) sulfolane, 3, 5- bis- fluoro- 3- (methyl fluoride) sulfolane, 4,4- bis- fluoro- 3- (methyl fluoride) sulfolane, 4,5- bis- fluoro- 3- (methyl fluoride) sulfolane, 5,5- bis- fluoro- 3- (methyl fluoride) sulfolane, 2,2,3- tri- fluoro- 3- (methyl fluoride) sulfolane, 2,2,4- tri- fluoro- 3- (methyl fluoride) ring Fourth sulfone, 2,2,5- tri- fluoro- 3- (methyl fluoride) sulfolane, 2,3,4- tri- fluoro- 3- (methyl fluoride) sulfolane, tri- fluoro- 3- (fluorine of 2,3,5- Methyl) sulfolane, 2,4,4- tri- fluoro- 3- (methyl fluoride) sulfolane, 2,4,5- tri- fluoro- 3- (methyl fluoride) sulfolane, 2,5,5- tri- Fluoro- 3- (methyl fluoride) sulfolane, 3,4,4- tri- fluoro- 3- (methyl fluoride) sulfolane, 3,4,5- tri- fluoro- 3- (methyl fluoride) sulfolane, 4,4,5- tri- fluoro- 3- (methyl fluoride) sulfolane, 4,5,5- tri- fluoro- 3- (methyl fluoride) sulfolane, tetra- fluoro- 3- (fluorine first of 2,2,3,4- Base) sulfolane, 2,2,3,5- tetra- fluoro- 3- (methyl fluoride) sulfolane, 2,2,4,4- tetra- fluoro- 3- (methyl fluoride) sulfolane, 2,2,4, 5- tetra- fluoro- 3- (methyl fluoride) sulfolane, 2,2,5,5- tetra- fluoro- 3- (methyl fluoride) sulfolane, tetra- fluoro- 3- (methyl fluoride) of 2,3,4,4- Sulfolane, 2,3,4,5- tetra- fluoro- 3- (methyl fluoride) sulfolane, 2,3,5,5- tetra- fluoro- 3- (methyl fluoride) sulfolane, 3,4,4,5- tetra- Fluoro- 3- (methyl fluoride) sulfolane, 3,4,5,5- tetra- fluoro- 3- (methyl fluoride) sulfolane, 4,4,5,5- tetra- fluoro- 3- (methyl fluoride) ring fourth Sulfone, 2,2,3,4,4- five fluoro- 3- (methyl fluoride) sulfolane, 2,2,3,4,5- five fluoro- 3- (methyl fluoride) sulfolane, 2,2,3,5,5- Five fluoro- 3- (methyl fluoride) sulfolane, 2,3,4,4,5- five fluoro- 3- (methyl fluoride) sulfolane, five fluoro- 3- (fluorine first of 2,3,4,5,5- Base) sulfolane, 2,2,3,4,4,5- hexafluoros -3- (methyl fluoride) sulfolane, 2,2,3,4,5,5- hexafluoros -3- (methyl fluoride) ring fourth Sulfone, 2,3,4,4,5,5- hexafluoros -3- (methyl fluoride) sulfolane, seven fluoro- 3- (methyl fluoride) sulfolane etc..
As the sulfolane derivative with fluoroalkyl substituent group and fluorine atom, it can be mentioned, for example：
2- fluoro- 3- (difluoromethyl) sulfolane, 3- fluoro- 3- (difluoromethyl) sulfolane, 4- fluoro- 3- (difluoromethyl) ring fourth Sulfone, 5- fluoro- 3- (difluoromethyl) sulfolane, 2,2- bis- fluoro- 3- (difluoromethyl) sulfolane, bis- fluoro- 3- (difluoromethyl) of 2,3- Sulfolane, 2,4- bis- fluoro- 3- (difluoromethyl) sulfolane, 2,5- bis- fluoro- 3- (difluoromethyl) sulfolane, bis- fluoro- 3- (two of 3,4- Methyl fluoride) sulfolane, 3,5- bis- fluoro- 3- (difluoromethyl) sulfolane, 4,4- bis- fluoro- 3- (difluoromethyl) sulfolane, 4,5- bis- Fluoro- 3- (difluoromethyl) sulfolane, 5,5- bis- fluoro- 3- (difluoromethyl) sulfolane, 2,2,3- tri- fluoro- 3- (difluoromethyl) ring fourth Sulfone, 2,2,4- tri- fluoro- 3- (difluoromethyl) sulfolane, 2,2,5- tri- fluoro- 3- (difluoromethyl) sulfolane, tri- fluoro- 3- of 2,3,4- (difluoromethyl) sulfolane, 2,3,5- tri- fluoro- 3- (difluoromethyl) sulfolane, 2,4,4- tri- fluoro- 3- (difluoromethyl) sulfolane, 2,4,5- tri- fluoro- 3- (difluoromethyl) sulfolane, 2,5,5- tri- fluoro- 3- (difluoromethyl) sulfolane, tri- fluoro- 3- (two of 3,4,4- Methyl fluoride) sulfolane, 3,4,5- tri- fluoro- 3- (difluoromethyl) sulfolane, 4,4,5- tri- fluoro- 3- (difluoromethyl) sulfolane, 4, 5,5- tri- fluoro- 3- (difluoromethyl) sulfolane, 2,2,3,4- tetra- fluoro- 3- (difluoromethyl) sulfolane, tetra- fluoro- 3- of 2,2,3,5- (difluoromethyl) sulfolane, 2,2,4,4- tetra- fluoro- 3- (difluoromethyl) sulfolane, 2,2,4,5- tetra- fluoro- 3- (difluoromethyl) ring Fourth sulfone, 2,2,5,5- tetra- fluoro- 3- (difluoromethyl) sulfolane, 2,3,4,4- tetra- fluoro- 3- (difluoromethyl) sulfolane, 2,3,4,5- Four fluoro- 3- (difluoromethyl) sulfolane, 2,3,5,5- tetra- fluoro- 3- (difluoromethyl) sulfolane, tetra- fluoro- 3- (difluoros of 3,4,4,5- Methyl) sulfolane, 3,4,5,5- tetra- fluoro- 3- (difluoromethyl) sulfolane, 4,4,5,5- tetra- fluoro- 3- (difluoromethyl) sulfolane, 2,2,3,4,4- five fluoro- 3- (difluoromethyl) sulfolane, 2,2,3,4,5- five fluoro- 3- (difluoromethyl) sulfolane, 2,2,3,5, 5- five fluoro- 3- (difluoromethyl) sulfolane, 2,3,4,4,5- five fluoro- 3- (difluoromethyl) sulfolane, five fluoro- 3- of 2,3,4,5,5- (difluoromethyl) sulfolane, 2,2,3,4,4,5- hexafluoros -3- (difluoromethyl) sulfolane, 2,2,3,4,5,5- hexafluoro -3- (difluoros Methyl) sulfolane, 2,3,4,4,5,5- hexafluoros -3- (difluoromethyl) sulfolane, seven fluoro- 3- (difluoromethyl) sulfolane etc..
As the sulfolane derivative with trifluoroalkyl substituent group and fluorine atom, it can be mentioned, for example：
2- fluoro- 3- (trifluoromethyl) sulfolane, 3- fluoro- 3- (trifluoromethyl) sulfolane, 4- fluoro- 3- (trifluoromethyl) ring fourth Sulfone, 5- fluoro- 3- (trifluoromethyl) sulfolane, 2,2- bis- fluoro- 3- (trifluoromethyl) sulfolane, bis- fluoro- 3- (trifluoromethyl) of 2,3- Sulfolane, 2,4- bis- fluoro- 3- (trifluoromethyl) sulfolane, 2,5- bis- fluoro- 3- (trifluoromethyl) sulfolane, bis- fluoro- 3- (three of 3,4- Methyl fluoride) sulfolane, 3,5- bis- fluoro- 3- (trifluoromethyl) sulfolane, 4,4- bis- fluoro- 3- (trifluoromethyl) sulfolane, 4,5- bis- Fluoro- 3- (trifluoromethyl) sulfolane, 5,5- bis- fluoro- 3- (trifluoromethyl) sulfolane, 2,2,3- tri- fluoro- 3- (trifluoromethyl) ring fourth Sulfone, 2,2,4- tri- fluoro- 3- (trifluoromethyl) sulfolane, 2,2,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, tri- fluoro- 3- of 2,3,4- (trifluoromethyl) sulfolane, 2,3,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, 2,4,4- tri- fluoro- 3- (trifluoromethyl) sulfolane, 2,4,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, 2,5,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, tri- fluoro- 3- (three of 3,4,4- Methyl fluoride) sulfolane, 3,4,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, 4,4,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, 4, 5,5- tri- fluoro- 3- (trifluoromethyl) sulfolane, 2,2,3,4- tetra- fluoro- 3- (trifluoromethyl) sulfolane, tetra- fluoro- 3- of 2,2,3,5- (trifluoromethyl) sulfolane, 2,2,4,4- tetra- fluoro- 3- (trifluoromethyl) sulfolane, 2,2,4,5- tetra- fluoro- 3- (trifluoromethyl) ring Fourth sulfone, 2,2,5,5- tetra- fluoro- 3- (trifluoromethyl) sulfolane, 2,3,4,4- tetra- fluoro- 3- (trifluoromethyl) sulfolane, 2,3,4,5- Four fluoro- 3- (trifluoromethyl) sulfolane, 2,3,5,5- tetra- fluoro- 3- (trifluoromethyl) sulfolane, tetra- fluoro- 3- (trifluoros of 3,4,4,5- Methyl) sulfolane, 3,4,5,5- tetra- fluoro- 3- (trifluoromethyl) sulfolane, 4,4,5,5- tetra- fluoro- 3- (trifluoromethyl) sulfolane, 2,2,3,4,4- five fluoro- 3- (trifluoromethyl) sulfolane, 2,2,3,4,5- five fluoro- 3- (trifluoromethyl) sulfolane, 2,2,3,5, 5- five fluoro- 3- (trifluoromethyl) sulfolane, 2,3,4,4,5- five fluoro- 3- (trifluoromethyl) sulfolane, five fluoro- 3- of 2,3,4,5,5- (trifluoromethyl) sulfolane, 2,2,3,4,4,5- hexafluoros -3- (trifluoromethyl) sulfolane, 2,2,3,4,5,5- hexafluoro -3- (trifluoros Methyl) sulfolane, 2,3,4,4,5,5- hexafluoros -3- (trifluoromethyl) sulfolane, seven fluoro- 3- (trifluoromethyl) sulfolane etc..
In above-mentioned sulfolane class compound, more preferably：
Sulfolane, 2- methyl sulfolanes, 3- methyl sulfolanes, 2,2- dimethylsulfolanes, 3,3- dimethylsulfolanes, 2, 3- dimethylsulfolanes, 2,4- dimethylsulfolanes, 2,5- dimethylsulfolanes, 2- fluorine sulfolane, 3- fluorine sulfolane, 2- are fluoro- The fluoro- 3- methyl sulfolanes of 3- methyl sulfolanes, 3-, the fluoro- 3- methyl sulfolanes of 4-, the fluoro- 3- methyl sulfolanes of 5-, the fluoro- 2- first of 2- The fluoro- 2- methyl sulfolanes of base sulfolane, 3-, the fluoro- 2- methyl sulfolanes of 4-, the fluoro- 2- methyl sulfolanes of 5-, the fluoro- 2,4- diformazans of 2- The fluoro- 2,4- dimethylsulfolanes of base sulfolane, 3-, the fluoro- 2,4- dimethylsulfolanes of 4-, the fluoro- 2,4- dimethylsulfolanes of 5-；
Particularly preferably：Sulfolane, 2- methyl sulfolanes, 3- methyl sulfolanes, 2- fluorine sulfolane, 3- fluorine sulfolane, 2- are fluoro- The fluoro- 3- methyl sulfolanes of 3- methyl sulfolanes, 3-, the fluoro- 3- methyl sulfolanes of 4-, the fluoro- 3- methyl sulfolanes of 5- etc..
In addition, when overusing by alkyl-substituted cyclic sulfones, viscosity can increase, so as to cause conductivity Reduction, in addition, during the cyclic sulfones for the fluorination that overuses, chemical stabilization is caused when being used as nonaqueous electrolyte battery Property reduce, and cause and reduced with the dissolubility of other solvents, be difficult to fully to show the effect of the present invention sometimes.
For cyclic sulfones described above, a kind of cyclic sulfones can be contained in nonaqueous electrolytic solution 4 of the invention The cyclic sulfones of more than two kinds are applied in combination in compound, ratio that can also be in any combination.In addition, cyclic sulfones chemical combination The manufacturing method of object is not particularly limited, and can arbitrarily select well known method manufacture.
Cyclic sulfones are usually 10 bodies compared with the concentration of nonaqueous solvents total amount in the nonaqueous electrolytic solution 4 of the present invention Product more than %, it is preferably more than 15 volume %, more preferably more than 20 volume %, in addition, usually below 70 volume %, preferably For below 60 volume %, more preferably below 50 volume %.Less than the scope lower limit when, by the present invention nonaqueous electrolytic solution 4 During in nonaqueous electrolyte battery, the nonaqueous electrolyte battery is difficult to show sufficiently the safety is improved effect sometimes, separately When outside, more than the upper limit of the scope, the viscosity of nonaqueous electrolytic solution can increase, and have the tendency of reduction so as to cause conductivity, Particularly, when carrying out the charge and discharge of nonaqueous electrolyte battery with high current density, charge/discharge capacity conservation rate reduces sometimes.
<1-3. " viscosity at 25 DEG C is in the compound of below 1.5mPas ">
The nonaqueous electrolytic solution 4 of the present invention must contain that " viscosity at 25 DEG C is in the chemical combination of below 1.5mPas Object ".As " viscosity at 25 DEG C is in the compound of below 1.5mPas ", when from for nonaqueous electrolyte battery Battery behavior it is excellent from the point of view of, be preferably selected from linear carbonate, chain carboxylate, chain ether and cyclic ether extremely Few a kind of compound.
As linear carbonate, preferably carbon number is 3~7, and as chain carboxylate, preferably carbon number is 3~7, As chain ether, preferably carbon number is 3~10, and as cyclic ether, preferably carbon number is 3~6.
Specifically, for example, linear carbonate as carbon number 3~7, can enumerate：Dimethyl carbonate, carbonic acid diethyl Ester, carbonic acid di-n-propyl ester, diisopropyl carbonate, carbonic acid n-propyl isopropyl esters, methyl ethyl carbonate, methyl n-propyl ester, Methyl n-butyl, methyl isobutyl, methylbutyl carbonate, carbonic acid ethyl n-propyl ester, carbonic acid ethyl are just Butyl ester, carbonic acid ethyl isobutyl base base, carbonic acid ethyl tert-butyl ester etc..
As the chain carboxylate of carbon atom 3~7, can enumerate：Methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, propionic acid isopropyl Ester, n-butyl propionate, isobutyl propionate, propanoic acid tert-butyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, Methyl isobutyrate, ethyl isobutyrate, isobutyric acid n-propyl, isopropyl isobutyrate etc..
As the chain ether of carbon number 3~10, can enumerate：Ether, diη-propyl ether, di-n-butyl ether, dimethoxy Methylmethane, dimethoxy-ethane, diethoxymethane, diethoxyethane, (ethoxymethyl) oxygroup methane, (ethoxymethyl) oxygroup second Alkane, ethylene glycol diη-propyl ether, ethylene glycol dibutyl ethers, diethylene glycol dimethyl ether etc..
As the cyclic ether of carbon number 3~6, can enumerate：Tetrahydrofuran, 2- methyltetrahydrofurans, 3- methyl tetrahydrochysenes Furans, 1,3- bis-Alkane, 2- methyl-1s, 3- bis-Alkane, 4- methyl-1s, 3- bis-Alkane, 1,4- bis-Alkane etc..
Specifically, in above-mentioned " viscosity at 25 DEG C is in the compound of below 1.5mPas ", preferred carbonic acid two Methyl esters, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, carbonic acid n-propyl isopropyl esters, methyl ethyl carbonate, carbonic acid first Base n-propyl ester, ether, diη-propyl ether, di-n-butyl ether, dimethoxymethane, dimethoxy-ethane, diethoxymethane, Diethoxyethane, (ethoxymethyl) oxygroup methane, ethyoxyl Ethyl Methyl Ether, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- bis-Alkane, 2- methyl-1s, 3- bis-Alkane, 4- methyl-1s, 3- bis-Alkane, 1,4- bis-Alkane, methyl acetate, ethyl acetate, acetic acid N-propyl, n-butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, n-butyl propionate, methyl butyrate, ethyl butyrate, Propyl butyrate, methyl isobutyrate, ethyl isobutyrate.
Among these, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dimethoxy-ethane, ethyoxyl are more highly preferred to Ethyl Methyl Ether, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- bis-Alkane, 1,4- bis-Alkane, methyl acetate, ethyl acetate, Methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl isobutyrate or ethyl isobutyrate.It is produced when being preserved from battery high-temperature From the viewpoint of solution gas estranged, among these more preferably dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl acetate, Ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl isobutyrate or ethyl isobutyrate.
In addition, the viscosity at 25 DEG C is using appointing in capillary viscometer, falling ball viscometer, vibration viscometer It anticipates a kind of numerical value of measure.When these viscosimeters is used to accurately measure the compound as Newtonian fluid, although all aobvious Same numerical value in the range of evaluated error is shown, but it is preferable to use capillary viscometers to be measured.In addition, manufacturing method It is not particularly limited, well known method can arbitrarily be selected to be manufactured,
It, can be independent in the nonaqueous electrolytic solution 4 of the present invention for specific low viscosity compound described above Containing any one, can also two or more be applied in combination with ratio in any combination.In addition, aftermentioned " be selected from containing unsaturation At least one kind of compound in the carbonic ester of key, the carbonic ester with halogen atom, mono-fluor phosphate and difluorophosphoric acid salt " is at 25 DEG C Under viscosity be below 1.5mPas when, can also be using the compound as " viscosity at 25 DEG C exists The compound of below 1.5mPas ".At this point, specific low viscosity compound is 30 bodies compared with nonaqueous electrolytic solution total amount During product more than %, the viscosity of nonaqueous electrolytic solution can be made to be reduced to the excellent of battery charging/discharging characteristic under high current density Scope.In addition, specific low viscosity compound compared with nonaqueous electrolytic solution total amount be below 8 volume % when, lithium can be formed The high electrode surface envelope of ionic conductivity.
In the present invention, the content of " viscosity at 25 DEG C is in the compound of below 1.5mPas " is not special Restriction, usually contained more than 30 volume % compared with the nonaqueous solvents total amount in nonaqueous electrolytic solution, be preferably 40 volume % with Upper, more preferably more than 50 volume %.During less than above-mentioned lower limit, since the viscosity of nonaqueous electrolytic solution becomes higher, exist The tendency that conductivity is caused to reduce, particularly, the heavy-current discharge characteristic of nonaqueous electrolyte battery reduces sometimes.In addition, usually Contain " gluing at 25 DEG C with below 90 volume %, preferably with below 85 volume %, more preferably with the concentration of below 80 volume % Property coefficient is in the compound of below 1.5mPas "." viscosity at 25 DEG C is in the compound of below 1.5mPas " When content is higher than above range, since the dielectric constant of the nonaqueous electrolytic solution 4 of the present invention reduces, reduced there are conductivity Tendency, particularly, sometimes resulting in the heavy-current discharge characteristic of nonaqueous electrolyte battery reduces.
Within the scope of the effect of the invention, the nonaqueous solvents in the nonaqueous electrolytic solution 4 in the present invention can contain There is the high polar solvent such as cyclic carbonate.For example, the combination based on following solvents can be enumerated：Sulfolane class and chain carbon Esters of gallic acid and cyclic carbonates, sulfolane class and chain ethers and cyclic carbonates, sulfolane class and chain esters and ring Shape carbonates.
One of preferred compositions of nonaqueous solvents are based on sulfolane class and linear carbonate class and cyclic carbonates Combination.Wherein, the ratio that sulfolane class and the total amount of cyclic carbonates account for nonaqueous solvents is more than 15 volume %, is preferably 20 More than volume %, more preferably more than 25 volume %, and usually below 70 volume %, be preferably below 60 volume %, more excellent It elects as below 50 volume %, also, the volume of cyclic carbonate is compared with the ratio of sulfolane class and the total amount of cyclic carbonates Example for more than 5 volume %, be preferably more than 10 volume %, more preferably more than 15 volume %, and usually below 90 volume %, Preferably below 80 volume %, more preferably below 70 volume %, also, linear carbonate accounts for the ratio of nonaqueous electrolytic solution solvent Usually more than 30 volume %, be preferably more than 40 volume %, more preferably more than 50 volume %, and usually 90 volume % with Under, be preferably below 85 volume %, more preferably below 80 volume %.Using these nonaqueous solvents combination when, made of it Battery cycle characteristics and high temperature dwell sustainability (residual capacity and high load discharge capacity particularly after High temperature storage) it is flat Weighing apparatus property is good, therefore preferably.
As sulfolane class and cyclic carbonates and the specific example of the preferred compositions of linear carbonate class, Ke Yilie It lifts：Sulfolane and ethylene carbonate and dimethyl carbonate, sulfolane and ethylene carbonate and diethyl carbonate, sulfolane and carbonic acid Ethyl and methyl ethyl carbonate, sulfolane and ethylene carbonate and dimethyl carbonate and diethyl carbonate, sulfolane and carbonic acid are sub- Ethyl ester and dimethyl carbonate and methyl ethyl carbonate, sulfolane and ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ring fourth Sulfone and ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc..
It can also enumerate, carbon is further added in the combination of these sulfolane and ethylene carbonate and linear carbonate class Combination obtained from sour Asia propyl ester, which is also preferably to combine.
During containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is preferably 99:1~40:60th, especially Preferably 95:5~50:50.In addition, the amount of propylene carbonate account for the ratio of nonaqueous electrolytic solution solvent total amount for 0.1 volume % with Upper, preferably more than 1 volume %, more preferably more than 2 volume %, in addition, its upper limit is usually below 20 volume %, is preferably Below 8 volume %, more preferably below 5 volume %.When containing propylene carbonate in the range, sulfolane and carbon can be kept Sour ethyl and the characteristic of dialkyl carbonates combination, while also there is more excellent low-temperature characteristics, therefore preferably.
In addition, in the present specification, the volume of nonaqueous solvents is the measured value at 25 DEG C, if ethylene carbonate this Compound at 25 DEG C of sample for solid then uses measured value during fusing point.
<1-4. " is selected from the carbonic ester with unsaturated bond, the carbonic ester with halogen atom, mono-fluor phosphate and difluoro phosphorus At least one kind of compound in hydrochlorate ">
In addition to substance in the nonaqueous electrolytic solution 4 of the present invention more than contain, also containing " being selected from unsaturated bond At least one kind of compound in carbonic ester, the carbonic ester with halogen atom, mono-fluor phosphate and difluorophosphoric acid salt " is (hereinafter referred to as For " specific compound ").The specific compound is respectively provided with the ability to form interface protective film, as the ingredient in electrolyte, Concept that can be unified as one.
<1-4-1. has the carbonic ester of unsaturated bond>
Carbonic ester (hereinafter sometimes referred to simply as " unsaturated carbon acid ester ") with unsaturated bond as long as with carbon-to-carbon double bond Or the carbonic ester of the carbon-to-carbon unsaturated bonds such as carbon-carbon triple bond, there is no particular limitation, can use arbitrary unsaturated carbon Acid esters.It should be noted that the carbonic ester with aromatic rings is also included in the carbonic ester with unsaturated bond.
Unsaturated carbon acid ester in nonaqueous electrolytic solution 4 is recorded identical with nonaqueous electrolytic solution 1.
<1-4-2. has the carbonic ester of halogen atom>
On the other hand, there is the carbonic ester (following, sometimes referred to simply as " halocarbonate ") of halogen atom as long as having halogen The carbonates of atom without other especially limitations, can use arbitrary halocarbonate.In nonaqueous electrolytic solution 4 Halocarbonate recorded with nonaqueous electrolytic solution 1 and 2 it is identical.
Can also use simultaneously there is the carbonic ester of unsaturated bond and halogen atom (to be referred to as " halogenated unsaturation below Carbonic ester ").Halogenated unsaturated carbon acid ester is not particularly limited, as long as not damaging the effect of the present invention significantly, can be used and be appointed The halogenated unsaturated carbon acid ester of meaning.Halogenated unsaturated carbon acid ester in nonaqueous electrolytic solution 4 is recorded identical with nonaqueous electrolytic solution 2.
Hereinafter, " carbonic ester with unsaturated bond " and " carbonic ester with halogen atom " is collectively referred to as " specific carbonic acid Ester ".The molecular weight of specific carbonic ester is not particularly limited, and can appoint as long as not damaging the effect of the present invention significantly The molecular weight of meaning, but usually more than 50, be preferably more than 80, and usually less than 250, be preferably less than 150.Molecular weight mistake When big, dissolubility of the specific carbonic ester in nonaqueous electrolytic solution reduces, and is difficult to fully show the effect of the present invention sometimes.Separately Outside, the manufacturing method of specific carbonic ester is not particularly limited, and well known method can arbitrarily be selected to be manufactured.
It can individually contain any one specific carbonic ester in the nonaqueous electrolytic solution 4 of the present invention, it can also be with arbitrary group It closes and specific carbonic ester of more than two kinds is applied in combination in ratio.In addition, nonaqueous electrolytic solution 4 total amount of the specific carbonic ester in the present invention In combined amount be not particularly limited, as long as do not damage the present invention effect as long as can be arbitrary combined amount, in the present invention Nonaqueous electrolytic solution 4 in, usually with more than 0.01 mass %, preferably with more than 0.1 mass %, more preferably with 0.3 mass % with On, and usually with below 8 mass %, preferably contain particular carbon with below 5 mass %, more preferably with the concentration of below 3 mass % Acid esters.When less than the lower limit of the scope, when the nonaqueous electrolytic solution 4 of the present invention is used in nonaqueous electrolyte battery, this is non-aqueous Electrolytic cell is difficult to show sufficient cycle characteristics improvement effect sometimes, in addition, when the ratio of specific carbonic ester is excessive, it will When the nonaqueous electrolytic solution 4 of the present invention is in nonaqueous electrolyte battery, the High temperature storage characteristic of the nonaqueous electrolyte battery has drop Low tendency, particularly, when gas generated excessive, discharge capacitance reduces sometimes.
<1-4-3. mono-fluor phosphates and difluorophosphoric acid salt>
For " mono-fluor phosphate, the difluorophosphoric acid salt " used in the present invention 4, including its species, content, there are fields for it It is identical described in nonaqueous electrolytic solution 1 including institute, analysis method, generating process etc..
It is not damaging in the effective scope of the present invention, nonaqueous electrolytic solution 4 of the invention can contain " other compounds ".Institute " other compounds " is stated, can be enumerated, the various compounds such as known overcharge preventing agent, auxiliary agent.
<1-5. overcharge preventing agent>
By containing overcharge preventing agent, battery occurs rupture, catches fire whens can inhibit overcharge etc..Nonaqueous electrolytic solution 4 In overcharge preventing agent recorded with nonaqueous electrolytic solution 1 it is identical.Preferred overcharge preventing agent can be listed below.
As overcharge preventing agent, can enumerate：Biphenyl, alkyl biphenyl, terphenyl, part hydride, the ring of terphenyl The aromatic compounds such as hexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether, dibenzofurans；2- fluorine biphenyl, adjacent cyclohexyl Fluorobenzene, the part hydride to the above-mentioned aromatic compound such as cyclohexyl fluorobenzene；2,4 difluorobenzene methyl ether, 2,5- difluorobenzene first Fluorine-containing benzyl ether compounds such as ether, 2,6- difluoroanisoles, 3,5- difluoroanisoles etc..Among these, preferably biphenyl, alkyl join Benzene, terphenyl, the part hydride of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether, dibenzofurans etc. Aromatic compound.They can combine two or more use.When two or more is applied in combination, from overcharge prevention characteristics and high temperature From the viewpoint of the balance of preservation characteristics, preferably：The combination of cyclohexyl benzene and tert-butyl benzene or tert-amyl benzene；Or selected from connection The oxygen-free virtues such as benzene, alkyl biphenyl, terphenyl, the part hydride of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene The group of compound in fragrant compounds of group and the compound in the oxygen-containing aromatic compound such as diphenyl ether, dibenzofurans It closes.
Ratio of the overcharge preventing agent in nonaqueous electrolytic solution 4 is as follows：It is usually 0.1 matter compared with nonaqueous electrolytic solution total amount It measures more than %, be preferably more than 0.2 mass %, particularly preferably more than 0.3 mass %, most preferably more than 0.5 mass %, The upper limit is usually below 5 mass %, is preferably below 3 mass %, particularly preferably below 2 mass %.The concentration ratio lower limit is low When, almost do not exhibit the effect of overcharge preventing agent.On the contrary, during excessive concentration, the battery behaviors such as high temperature dwell sustainability have reduction Tendency.
<1-6. auxiliary agent>
It as auxiliary agent, can enumerate, carbonic acid erythrite ester, carbonic acid spiral shell-bis--dimethylene ester, methyl methoxyl group second The carbonate products such as base ester；Succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, two The anhydride compounds such as glycol acid anhydrides, cyclohexane cyclohexanedimethanodibasic acid anhydride, cyclopentane tetracarboxylic acid dianhydride and phenylsuccinic acid acid anhydride；2,4,8,10- The spiro compounds such as four oxaspiros [5.5] hendecane, 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] hendecane Object；Sulfurous acid glycol ester, 1,3- propane sultones, 1,4- butyl sultones, methyl mesylate, ethyl methane sulfonate, diformazan sulphur The sulfur-bearings such as acid butyl ester, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, N, N- dimethyl methyls sulfonamide, N, N- diethyl Methanesulfomides Compound；1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2-Oxazolidone, 1,3- dimethyl -2- imidazoles The nitrogenous compounds such as alkanone and N methyl succinimide；The hydrocarbon compounds such as heptane, octane, nonane, decane, cycloheptane；Fluorine Aromatic fluorine compounds such as benzene, difluorobenzene, phenyl-hexafluoride, trifluoro-benzene etc..Two or more can be applied in combination in these compounds.
Ratio of these auxiliary agents in nonaqueous electrolytic solution 4 is as follows：Total amount compared with nonaqueous electrolytic solution 4 is usually 0.01 matter It measures more than %, be preferably more than 0.1 mass %, particularly preferably more than 0.2 mass %, the upper limit of the ratio is usually 5 matter It measures below %, be preferably below 3 mass %, particularly preferably below 1 mass %.By adding these auxiliary agents, height can be improved Capacity maintenance characteristics and cycle characteristics after temperature preservation.When the concentration ratio lower limit is low, the effect of auxiliary agent is not almost exhibited.Phase Instead, during excessive concentration, the battery behaviors such as high load flash-over characteristic have the tendency of reduction.
<The preparation of 1-7. nonaqueous electrolytic solutions>
The nonaqueous electrolytic solution 4 of the present invention by by electrolyte, cyclic sulfones, " viscosity at 25 DEG C is The compound of below 1.5mPas ", specific compound and " other compounds " optionally added are mutually dissolved and prepare. When preparing nonaqueous electrolytic solution 4, moisture during electrolyte is made to reduce, is preferably dehydrated each raw material in advance.It usually can be with Dehydration is dehydrated to below 50ppm, preferably to below 30ppm, particularly preferably dehydration to below 10ppm.Alternatively, it is also possible to prepare Implement dehydration, depickling processing etc. after electrolyte.
In nonaqueous electrolyte battery, nonaqueous electrolytic solution 4 of the invention is secondary preferably as secondary cell purposes, such as lithium Electrolyte in battery use uses.The nonaqueous electrolyte battery 4 of the electrolyte to having used the present invention illustrates below.
[2. nonaqueous electrolyte battery]
The nonaqueous electrolyte battery 4 of the present invention has the cathode that can occlude and release ion and anode and above-mentioned hair Bright nonaqueous electrolytic solution 4.
<2-1. battery structure>
The battery structure of non-aqueous electrolyte secondary battery 4 of the present invention and institute in the content of non-aqueous electrolyte secondary battery 1 The structure of record is identical.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution 4 of the invention described above is used.As long as in addition, the present invention 4 is not being departed from Purport in the range of, can the present invention nonaqueous electrolytic solution 4 in mix other nonaqueous electrolytic solutions use.
<2-3. cathode>
The cathode of non-aqueous electrolyte secondary battery 4 is identical described in the cathode of non-aqueous electrolyte secondary battery 1.
<2-4. anode>
The anode of non-aqueous electrolyte secondary battery 4 is identical described in the anode of non-aqueous electrolyte secondary battery 1.
<2-5. partition plate>
The partition plate of non-aqueous electrolyte secondary battery 4 is identical with the record of the partition plate in non-aqueous electrolyte secondary battery 1.
<2-6. battery design>
The record of the battery design of non-aqueous electrolyte secondary battery 4 and the battery design in non-aqueous electrolyte secondary battery 1 It is identical.
The non-aqueous electrolyte secondary battery 5 of the present invention includes nonaqueous electrolytic solution, occlusion and the anode and cathode of releasing lithium.Separately Outside, non-aqueous electrolyte secondary battery 5 of the invention can also have other structures.
<I. nonaqueous electrolytic solution>
(embodiment 5-1)
The nonaqueous electrolytic solution 5 of the present invention includes lithium salts and dissolves the non-water system organic solvent of the lithium salts.The non-water system is organic Solvent contains cyclic polyamine compounds and/or Cyclic polyamides compound, and further contains selected from unsaturated carbon acid ester, contains At least one kind of compound in fluorine carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt.As " embodiment 5-1 ".
[1. cyclic polyamine compounds]
[1-1. species]
(following, properly termed as " ring-type of the present invention 5 is more for cyclic polyamine compounds contained by the nonaqueous electrolytic solution 5 of the present invention Amine compounds ") it is cyclic compound and their derivative that amine is condensed the structure formed.That is, multiple nitrogen-atoms pass through Asia Cyclic compound that alkyl is combined into and the hydrogen atom being incorporated on the nitrogen-atoms of cyclic compound are substituted and obtained by alkyl The derivative arrived.
The number for forming the nitrogen-atoms of ring is preferably more than 3, particularly preferably more than 4, additionally, it is preferred that being less than 6, special Preferably less than 4.In addition, as alkylidene, it is not particularly limited, but preferably ethylidene, methyl ethylidene, propylidene, Asia The alkyl of the carbon numbers such as butyl 2~4, particularly preferred ethylidene or propylidene.Alternatively, it is also possible to include alkylene of more than two kinds Base.
In addition, the alkyl for the hydrogen atom being incorporated in as substitution on nitrogen-atoms, can enumerate alkyl, aryl, aralkyl etc..Its In, optimizing alkyl.If enumerating, as alkyl, methyl, ethyl, propyl, isopropyl, butyl etc. can be enumerated, as virtue Base can enumerate the aryl of the carbon numbers such as phenyl, p-methylphenyl, ethylphenyl, 3,5-dimethylphenyl 6~8.It, can as aralkyl Enumerate benzyl, styryl etc..
In addition, the molecular weight of cyclic polyamine compounds is preferably more than 120, more preferably more than 170 in the present invention 5, separately Outside, it is preferably less than 800, more preferably less than 400, particularly preferably less than 300.More than the scope the upper limit when, it is polyaminated Closing compatibility or dissolubility of the object in nonaqueous electrolytic solution reduces, and particularly low temperature capacity reduces sometimes.
Hereinafter, the specific example of the cyclic polyamine compounds of the present invention 5, but the cyclic polyamine compounds of the present invention 5 are enumerated It is not limited to example below.
The specific example of cyclic polyamine compounds as the present invention 5, can enumerate,
1,4,7- 7-triazacyclononanes, tri- azepine cyclodecane of 1,4,7-, tri- azacyclo- hendecanes of 1,4,8-, tri- nitrogen of 1,5,9- The three azacycloalkyl hydro carbons such as triazacyclododecane, tri- azepine cyclopentadecanes of 1,6,11-；
Cyclen (alias：Cyclen (サ イ Network レ Application)), 1,4,7,10- tetraazacyclododecanes ten Three alkane, 1,4,7,11- tetraazacyclododecane tetradecanes, 1,4,8,11- tetraazacyclododecane tetradecane (alias：cyclam(サイクラ System)), 1,4,8,12- tetraazacyclododecanes pentadecane, the tetraazacyclododecanes alkanes such as 1,5,9,13- tetraazacyclododecane hexadecanes；
The five-nitrogen heterocyclics alkane such as 1,4,7,10,13- five-nitrogen heterocyclics pentadecane, 1,4,7,10,13- five-nitrogen heterocyclic hexadecanes Class；
1,4,7,10,13,16- hexanitrogen heterocycle octadecane (alias：Hexacyclen), six azepines of 1,4,7,10,13,16- The hexanitrogen heterocycles alkanes such as ring nonadecane；
1,4,7- trimethyl -1,4,7- 7-triazacyclononanes, 2,5,8- trimethyl -1,4,7- 7-triazacyclononanes, 1,4, 7- triethyl group -1,4,7- 7-triazacyclononanes, 1,4,7- triphenyl -1,4,7- 7-triazacyclononanes, 1,4,7- tribenzyl -1,4, 7- 7-triazacyclononanes, 1,5,9- trimethyl -1,5,9- triazododecanes, three azacyclo-s of 1,5,9- triethyl groups -1,5,9- Dodecane, 1,5,9- triphenyl -1,5,9- triazododecanes, 1,5,9- tribenzyl -1,5,9- triazododecanes etc. Alkyl substitutes three azacycloalkyl hydro carbons；
2,5,8,11- tetramethyls-Cyclen, four nitrogen of 1,4,7,10- tetramethyls -1,4,7,10- Triazacyclododecane, 1,4,7,10- tetraethyls-Cyclen, 1,4,7,10- tetraphenyls -1,4,7,10- Tetraazacyclododecanand, 1,4,7,10- tetrabenzyls-Cyclen, 1,4,8,11- tetramethyl -1,4,8, 11- tetraazacyclododecane tetradecanes, 1,4,8,11- tetraethyl -1,4,8,11- tetraazacyclododecane tetradecanes, 1,4,8,11- tetraphenyl -1, 4,8,11- tetraazacyclododecane tetradecanes, 1,4,8,11- tetrabenzyl -1,4,8,11- tetraazacyclododecane tetradecanes, 1,4,8,12- tetramethyls Base -1,4,8,12- tetraazacyclododecanes pentadecane, 1,4,8,12- tetraethyl -1,4,8,12- tetraazacyclododecanes pentadecane, 1,4,8,12- The alkyl such as tetraphenyl -1,4,8,12- tetraazacyclododecanes pentadecane, 1,4,8,12- tetrabenzyl -1,4,8,12- tetraazacyclododecane pentadecanes Substitute tetraazacyclododecane alkanes；
1,4,7,10,13,16- vegolysens, 4,7,10,13,16- hexanitrogen heterocycles octadecane, 1,4,7,10,13,16- six Ethyl -1,4,7,10,13,16- hexanitrogen heterocycles octadecane, six nitrogen of 1,4,7,10,13,16- hexaphenyls -1,4,7,10,13,16- The alkyl such as heterocycle octadecane, six benzyl -1,4,7,10,13,16- hexanitrogen heterocycle octadecanes of 1,4,7,10,13,16- substitute six nitrogen Heterocycloalkane class etc..
Among these, more preferably：
The three azacycloalkyl hydro carbons such as 1,4,7- 7-triazacyclononanes, 1,5,9- triazododecanes；
Cyclen (alias：Cyclen), 1,4,8,11- tetraazacyclododecane tetradecanes (alias： Cyclam), the tetraazacyclododecanes alkanes such as 1,4,8,12- tetraazacyclododecanes pentadecane；
1,4,7,10,13,16- hexanitrogen heterocycle octane (alias：Hexacyclen), three nitrogen of 1,4,7- trimethyls -1,4,7- Ononane, 1,5,9- trimethyl -1,5,9- triazododecanes, 1,4,7,10- tetramethyl -1,4,7,10- tetraazacyclododecanes Dodecane, 1,4,8,11- tetramethyl -1,4,8,11- tetraazacyclododecane tetradecanes, four nitrogen of 1,4,8,12- tetramethyls -1,4,8,12- Methyl substituted nitrogen heterocyclic cycloalkane such as heterocycle pentadecane etc..
Among these, particularly preferably：
The three azacycloalkyl hydro carbons such as 1,4,7- 7-triazacyclononanes, 1,5,9- triazododecanes；
Cyclen (alias：Cyclen), 1,4,8,11- tetraazacyclododecane tetradecanes (alias： Cyclam), the tetraazacyclododecanes alkanes such as 1,4,8,12- tetraazacyclododecanes pentadecane；
The methyl such as 1,4,8,11- tetramethyl -1,4,8,11- tetraazacyclododecane tetradecanes substitution tetraazacyclododecane alkanes etc..
The cyclic polyamine compounds of the present invention 5 can be used alone, and can also combine in any combination and ratio makes Use two or more.
The molecular weight of these cyclic polyamine compounds is not very big, can be readily dissolved in non-water system organic solvent, Part of it is aoxidized by anode.Stable envelope is formed on anode at this time, it is therefore, more using the ring-type containing the present invention 5 During the nonaqueous electrolytic solution of amine compounds, the trickle charge characteristic of non-aqueous electrolyte secondary battery is improved.
[1-2. compositions]
As long as the content of the cyclic polyamine compounds of the present invention 5 is soluble in the non-system's organic solvent of aftermentioned water i.e. Can, it is not particularly limited, content is usually more than 0.001 mass %, is preferably 0.01 compared with nonaqueous electrolytic solution total amount More than quality %, in addition, usually below 5 mass %, preferably below 1 mass %, particularly preferably below 0.2 mass %. Less than the scope lower limit when, can hardly show sometimes the present invention 5 effect, in addition, more than above range the upper limit when, It generates using cyclic polyamine compounds as batteries such as the decomposition reaction of the non-water system organic solvent such as the carbonic ester of catalyst, speed characteristics Characteristic reduces sometimes.In addition, when of the invention 5 cyclic polyamine compounds of more than two kinds are applied in combination, the present invention 5 that uses The total concentrations of cyclic polyamine compounds should control within the above range.
[2. Cyclic polyamides compound]
[2-1. species]
Contained Cyclic polyamides compound (below, is properly termed as " the ring of the present invention 5 in the nonaqueous electrolytic solution 5 of the present invention Shape polyamide compound ") it is the compound in cyclic skeleton with multiple amido bonds (- NHCO-).Form the number of the amido bond of ring Mesh is preferably more than 2, additionally, it is preferred that being less than 6, particularly preferably less than 4.Cyclic polyamides chemical combination with 2 amido bonds Object is such as that can synthesize by making chain polyamine compounds and malonate derivative is reacted, in addition, with 3 or more The Cyclic polyamides compound of amido bond can react to synthesize by the cyclopolymerization of various amino acid.
In addition, the molecular weight of the Cyclic polyamides compound of the present invention 5 is preferably more than 160, more preferably more than 200, And preferably less than 800, more preferably less than 600, particularly preferably less than 500.More than the scope the upper limit when, the present invention 5 Compatibility of the Cyclic polyamides compound in non-water system organic solvent or dissolubility reduce, particularly become low temperature sometimes The main reason for capacity reduces.
In the following, the specific example of the Cyclic polyamides compound of the present invention 5 is enumerated, but the Cyclic polyamides of the present invention 5 It closes object and is not limited to the substance being set forth below.
The specific example of Cyclic polyamides compound as the present invention 5, can as the compound with 2 amido bonds To enumerate：
Tri- azepine cyclodecane -8,10- diketone of 1,4,7-, 9- methyl-1s, tri- azepine cyclodecane -8,10- diketone of 4,7-, 9, 9 '-dimethyl -1,4,7-, three azepine cyclodecane -8,10- diketone, three azepine cyclodecane -8,10- diketone of 9- ethyls -1,4,7-, 9- Three azepine cyclodecane -8,10- diketone of phenyl -1,4,7-, three azepine cyclodecane -8,10- diketone of 9- benzyls -1,4,7-, 1,5,9- Triazododecane -6,8- diketone, 7- methyl-1s, 5,9- triazododecane -6,8- diketone, 7,7 '-methyl-1,5,9- Triazododecane -6,8- diketone, 7- ethyl -1,5,9- triazododecane -6,8- diketone, 7- phenyl -1,5,9- three (substitution) three azacycloalkyls such as azepine cyclododecane -6,8- diketone, 7- benzyl -1,5,9- triazododecane -6,8- diketone Hydrocarbon diones；
1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 12- methyl-1s, 4,7,10- tetraazacyclododecanes tridecane - 11,13- diketone, 12,12 '-dimethyl -1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 12- ethyls -1,4,7,10- Tetraazacyclododecane tridecane -11,13- diketone, 12- phenyl -1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 12- benzyls - 1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 6- methyl-1s, 4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 6,6 '-dimethyl -1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 6- ethyl -1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 6- phenyl -1,4,8,11- tetraazacyclododecane tetradecanes -5,7- two Ketone, 6- benzyl -1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 1,4,8,12- tetraazacyclododecane pentadecane -9,11- diketone, 10- methyl-1s, 4,8,12- tetraazacyclododecane pentadecane -9,11- diketone, 10,10 '-dimethyl -1,4,8,12- tetraazacyclododecanes 15 Alkane -9,11- diketone, 10- ethyl -1,4,8,12- tetraazacyclododecane pentadecane -9,11- diketone, four nitrogen of 10- phenyl -1,4,8,12- (substitution) four azepines such as heterocycle pentadecane -9,11- diketone, 10- benzyl -1,4,8,12- tetraazacyclododecane pentadecane -9,11- diketone Cycloalkane diones；
1,4,7,10,13,16- hexanitrogen heterocycle nonadecane -17,19- diketone, 18- methyl-1s, six nitrogen of 4,7,10,13,16- Heterocycle nonadecane -17,19- diketone, 18,18 '-diethyl -1,4,7,10,13,16- hexanitrogen heterocycle nonadecane -17,19- diketone, 18- ethyl -1,4,7,10,13,16- hexanitrogen heterocycle nonadecane -17,19- diketone, six nitrogen of 18- phenyl -1,4,7,10,13,16- Heterocycle nonadecane -17,19- diketone, 18- benzyl -1,4,7,10,13,16- hexanitrogen heterocycle nonadecane -17,19- diketone etc. (take Generation) tetraazacyclododecane alkane diones etc..
In addition, as the compound with the amido bond of 3 or more, can enumerate：
Ring (- glycyl) 3, ring (β-alanyl) 3,3 grade ring-types trigalloyl amine of ring (- prolyl)；
Ring (- glycyl) 4, ring (β-alanyl) 4, ring (β-alanyl glycyl-β-alanyl glycyl), ring (β-the third Aminoacyl prolyl-β-alanyl prolyl), ring (- glycyl) 4, annular four amides of 4 grade of ring (β-alanyl)；
Annular six amides of ring (- glycyl) 6, ring (- prolyl-glycyl) 3 grades etc..
Among these, preferably：
Three azacyclo-s such as tri- azepine cyclodecane -8,10- diketone of 1,4,7-, 1,5,9- triazododecane -6,8- diketone Alkane diones；
1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, The tetraazacyclododecanes alkane diones such as 1,4,8,12- tetraazacyclododecane pentadecane -9,11- diketone；
Ring (β-alanyl glycyl-β-alanyl glycyl), six amides of ring (- prolyl-glycyl) 3 grade etc..
In these compounds, particularly preferably：
1,4,7,10- tetraazacyclododecane tridecane -11,13- diketone, 1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone, 1,4,8,12- tetraazacyclododecane pentadecane -9,11- diketone, ring (β-alanyl glycyl-β-alanyl glycyl) etc..
In addition, the Cyclic polyamides compound of the invention described above 5 can be used alone, can also in any combination and Two or more is applied in combination in ratio.
The molecular weight of these Cyclic polyamides compounds of the present invention 5 is not very big, can be readily dissolved in non-water system In organic solvent, part of it is aoxidized by anode.Stable envelope is formed on anode at this time, therefore, using containing this hair During the nonaqueous electrolytic solution of bright 5 Cyclic polyamides compound, the trickle charge characteristic of non-aqueous electrolyte secondary battery is improved.
[2-2. compositions]
As long as the content of the Cyclic polyamides compound of the present invention 5 is soluble in aftermentioned non-water system organic solvent , it is not particularly limited, content is usually more than 0.001 mass %, preferably compared with nonaqueous electrolytic solution total amount More than 0.01 mass %, in addition, usually below 5 mass %, be preferably below 1 mass %, particularly preferably 0.2 mass % with Under.Less than the scope lower limit when, can hardly show sometimes the present invention 5 effect, in addition, the upper limit more than above range When, the envelope being formed on anode is thickening, and resistance becomes higher, and hinders the batteries such as the movement of lithium (Li) ion, speed characteristic sometimes Characteristic reduces.In addition, when of more than two kinds of the invention 5 Cyclic polyamides compound is applied in combination, the ring of the present invention 5 used The total concentration of shape polyamide compound should control within the above range.
[3. at least one kind of chemical combination in unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt Object]
The nonaqueous electrolytic solution 5 of the present invention also contains selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluoro At least one kind of compound in phosphate.In order to form overlay film on cathode, improving battery behavior etc. and contain these compounds.
[3-1. species]
As unsaturated carbon acid ester, as long as the carbonic ester with carbon-to-carbon unsaturated bond, it, can without other limitations Use arbitrary unsaturated carbonic acid esters.Such as it can enumerate：Carbonic ester containing aromatic rings has carbon-to-carbon double bond, carbon-to-carbon three Carbonic ester of the carbon-to-carbon unsaturated bonds such as key etc..On unsaturated carbon recorded in unsaturated carbon acid ester, with nonaqueous electrolytic solution 1 Acid esters is identical.
As fluorine-containing carbonic ester, as long as the carbonic ester containing fluorine atom, without other limitations, can be used and arbitrarily contain Fluorine carbonic ester.
If citing, can enumerate：Fluorine ethylene carbonate, 1,1- difluoros ethylene carbonate, cis-difluoro carbonic acid Asia second The fluorine-containing cyclic carbonates such as ester, trans-difluoro ethylene carbonate, fluorine propylene carbonate, trifluoromethyl ethylene carbonate；
Methyl methyl ester trifluoroacetate, carbonic acid ethyl methyl ester trifluoroacetate, methyl 2- fluoro ethyls ester, carbonic acid ethyl 2- fluorine Ethyl ester, methyl 2,2,2- trifluoroethyls ester, carbonic acid ethyl 2,2,2- trifluoroethyls ester, carbonic acid two (trifluoromethyl) ester, The fluorine-containing linear carbonates such as carbonic acid two (2- fluoro ethyls) ester, carbonic acid two (2,2,2- trifluoroethyls) ester；Deng.
Wherein, the fluorine-containing annular carbon such as fluorine ethylene carbonate, cis-difluoro ethylene carbonate, trans-difluoro ethylene carbonate Acid esters can form stable interface protection envelope on cathode, therefore preferably.
In addition, fluorine-containing carbonic ester can be used alone a kind, two or more can be also used in mixed way in any combination with ratio.
As mono-fluor phosphate and difluorophosphoric acid salt, arbitrary mono-fluor phosphate and difluorophosphoric acid salt can be used.On can For " mono-fluor phosphate, the difluoro phosphorus of the present invention 5 (all including embodiment 5-1, embodiment 5-2, embodiment 5-3) Hydrochlorate ", including its species, content, its there are place, analysis method, generating process etc., with described in nonaqueous electrolytic solution 1 It is identical.As particularly preferred mono-fluor phosphate and difluorophosphoric acid salt, if citing, can enumerate, single lithium fluophosphate, single fluorine phosphorus Sour sodium, single fluorophosphoric acid potassium, difluorophosphate, difluorophosphoric acid sodium, difluorophosphoric acid potassium etc..Wherein, preferably single lithium fluophosphate, difluoro phosphorus Sour lithium.In addition, mono-fluor phosphate or difluorophosphoric acid salt can be used alone a kind, two or more in any combination and can also be compared Example is used in mixed way.
[3-2. compositions]
In addition, it is selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluoro in nonaqueous electrolytic solution 5 The concentration of at least one kind of compound in phosphate is usually more than 0.01 mass %, preferably compared with whole nonaqueous electrolytic solutions For more than 0.1 mass %, more preferably more than 0.3 mass %, in addition, usually below 10 mass %, be preferably 7 mass % with Under, more preferably below 5 mass %.If its concentration is excessive, the envelope formed on cathode is thickening, due to high resistance, electricity Tankage reduces.And under the high temperature conditions, gas generating amount increases sometimes, and resistance further increases, and capacity reduces.In addition, If concentration is too small, the effect of the present invention 5 cannot be given full play to sometimes.
[effect]
Here, just the nonaqueous electrolytic solution 5 of the preferred present invention contains selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, single fluorine phosphorus The reasons why at least one kind of compound in hydrochlorate and difluorophosphoric acid salt, illustrates, but the present invention 5 is not limited to the reason.Also It is to say, the polyamine compounds and/or polyamide compound of the present invention 5 are aoxidized in anode with the current potential also lower than solvent, are risen The effect of envelope is protected to anode, inhibits the oxidation reaction of follow-up solvent, can especially improve the performance degradation of high-voltage battery.But These compounds are reduced in cathode, form high resistance envelope, generate harmful effect to battery behaviors such as high load characteristics sometimes. Therefore, if coexisted in electrolyte in unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt At least one kind of compound, then they be reduced in cathode with current potential more higher than polyamine compounds and/or polyamide compound, shape Into protection envelope, inhibit the reaction of polyamine compounds and/or polyamide compound in cathode.As a result, it is formed on anode steady Fixed envelope and inhibit the reaction of electrolyte and anode, and high resistance envelope will not be formed on cathode, therefore, be remarkably improved The trickle charge characteristic of non-aqueous electrolyte secondary battery.
[4. non-water system organic solvent]
Non- water system organic solvent is not particularly limited, can be arbitrarily using well known as long as aftermentioned electrolyte can be dissolved Solvent.To citing, then can enumerate, linear carbonate class, cyclic carbonates, chain esters, cyclic ester (lactone compound Object) class, chain ethers, ring-type ethers, sulfur-bearing organic solvent etc..Wherein, as the solvent for showing high ion conductivity, usually It is preferred that linear carbonate class, cyclic carbonates, chain esters, annular esters, chain ethers or ring-type ethers.It is molten on these Agent, it is identical with the solvent described in nonaqueous electrolytic solution 1~4, but preferred following solvents.
If enumerating the concrete example of linear carbonate class, it can be cited for example that, dimethyl carbonate, diethyl carbonate, carbonic acid Methyl ethyl ester, methylpropyl carbonate, ethylpropyl carbonate etc..
If in addition, enumerate the concrete example of cyclic carbonates, it can be cited for example that, ethylene carbonate, propylene carbonate, Butylene carbonate, fluorine ethylene carbonate, difluoro ethylene carbonate, fluorine propylene carbonate, trifluoromethyl ethylene carbonate etc..
If in addition, enumerate the concrete example of chain ethers, it can be cited for example that, 1,2- dimethoxy-ethane, 1,2- diethyls Oxygroup ethane, ether etc..
If in addition, enumerate the concrete example of ring-type ethers, it can be cited for example that, tetrahydrofuran, 2- methyltetrahydrofurans, 1, Miscellaneous penta ring of 3- dioxolanes, 4- methyl-1,3-dioxies etc..
If in addition, enumerate the concrete example of chain esters, it can be cited for example that, methyl formate, methyl acetate, methyl propionate Deng.
If in addition, enumerate the concrete example of annular esters, it can be cited for example that, gamma-butyrolacton, gamma-valerolactone etc..
Moreover, non-water system organic solvent can be used alone a kind, two or more can also be combined in any combination and ratio It uses.In order to reach desired characteristic i.e. trickle charge characteristic, preferred compositions use two or more non-water system organic solvent.It is special It is not preferably formed non-aqueous with cyclic carbonates and linear carbonate class or based on cyclic carbonates and annular esters It is organic solvent.It is formed, specifically referred to containing non-water system organic solvent cyclic carbonates based on mentioned here With the total amount of linear carbonate class or cyclic carbonates and annular esters compared with whole nonaqueous electrolytic solutions for 70 mass % with On.
When two or more non-water system organic solvent is applied in combination, as preferred combination example, it can enumerate, ethylene carbonate With 2 yuan of system solvents such as methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and gamma-butyrolacton；Carbonic acid is sub- Ethyl ester and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and 3 yuan of methyl ethyl-methyl ester and diethyl carbonate etc. System solvent etc..Mainly contain these solvents non-water system organic solvent can balance fully meet various characteristics well, because This it is preferable to use.
In addition, during using organic solvent as non-water system organic solvent, the carbon number of the organic solvent be usually 3 with On, in addition, usually less than 13, be preferably less than 7.If carbon number is excessive, it is deteriorated, has to the impregnability of partition plate and cathode Shi Wufa realizes sufficient capacity.On the other hand, if carbon number is very few, volatility enhancing, sometimes as cell internal pressure The main reason for increase.
In addition, the molecular weight of non-water system organic solvent is usually more than 50, is preferably more than 80, in addition, usually 250 with Under, be preferably less than 150.If molecular weight is excessive, it is deteriorated to the impregnability of partition plate and cathode, can not realizes sufficient appearance sometimes Amount.On the other hand, if molecular weight is too low, volatility enhancing, the main reason for increase sometimes as cell internal pressure.
In addition, when two or more non-water system organic solvent is applied in combination, the ratio of cyclic carbonate in the non-water system organic solvent Example compared with all non-water system organic solvents is usually more than 5 mass %, is preferably more than 10 mass %, more preferably 15 matter Measure more than %, particularly preferably more than 20 mass %, also, usually below 60 mass %, preferably below 50 mass %, spy It You Xuanwei not below 40 mass %.If less than the lower limit of above range, the dissociation for causing Li salt is not easy, electrical conductivity reduces, because This high load capacity easily reduces；When on the other hand, more than the upper limit, viscosity is excessively high, and Li ions are not easily shifted, therefore sometimes high negative Capacity is carried to reduce.
[5. lithium salts]
As the lithium salts for electrolyte, any one of inorganic lithium salt and organic lithium salt can be used, can enumerate with it is upper " lithium salts " the same lithium salts recorded in the part of nonaqueous electrolytic solution 1 as " electrolyte " is stated, if enumerating the example of inorganic lithium salt, LiPF can be enumerated6、LiAsF6、LiBF4、LiSbF6Etc. inorganic fluoride salts；LiAlCl4Wait butters salt；LiClO4、 LiBrO4、LiIO4Wait perhalides etc..If in addition, enumerating the example of organic lithium salt, CF can be enumerated3SO3Li、C4F9SO3Li Etc. perfluoroalkanesulfosalt salts；CF3Perfluoroalkane carboxylic acids' salt such as COOLi；(CF3CO)2The perfluoroalkanes imide salts such as NLi； (CF3SO2)2NLi、(C2F5SO2)2Fluorine-containing organic lithium salts such as the perfluoroalkanesulfonyls inferior amine salt such as NLi etc..
Wherein, from the point of view of being soluble in solvent and showing high dissociation degree, preferably LiPF6、LiBF4、CF3SO3Li、 (CF3SO2)2NLi etc..It should be noted that electrolyte can be used alone a kind, two or more in any combination and can also be compared Example is applied in combination.In addition, LiPF is particularly preferably applied in combination6And LiBF4Or LiPF6(CF3SO2)2NLi, because it connects to improving Continuous charge characteristic has effect.
Compared with nonaqueous electrolytic solution, the concentration of the electrolyte in nonaqueous electrolytic solution is usually more than 0.5mol/L, is preferably More than 0.75mol/L, also, usually below 2mol/L, preferably below 1.75mol/L.It is sometimes non-aqueous if concentration is too low The conductivity of electrolyte is insufficient.On the other hand, if excessive concentration, since viscosity rises, conductivity declines, and in low temperature It is easily precipitated, the performance of non-aqueous electrolyte secondary battery has the tendency of reduction.
[6. other auxiliary agents]
In order to improve the wetability of nonaqueous electrolytic solution, overcharge electrical characteristics etc., in the scope for the effect for not influencing the present invention 5 Interior, nonaqueous electrolytic solution 5 of the invention can also contain " other auxiliary agents ".As the example of " other auxiliary agents ", horse can be enumerated Carry out the acid anhydrides such as acid anhydrides, succinic anhydride, glutaric anhydride；The carboxylates such as vinyl acetate, vinyl hexanediacetate, allyl acetate； Diphenyl disulfide ether, 1,3- propane sultones, 1,4- butyl sultones, dimethyl sulfone, divinylsulfone, dimethyl sulfite, The sulfur-containing compounds such as sulfurous acid glycol ester, 1,4- butanediols bis-mesylate, methyl mesylate, methanesulfonic acid 2- propynyl esters；Uncle Butyl benzene, biphenyl, ortho-terphenyl, 4- fluorine biphenyl, fluorobenzene, 2,4 difluorobenzene, cyclohexyl benzene, diphenyl ether, 2,4 difluorobenzene first Compound etc. obtained from the aromatic compounds such as ether, trifluoromethylbenzene and the aromatic compound are replaced by fluorine atoms.Separately Outside, " other auxiliary agents " can be used alone a kind, and also two or more can be applied in combination in any combination and ratio.
In addition, compared with whole nonaqueous electrolytic solutions, the concentration of " other auxiliary agents " in nonaqueous electrolytic solution is usually 0.01 matter It measures more than %, be preferably more than 0.05 mass %, also, usually below 10 mass %, preferably below 5 mass %.It needs Illustrate, two or more be applied in combination " other auxiliary agents " when, make the total concentration of these auxiliary agents within the above range.
[states of 7. nonaqueous electrolytic solutions]
Nonaqueous electrolytic solution 5 usually exists with liquid condition, its gelation can be also made by macromolecule and as semi-solid Electrolyte.Macromolecule for gelation is arbitrary macromolecule, it can be cited for example that, Kynoar, Kynoar and six Copolymer, polyethylene glycol oxide, polyacrylate, polymethacrylates of fluoropropene etc..It should be noted that for gelation Macromolecule can be used alone a kind, two or more can be also applied in combination in any combination and ratio.
In addition, nonaqueous electrolytic solution 5 is used as semi-solid electrolyte in use, nonaqueous electrolytic solution is in semi-solid electrolyte Shared ratio is as follows：Compared with the total amount of semi-solid electrolyte, be usually more than 30 mass %, be preferably 50 mass % with Upper, particularly preferably more than 75 mass %, and usually below 99.95 mass %, be preferably below 99 mass %, especially excellent It elects as below 98 mass %.If the ratio of nonaqueous electrolytic solution is excessive, the holding of electrolyte becomes difficult, and leakage, phase easily occurs Instead, it is sometimes insufficient in terms of efficiency for charge-discharge or capacity if the ratio of nonaqueous electrolytic solution is very few.
[preparation methods of 8. nonaqueous electrolytic solutions]
The nonaqueous electrolytic solution 5 of the present invention can be prepared by following methods：Lithium salts, this hair are dissolved in non-water system organic solvent Cyclic polyamine compounds and/or Cyclic polyamides compound in bright 5, " selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, single fluorine At least one kind of compound in phosphate and difluorophosphoric acid salt " and " other auxiliary agents " as needed.
When preparing nonaqueous electrolytic solution 5, preferably by each raw material of nonaqueous electrolytic solution, i.e. cyclic polyamine in lithium salts, the present invention 5 Compound and/or Cyclic polyamides compound, non-water system organic solvent and " other auxiliary agents " as needed are dehydrated in advance. Degree as dehydration, it is often desirable that be dehydrated to below 50ppm, be preferably dehydrated to below 30ppm.It should be noted that at this In specification, ppm refers to the ratio on the basis of weight.
If the electrolysis of water, the reaction of water and lithium metal, the hydrolysis of lithium salts occur sometimes there are water in nonaqueous electrolytic solution Deng.As the method for dehydration, be not particularly limited, for example, dehydration object for non-water system organic solvent when liquid, can be used point Son sieve etc..In addition, dehydration object for lithium salts when solids, can be dried below the temperature for causing decomposition.
(embodiment 5-2)
In addition, another purport of the present invention 5 is the non-aqueous of the non-water system organic solvent containing lithium salts and dissolving lithium salts Electrolyte, wherein, the non-water system organic solvent contains cyclic polyamine compounds, and compared with whole nonaqueous electrolytic solutions, contains There are 5~40 mass % cyclic carbonates.As " embodiment 5-2 ".
[1. cyclic polyamine compounds]
[1-1. species]
It is same as described above.
[1-2. compositions]
It is same as described above.
[2. cyclic carbonate]
As long as described cyclic carbonate cyclic carbonate, is not particularly limited in the present invention 5, part or complete Portion's hydrogen atom can be substituted by halogens such as fluorine, chlorine.To enumerate example, it is sub- that ethylene carbonate, propylene carbonate, carbonic acid can be enumerated Butyl ester, fluorine ethylene carbonate, difluoro ethylene carbonate, fluorine propylene carbonate, trifluoromethyl ethylene carbonate etc..Cyclic carbonate It can be used alone a kind, two or more can be also applied in combination in any combination and ratio.
Particularly preferably using the group of the combination of ethylene carbonate and propylene carbonate, ethylene carbonate and fluorine ethylene carbonate The combination of conjunction, ethylene carbonate and propylene carbonate and fluorine ethylene carbonate.
The present invention 5 is characterized in that it is 5~40 matter that non-water system organic solvent, which contains compared with all non-water system organic solvents, Measure the cyclic carbonate of %.It is preferably more than 8 mass %, particularly preferably more than 10 mass %, further preferred as lower limit For more than 12 mass %.It is preferably below 35 mass %, particularly preferably below 30 mass %, further preferred as the upper limit For below 25 mass %.When two or more cyclic carbonate is applied in combination, total amount also can be within the above range.
When the amount of cyclic carbonate is less than the lower limit of the scope, the dissociation for causing Li salt is not easy, it is high since electrical conductivity reduces Load capacity is easily reduced；When the amount of cyclic carbonate is higher than the upper limit, trigger the cyclic carbonate using polyamine compounds as catalyst The decomposition reaction of the non-water system organic solvent such as ester.Therefore, it is a large amount of to generate carbon dioxide etc. at high temperature during trickle charge Gas, resistance increase, recover capacity reduces sometimes.
In addition, the carbon number of cyclic carbonate is usually more than 3, and usually less than 13, be preferably less than 5.If Carbon number is excessive, then is deteriorated to the impregnability of partition plate and cathode, can not realize sufficient capacity sometimes.If on the contrary, carbon atom Number is too small, then volatility enhances, the major reason risen sometimes as cell internal pressure.
[3. non-water system organic solvent]
It is same as described above.
[4. lithium salts]
It is same as described above.
[5. at least one kind of chemical combination in unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt Object]
In embodiment 5-2, preferably comprise selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluoro At least one kind of compound in phosphate.These compounds are same as described above.
[6. other auxiliary agents]
It is same as described above.
[states of 7. nonaqueous electrolytic solutions]
It is same as described above.
[manufacturing methods of 8. nonaqueous electrolytic solutions]
It is same as described above.
(embodiment 5-3)
In addition, another purport of the present invention 5 be it is non-containing lithium salts and the non-water system organic solvent for dissolving the lithium salts Water electrolysis liquid, the nonaqueous electrolytic solution contain Cyclic polyamides compound.As " embodiment 5-3 ".
[1. Cyclic polyamides compound]
[1-1. species]
It is same as described above.
[1-2. compositions]
It is same as described above.
[2. non-water system organic solvent]
Workable nonaqueous solvents is same as described above.
Here, Cyclic polyamides compound can individually achieve the effect that the reasons why present invention is as follows：In Cyclic polyamides In compound, due to the influence of adjacent carbonyl delocalization occurs for the unshared electron pair on nitrogen, alkalescence is far below ring-type Polyamine compounds.Therefore, even if when largely using cyclic carbonate equal solvent, it is not easy to react on cathode.Therefore, The solvent species and its composition used is not particularly limited.
[3. lithium salts]
It is same as described above.
[4. cyclic carbonate]
In embodiment 5-3, cyclic carbonate is preferably comprised.It is same as described above for cyclic carbonate.
[5. at least one kind of chemical combination in unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt Object]
In embodiment 5-3, preferably comprise selected from unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluoro At least one kind of compound in phosphate.These compounds are same as described above.
[6. other auxiliary agents]
It is same as described above.
[states of 7. nonaqueous electrolytic solutions]
It is same as described above.
[preparation methods of 8. nonaqueous electrolytic solutions]
It is same as described above.
[II. non-aqueous electrolyte secondary batteries]
The non-aqueous electrolyte secondary battery 5 of the present invention has the cathode that can occlude/release ion and anode and above-mentioned The nonaqueous electrolytic solution of invention.
<2-1. battery structure>
The battery structure of non-aqueous electrolyte secondary battery 5 of the present invention and the knot described in 1 part of non-aqueous electrolyte secondary battery Structure is identical.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution 5 of the invention described above is used.In addition, in the purport without departing from the present invention 5 In the range of, nonaqueous electrolytic solution 5 of the invention can be also used in mixed way with other nonaqueous electrolytic solutions.
<2-3. cathode>
The cathode of non-aqueous electrolyte secondary battery 5 is identical with the record on cathode in non-aqueous electrolyte secondary battery 1.
<2-4. anode>
The anode of non-aqueous electrolyte secondary battery 5 is identical with the record of anode in non-aqueous electrolyte secondary battery 1.
<2-5. partition plate>
The partition plate of non-aqueous electrolyte secondary battery 5 is identical with the record of partition plate in non-aqueous electrolyte secondary battery 1.
<2-6. battery design>
The record phase of the battery design of non-aqueous electrolyte secondary battery 5 and battery design in non-aqueous electrolyte secondary battery 1 Together.
[1. nonaqueous electrolytic solution 6]
The nonaqueous electrolytic solution 6 of the present invention is identical with common nonaqueous electrolytic solution, containing electrolyte and dissolves the electrolyte Nonaqueous solvents.
<1-1. electrolyte>
The electrolyte used in the nonaqueous electrolytic solution 6 of the present invention is not particularly limited, and can arbitrarily be used in mixed way as mesh The well known electrolyte used in target non-aqueous electrolyte secondary battery as electrolyte.In addition, by the present invention non-water power When solving liquid 6 and being used for non-aqueous electrolyte secondary battery, preferred lithium salts.Electrolyte in nonaqueous electrolytic solution 6 and institute in nonaqueous electrolytic solution 1 The electrolyte phase stated is same.
The nonaqueous electrolytic solution 6 of the present invention is containing electrolyte and dissolves the nonaqueous solvents of the electrolyte, the nonaqueous electrolytic solution 6 Contain " the annular di-sulfonyl imides salt shown at least one kind of general formula (8) " and " mono-fluor phosphate and/or difluorophosphoric acid salt ".
[chemical formula 7]
[in formula, R is represented optionally by the alkylidene of alkyl-substituted carbon number 1~12, and the alkyl and alkylidene can also be into One step is replaced by fluorine atoms.In addition, n is 1~3 integer, M represents 1 in the 1st race of periodic table, the 2nd race and the 13rd race Kind or more metal or season。]
<Annular di-sulfonyl imides salt represented by 1-2. general formulas (8)>
In the annular di-sulfonyl imides salt represented by general formula (8), R represent optionally by alkyl-substituted carbon number 1~ 12nd, preferably the alkylidene of carbon number 2~8, the alkyl and alkylidene can be also further replaced by fluorine atoms.In carbon number mistake When more, the molecular weight increase of every 1 molecule makes expected effect be deteriorated sometimes.
As the unsubstituted alkylidene of carbon number 1~12, ethylidene, trimethylene, tetramethylene, five can be enumerated Methylene etc..Carbon number 1~8, particularly preferred carbon number 1~4 can be preferably listed in the alkyl imported as substituent group Straight or branched alkyl, can also further be substituted by the fluorine atom of 1 or more.It, can as by alkyl-substituted alkylidene To enumerate for example, propylidene, 2- methyl-1s, 3- propylidene, sub- neopentyl etc..
Fluorine atom can be led in any position of these unsubstituted alkylidenes or alkyl-substituted alkylidene, with any amount Enter, wherein, from being industrially easily obtained, simplicity of manufacture etc. consideration, preferably perfluorinated alkylidene, particularly preferably for example, Perfluor ethylidene, perfluor -1,3- propylidene.
In the annular di-sulfonyl imides salt represented by general formula (8), M is selected from the 1st race of periodic table, the 2nd race and the 13rd race One or more of metal (following, sometimes referred to simply as " special metal ") or season。
As the concrete example of the 1st race's metal of periodic table, lithium, sodium, potassium, caesium etc. can be enumerated.Wherein, preferably lithium, sodium, especially It is preferred that lithium.
As the concrete example of periodic table group II metal, magnesium, calcium, strontium, barium etc. can be enumerated.Wherein, preferably magnesium, calcium, especially Preferably magnesium.
As the concrete example of metal belonging to group 13 of periodic table, aluminium, gallium, indium, thallium etc. can be enumerated.Wherein, preferably aluminium, gallium, it is special Not preferred aluminium.
In these special metals, preferably lithium, sodium, magnesium, calcium, aluminium or gallium, more preferable lithium, magnesium or aluminium, particularly preferred lithium.
Annular di-sulfonyl imides salt represented by general formula (8) can be used one kind or two or more.Alternatively, it is also possible to being same Mn+With annular di-sulfonyl imides anion of more than two kinds.That is, two or more annular two sulphur may also be contained in 1 molecule Imide anion.
As the concrete example of annular di-sulfonyl imides salt shown in general formula (8), it can be cited for example that, ring-type 1,2- second disulfonyls Imidization lithium, ring-type the third di-sulfonyl imides of 1,3- lithium, ring-type 1,2- perfluor second di-sulfonyl imides lithium, ring-type 1,3- perfluors third Di-sulfonyl imides lithium, ring-type 1,4- perfluor fourth di-sulfonyl imides lithiums etc..
Wherein, preferably 1,2- of ring-type perfluor second di-sulfonyl imides lithium, ring-type 1,3- perfluor the third di-sulfonyl imides lithiums.
Concentration of the annular di-sulfonyl imides salt in nonaqueous electrolytic solution represented by general formula (8) is preferably 0.001~1mol/ L.If the concentration of annular di-sulfonyl imides salt is too low, it is sometimes difficult to fully inhibit the generation of gas and capacity during High temperature storage Deterioration.If on the contrary, the excessive concentration of annular di-sulfonyl imides salt, sometimes the battery behavior reduction after High temperature storage.Ring-type two The concentration of sulfimide salt is more preferably more than 0.01mol/L, particularly preferably more than 0.02mol/L, is more preferably More than 0.03mol/L.It is preferably below 0.5mol/L, more preferably below 0.3mol/L, especially excellent in addition, as upper limit value Elect below 0.2mol/L as.
<1-3. nonaqueous solvents>
As long as the nonaqueous solvents that the nonaqueous electrolytic solution 6 of the present invention contains will not bring not battery behavior when being formed into battery The solvent of good influence, is not particularly limited, but one or more of solvent preferably used in following nonaqueous electrolytic solutions.
As the example of usually used nonaqueous solvents, chain and cyclic carbonate, chain and cyclic carboxylic acids can be enumerated Ester, chain and cyclic ether, phosphorous organic solvent, sulfur-bearing organic solvent etc..Itself and nonaqueous solvents described in nonaqueous electrolytic solution 1~5 It is identical.
<1-4. mono-fluor phosphates, difluorophosphoric acid salt>
On " mono-fluor phosphate, the difluorophosphoric acid salt " used in the present invention 6, including its species, content, there are fields for it It is identical recorded in nonaqueous electrolytic solution 1 including institute, analysis method, generating process etc..
<1-5. additive>
The nonaqueous electrolytic solution 6 of the present invention can also contain various additions in the range of the effect of the unobvious damage present invention 6 Agent.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that additive can 1 kind is used alone, two or more can be also applied in combination in any combination and ratio.
As the example of additive, overcharge preventing agent can be enumerated, keep special for improving the capacity after High temperature storage The auxiliary agent etc. of property, cycle characteristics.Wherein, as improving the auxiliary agent of the capacity maintenance characteristics after High temperature storage, cycle characteristics, It is preferred that add carbonic ester (following, sometimes referred to simply as " the specific carbonic acid containing at least one of unsaturated bond and halogen atom Ester ").Hereinafter, specific carbonic ester and other additives are illustrated respectively.
<The specific carbonic esters of 1-5-1.>
Specific carbonic ester is the carbonic ester containing at least one of unsaturated bond and halogen atom, and specific carbonic ester can be only It containing unsaturated bond, can also only contain halogen atom, can also have both unsaturated bond and halogen atom.
The molecular weight of specific carbonic ester is not particularly limited, and then can be to appoint as long as not damaging the effect of the present invention 6 Anticipate molecular weight, but usually more than 50, be preferably more than 80, and usually less than 250, be preferably less than 150.If molecule Measure excessive, then dissolubility of the specific carbonic ester in nonaqueous electrolytic solution reduces, and is sometimes difficult to obtain sufficient effect.
In addition, the preparation method of specific carbonic ester is it is not also specifically limited, can arbitrarily select well known method to be prepared.
In addition, in the nonaqueous electrolytic solution 6 of the present invention, it can individually contain arbitrary a kind of specific carbonic ester, it can also be with arbitrary Combination and ratio simultaneously contain two or more specific carbonic ester.
In addition, use level of the specific carbonic ester of the present invention in nonaqueous electrolytic solution 6 is not particularly limited, as long as not damaging The effect of the present invention 6 can be then arbitrary use level, but compared with the nonaqueous electrolytic solution 6 of the present invention, the specific carbonic acid contained The concentration of ester is usually more than 0.01 mass %, is preferably more than 0.1 mass %, more preferably more than 0.3 mass %, and leading to Often it is below 70 mass %, is preferably below 50 mass %, more preferably below 40 mass %.
If less than the lower limit of the scope, when in non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution 6 of the present invention, Non-aqueous electrolyte secondary battery is sometimes difficult to show sufficient cycle characteristics improvement effect.If the in addition, ratio of specific carbonic ester Example is excessive, then when the nonaqueous electrolytic solution 6 of the present invention is used in non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery High temperature storage characteristic and trickle charge characteristic have the tendency of reduction, especially gas generating amount increases, sometimes capacity retention ratio It reduces.
(1-5-1-1. unsaturated carbon acid esters)
In the specific carbonic ester of the present invention 6, the carbonic ester with unsaturated bond (below, is sometimes referred to simply as " unsaturated carbonic acid Ester ") it is identical with the carbonic ester containing unsaturated bond described in nonaqueous electrolytic solution 1.
(1-5-1-2. halocarbonates)
On the other hand, in the specific carbonic ester of the present invention 6, as the carbonic ester with halogen atom (below, sometimes referred to simply as " halocarbonate "), as long as with halogen atom, without other special limitations, arbitrary halocarbonate can be used. " halocarbonate " is identical with the halocarbonate described in nonaqueous electrolytic solution 2.
(the halogenated unsaturated carbon acid esters of 1-5-1-3.)
In addition, as specific carbonic ester, can also use and meanwhile there is unsaturated bond and the carbonic ester of halogen atom (suitably It is referred to as " halogenated unsaturated carbon acid ester ").It as halogenated unsaturated carbon acid ester, is not particularly limited, as long as unobvious are damaged Arbitrary halogenated unsaturated carbon acid ester can be used in the effect of the evil present invention 6." halogenated unsaturated carbon acid ester " and non-aqueous solution electrolysis Halogenated unsaturated carbon acid ester described in liquid 2 is identical.
<The other additives of 1-5-2.>
Hereinafter, the additive just in addition to specific carbonic ester illustrates.It, can as the additive beyond specific carbonic ester To enumerate overcharge preventing agent, for improving auxiliary agent of the capacity maintenance characteristics after High temperature storage, cycle characteristics etc..
<1-5-2-1. overcharge preventing agent>
" overcharge preventing agent " is identical with the overcharge preventing agent described in nonaqueous electrolytic solution 1.
<1-5-2-2. auxiliary agent>
It, can be in addition, as improving the concrete example of the auxiliary agent of the capacity maintenance characteristics after High temperature storage, cycle characteristics Enumerate the auxiliary agent identical with auxiliary agent recorded in nonaqueous electrolytic solution 1.
[2. non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery 6 of the present invention has and can occlude and release the cathode of ion and anode and above-mentioned The nonaqueous electrolytic solution 6 of the present invention.
<2-1. battery structure>
Described in the battery structure of the non-aqueous electrolyte secondary battery 6 of the present invention and 1 part of non-aqueous electrolyte secondary battery Structure is identical.
<2-2. nonaqueous electrolytic solution>
As nonaqueous electrolytic solution, the nonaqueous electrolytic solution 6 of the invention described above is used.It should be noted that without departing from this hair In the range of bright 6 purport, the nonaqueous electrolytic solution 6 of the present invention can be used in mixed way with other nonaqueous electrolytic solutions.
<2-3. cathode>
The cathode of non-aqueous electrolyte secondary battery 6 is identical with the cathode described in non-aqueous electrolyte secondary battery 1.
<2-4. anode>
The anode of non-aqueous electrolyte secondary battery 6 is identical with the anode described in non-aqueous electrolyte secondary battery 1.
<2-5. partition plate>
The partition plate of non-aqueous electrolyte secondary battery 6 is identical with the partition plate described in non-aqueous electrolyte secondary battery 1.
<2-6. battery design>
The battery design of non-aqueous electrolyte secondary battery 6 is identical with battery design described in non-aqueous electrolyte secondary battery 1.
Embodiment
Hereinafter, embodiment and comparative example are enumerated, more specific description is carried out to the present invention, but the present invention is without departing from its master It is not limited to these embodiments restrictions in the range of purport.
The embodiment 1 of nonaqueous electrolytic solution 1
<The making -1 of non-aqueous electrolyte secondary battery>
[making of anode]
Use 85 mass parts LiCoO2(" C5 " of the manufacture of Japan Chemical Industry company) as a positive electrode active material, mixes 6 Mass parts of carbon black and 9 mass parts Kynoar (Wu Yu chemistry company systems are made, trade name " KF-1000 ") add in N- methyl -2- Pyrrolidones prepares slurry, which is uniformly coated on to the aluminium foil two sides of 15 μm of thickness, and compacting is carried out after dry so that anode The density of active material layer is 3.0g/cm3, as anode.
[making of cathode]
The addition in 98 mass parts Delanium powder KS-44 (timcal (テ ィ system カ Le) company manufactures, trade name) 100 mass parts as the sodium carboxymethylcellulose of thickener aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 matter Measure %), 2 mass parts as the SBR styrene butadiene rubbers of adhesive aqueous liquid dispersion (SBR styrene butadiene rubbers it is dense Spend for 50 mass %), it is mixed with disperser, slurry is made.Obtained slurry is uniformly coated on to the copper foil of 12 μm of thickness A face on, and be dried, then carry out compacting so that the density of negative electrode active material layer is 1.5g/cm3, as negative Pole.
[nonaqueous electrolytic solution]
Under dry argon atmosphere, respectively by fully dry LiPF6It is dissolved in the nonaqueous solvents mixed with ratio described in table 1 In, its concentration is made to prepare nonaqueous electrolytic solution for 1mol/L, then mono-fluor phosphate and/or difluorophosphoric acid salt are dissolved in this respectively In nonaqueous electrolytic solution, make its concentration that desired nonaqueous electrolytic solution be made for concentration described in table 1.
[assembling of non-aqueous electrolyte secondary battery]
By the partition plate of above-mentioned anode, cathode and polyethylene according to cathode, partition plate, anode, partition plate, cathode order It is laminated, makes cell device (Electricity ponds element).The cell device is inserted into following bags, and makes the terminal of anode and cathode It is provided projectingly, the bag is made of the laminated film that resin bed is coated on the two sides of aluminium (40 μm thick), is then injected into bag 0.5mL nonaqueous electrolytic solutions carry out vacuum sealing, make small disc type batteries.
<The evaluation of the High temperature storage characteristic of non-aqueous electrolyte secondary battery>
In order to improve interelectrode adaptation, by above-mentioned small disc type batteries with by the state that glass plate clamps at 25 DEG C with phase When under the constant current in 0.2C, charge and discharge are carried out with end of charge voltage 4.2V, final discharging voltage 3V, by the charge and discharge into Row 3, which cycles, simultaneously to be stabilized it, and the 4th circulates in be equivalent under the electric current of 0.5C and charge until end of charge voltage 4.4V, is further continued for the current value for charge until charging current value becomes being equivalent to 0.05C, that is, it is permanent to carry out 4.4V constant currents Constant-voltage charge (CCCV chargings) (0.05C cut-outs) then carries out 3V electric discharges to be equivalent to the constant current value of 0.2C, measures high Discharge capacity before temperature preservation.It carries out 4.4V-CCCV (0.05C cut-outs) again to charge, then the high temperature dwell under conditions of 85 DEG C Deposit 24 it is small when.
Before and after the High temperature storage is carried out, small disc type batteries are immersed in ethanol bath, generation is obtained by volume change Gas flow.Battery after preservation is subjected to electric discharge until final discharging voltage 3V, obtains at 25 DEG C with the constant current of 0.2C Remaining capacity after food preservation test.4.4V-CCCV (0.05C cut-outs) is carried out again to charge, and is put with the current value for being equivalent to 0.2C Electricity measures 0.2C capacity, obtains the 0.2C capacity after food preservation test, as recovery capacity to voltage 3V.Here, 1C is represented 1 can be fully charged when small current value.
Residual capacity and recovery capacity (%) when using the discharge capacity before High temperature storage as 100 are shown in table 1.
The embodiment 55 of 2~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1, the comparative example 1 of nonaqueous electrolytic solution 1~non- The comparative example 12 of water electrolysis liquid 1
Except by nonaqueous solvents, mono-fluor phosphate and/or difluorophosphoric acid salt described in 1~table of table 5 with recorded in 1~table of table 5 Content use beyond, prepare desired nonaqueous electrolytic solution according to the 1 same method of embodiment with nonaqueous electrolytic solution 1, make Into after non-aqueous electrolyte secondary battery, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 1, High temperature storage characteristic is carried out Evaluation.As a result as shown in 1~table of table 5.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
If 1~table of table 5 is understood, using the carbonic ester not only included at least containing a kind of halogen atom, but also contain single fluorophosphoric acid The nonaqueous electrolytic solution 1 of the present invention of salt and/or difluorophosphoric acid salt and manufactured non-aqueous electrolyte secondary battery 1, are only wrapped with using It is (non-containing the carbonic ester at least containing a kind of halogen atom or the nonaqueous electrolytic solution only containing mono-fluor phosphate and/or difluorophosphoric acid salt The comparative example 2 of water electrolysis liquid 1, the comparative example 3 of nonaqueous electrolytic solution 1, the comparative example 5~12 of nonaqueous electrolytic solution 1) and it is manufactured non-aqueous Nonaqueous electrolytic solution (the comparison of nonaqueous electrolytic solution 1 of above-mentioned 2 kinds of compounds is compared or be free of with using to electrolyte secondary battery The comparative example 4 of example 1, nonaqueous electrolytic solution 1) and manufactured non-aqueous electrolyte secondary battery is compared, and can not only inhibit High temperature storage When expansion, and may also suppress residual capacity and recover capacity represented by battery behavior deterioration.
Specifically, 1~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1 embodiment 55 make electrolyte with it is non- The comparative example 1 of water electrolysis liquid 1 and the comparative example 4 of nonaqueous electrolytic solution 1 are compared, and be can inhibit expansion during High temperature storage, can also be pressed down The deterioration of battery behavior processed.In addition, with only including the carbonic ester with halogen atom or only including mono-fluor phosphate and/or two The comparative example of the nonaqueous electrolytic solution 1 of fluorophosphate is compared, and containing there are two types of in the embodiment of the nonaqueous electrolytic solution 1 of compound, is confirmed It is enhanced simultaneously (for example, the reality of nonaqueous electrolytic solution 1 to both expansion when inhibiting High temperature storage and the deterioration for inhibiting battery behavior Apply the comparative example 2 of example 1 and nonaqueous electrolytic solution 1, the embodiment 8 of 1~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1 and non-aqueous The comparative example 5 of the comparative example 3 of electrolyte 1, the embodiment 13 of nonaqueous electrolytic solution 1 and nonaqueous electrolytic solution 1).In addition, nonaqueous electrolytic solution In containing vinylene carbonate as one of specific carbonic ester when, also confirm same effect.
The embodiment 74 of 56~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1, the comparative example 13 of nonaqueous electrolytic solution 1~ The comparative example 24 of nonaqueous electrolytic solution 1
<The making -2 of non-aqueous electrolyte secondary battery>
In the following, by the cathode used in embodiment 1 of above-mentioned nonaqueous electrolytic solution 1 with the silicon alloy cathode generation of following record It replaces, it will be in the comparative example of the embodiment of each nonaqueous electrolytic solution 1 and nonaqueous electrolytic solution 1 row in nonaqueous electrolytic solution and 6~table of table 8 In nonaqueous solvents, " mono-fluor phosphate and/or difluorophosphoric acid salt " column recorded compound according to the ratio recorded in the column into Row mixing, then by LiPF6As dissolving electrolyte salt wherein, and LiPF is made6Concentration is 1mol/L, is prepared desired non-aqueous Electrolyte (embodiment 74 of 56~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1 and the comparative example 13 of nonaqueous electrolytic solution 1 The nonaqueous electrolytic solution of the comparative example 24 of~nonaqueous electrolytic solution 1), in addition to above-mentioned nonaqueous electrolytic solution is used, according to above-mentioned non-water power Solve the identical method making non-aqueous electrolyte secondary battery of the embodiment 1 of liquid 1.
[making of silicon alloy cathode]
Using 73.2 parts by weight as the silicon of non-carbon material and 8.1 parts by weight copper and 12.2 parts by weight graphous graphite powders End (Timcal companies manufacture, trade name " KS-6 ") adds in contain Kynoar (poly thereto as negative electrode active material Vinylidene fluoride) (hreinafter referred to as " PVDF ") 12 parts by weight 54.2 weight of N-Methyl pyrrolidone solution Part and 50 parts by weight N-Methyl pyrrolidones, are mixed with disperser, slurry are made.Using gained slurry be uniformly coated on as On the copper foil of 18 μm of the thickness of negative electrode collector, after natural drying, finally diel is dried under reduced pressure at 85 DEG C.Then, pressed System is so that electrode density is 1.5g/cm3Left and right, as cathode.
<The evaluation of the High temperature storage characteristic of non-aqueous electrolyte secondary battery>
In order to improve interelectrode adaptation, by above-mentioned small disc type batteries with by the state that glass plate clamps at 25 DEG C with phase When under the constant current in 0.2C, charge and discharge are carried out with end of charge voltage 4.2V, final discharging voltage 3V, by the charge and discharge into Row 3, which cycles, simultaneously to be stabilized it, and the 4th circulates in be equivalent under the electric current of 0.5C and charge until end of charge voltage 4.2V, is further continued for the current value for charge until charging current value becomes being equivalent to 0.05C, that is, it is permanent to carry out 4.2V constant currents Constant-voltage charge (CCCV chargings) (0.05C cut-outs) then carries out 3V electric discharges to be equivalent to the constant current value of 0.2C, measures high Discharge capacity before temperature preservation.It carries out 4.2V-CCCV (0.05C cut-outs) again to charge, then the high temperature dwell under conditions of 85 DEG C It deposits 3 days.
Before and after the High temperature storage is carried out, small disc type batteries are immersed in ethanol bath, generation is obtained by volume change Gas flow.By the battery after preservation at 25 DEG C using the constant current of 0.2C carry out electric discharge until final discharging voltage as 3V, obtain Remaining capacity after to food preservation test.It carries out 4.2V-CCCV (0.05C cut-outs) again to charge, to be equivalent to the current value of 0.2C Electric discharge is carried out until voltage is 3V, measure 0.2C capacity obtains the 0.2C capacity after food preservation test, as recovery capacity. Here, 1C represent 1 it is small when can be fully charged current value.
Residual capacity and recovery capacity (%) such as 6~table of table, 8 institute when using the discharge capacity before High temperature storage as 100 Show.
[table 6]
[table 7]
[table 8]
If 6~table of table 8 is understood, when containing the silicon as non-carbon material in negative electrode active material, with carbon material is used to make It is identical for the situation of active material, using not only comprising at least one kind of carbonic ester containing halogen atom, but also contain mono-fluor phosphate And/or (the implementation of 56~nonaqueous electrolytic solution of embodiment 1 of nonaqueous electrolytic solution 1 of nonaqueous electrolytic solution 1 of the present invention of difluorophosphoric acid salt Example 74) and manufactured non-aqueous electrolyte secondary battery, with using only comprising at least one kind of carbonic ester containing halogen atom or containing only There are the nonaqueous electrolytic solution of mono-fluor phosphate and/or difluorophosphoric acid salt (comparative example 14 of nonaqueous electrolytic solution 1, the ratio of nonaqueous electrolytic solution 1 Compared with example 15, the comparative example 17~24 of nonaqueous electrolytic solution 1) and manufactured non-aqueous electrolyte secondary battery is compared or with using not Nonaqueous electrolytic solution (comparative example 13,16 of nonaqueous electrolytic solution 1) containing above-mentioned 2 kinds of compounds and manufactured nonaqueous electrolyte is secondary Battery is compared, and can not only inhibit expansion during High temperature storage, but also be may also suppress residual capacity and recovered represented by capacity Battery behavior deterioration.In addition, when containing the vinylene carbonate as one of specific carbonic ester in nonaqueous electrolytic solution, also really Recognize same effect.
The embodiment 1 of nonaqueous electrolytic solution 2
<The making of non-aqueous electrolyte secondary battery>
[making of anode]
It is made according to [making of anode] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method.
[making of cathode]
It is made according to [making of cathode] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method.
[nonaqueous electrolytic solution]
Under dry argon atmosphere, with the ratio recorded in table 9 by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and As " at 25 DEG C for liquid and dielectric constant more than 5, viscosity in below 0.6cP, and with being formed containing hetero atom Skeleton group (except backbone carbonyl) compound " dimethoxy-ethane (DME) mixed, after above-mentioned mixing To nonaqueous solvents in dissolve LiPF fully dried respectively6, make its concentration for 1mol/L, prepare nonaqueous electrolytic solution, then will Mono-fluor phosphate and/or difluorophosphoric acid salt are dissolved in the nonaqueous electrolytic solution, and it is respectively the concentration recorded in table 9 to make its concentration, Desired nonaqueous electrolytic solution is made.
[assembling of non-aqueous electrolyte secondary battery]
It is carried out according to [assembling of non-aqueous electrolyte secondary battery] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method It makes.
<The evaluation of the High temperature storage characteristic of non-aqueous electrolyte secondary battery>
In order to improve interelectrode adaptation, by above-mentioned small disc type batteries with by the state that glass plate clamps at 25 DEG C with phase When under the constant current in 0.2C, charge and discharge are carried out with end of charge voltage 4.2V, final discharging voltage 3V, by the charge and discharge into Row 3, which cycles, simultaneously to be stabilized it, and the 4th circulates in be equivalent under the electric current of 0.5C and charge until end of charge voltage 4.2V, is further continued for the current value for charge until charging current value becomes being equivalent to 0.05C, that is, it is permanent to carry out 4.2V constant currents Constant-voltage charge (CCCV chargings) (0.05C cut-outs) then carries out 3V electric discharges to be equivalent to the constant current value of 0.2C, measures high Discharge capacity before temperature preservation.It carries out 4.2V-CCCV (0.05C cut-outs) again to charge, then the high temperature dwell under conditions of 85 DEG C Deposit 24 it is small when.
Before and after the High temperature storage, small disc type batteries are immersed in ethanol bath, the gas of generation is obtained by volume change Amount, using the gas flow as " preserving expansion (mL) ".Battery after preservation is put at 25 DEG C with the constant current of 0.2C Electricity obtains the remaining capacity after food preservation test (%) until final discharging voltage 3V.Carrying out 4.2V-CCCV again, (0.05C is cut It is disconnected) it charges, electric discharge is carried out until 3V, measures 0.2C capacity, obtain the 0.2C after food preservation test to be equivalent to the current value of 0.2C Capacity, as " recovering capacity (%) ".Further, carry out 4.2V-CCCV (0.05C cut-outs) again to charge, to be equivalent to The current value of 1C carries out electric discharge until 3V, measures 1C capacity, the 1C capacity after food preservation test is obtained, by its ratio with 0.2C capacity Value is used as " load characteristic (%) ".
Preserve expansion (mL), using the discharge capacity before High temperature storage as 100 when residual capacity (%), recovery capacity (%) And load characteristic (%) is shown in table 9.Wherein, 1C represent 1 it is small when can be fully charged current value.
The embodiment 10 of 2~nonaqueous electrolytic solution of embodiment 2 of nonaqueous electrolytic solution 2, the comparative example 4 of nonaqueous electrolytic solution 2
Except nonaqueous solvents, mono-fluor phosphate and/or the difluorophosphoric acid salt recorded in table 9 are changed to recorded in table 9 Species and content are carried out beyond use, according to the 1 same method of embodiment with nonaqueous electrolytic solution 2, are prepared desired non- Water electrolysis liquid after non-aqueous electrolyte secondary battery is made, according to the 1 same method of embodiment with nonaqueous electrolytic solution 2, carries out high The evaluation of warm preservation characteristics.The results are shown in Table 9.
The comparative example 3 of 1~nonaqueous electrolytic solution of comparative example 2 of nonaqueous electrolytic solution 2
Nonaqueous solvents is used only with the content recorded in table 9, in addition, according to 1 phase of embodiment with nonaqueous electrolytic solution 2 Same method, prepares desired nonaqueous electrolytic solution, after non-aqueous electrolyte secondary battery is made, according to the reality of nonaqueous electrolytic solution 2 1 same method of example is applied, carries out the evaluation of High temperature storage characteristic.The results are shown in Table 9.
The embodiment 12 of 11~nonaqueous electrolytic solution of embodiment 2 of nonaqueous electrolytic solution 2, the comparative example 5 of nonaqueous electrolytic solution 2~non- The comparative example 7 of water electrolysis liquid 2
According to the content recorded in table 9 using nonaqueous solvents, and compared with whole nonaqueous electrolytic solutions, use 1 mass % Vinylene carbonate (VC), in addition, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 2, prepare desired Nonaqueous electrolytic solution after non-aqueous electrolyte secondary battery is made, according to the 1 same method of embodiment with nonaqueous electrolytic solution 2, carries out The evaluation of High temperature storage characteristic.The results are shown in Table 9.
Here, the mark of nonaqueous solvents, its dielectric constant and viscosity are as described below in table 9.
EC：Ethylene carbonate (dielectric constant:90th, viscosity:1.9)
EMC：Methyl ethyl carbonate (dielectric constant:2.9th, viscosity:0.7)
DME：Dimethoxy-ethane (dielectric constant:7.1st, viscosity:0.5)
EME：Ethyoxyl Ethyl Methyl Ether (dielectric constant:5.7th, viscosity:0.5)
DEE：Diethoxyethane (dielectric constant:5th, viscosity:0.6)
AN：Acetonitrile (dielectric constant:37.5, viscosity:0.4)
PN：Propionitrile (dielectric constant:27.7, viscosity:0.4)
[table 9]
If table 9 is understood, in the present invention, using comprising " at 25 DEG C being liquid and dielectric constant more than 5, viscosity In below 0.6cP, and there is the compound for forming the group (except backbone carbonyl) containing heteroatomic skeleton " and containing single fluorine The nonaqueous electrolytic solution of the present invention of phosphate and/or difluorophosphoric acid salt and manufactured non-aqueous electrolyte secondary battery, with using only Containing " at 25 DEG C for liquid and dielectric constant more than 5, viscosity in below 0.6cP, and with being formed containing hetero atom Skeleton group (except backbone carbonyl) compound " or only containing mono-fluor phosphate and/or difluorophosphoric acid salt compound Nonaqueous electrolytic solution and manufactured non-aqueous electrolyte secondary battery is compared or the non-water power of both compounds is not contained with using Solve liquid and manufactured non-aqueous electrolyte secondary battery is compared, not only maintain " at 25 DEG C for liquid and dielectric constant 5 with Upper, viscosity has the compound for forming the group (except backbone carbonyl) containing heteroatomic skeleton in below 0.6cP " Make possessed by script resistance inhibit in low-level advantage, and can be by High temperature storage when expansion inhibition can work in battery In the range of, and may also suppress residual capacity and recover the deterioration of the battery behavior represented by capacity.Moreover, also maintain height Load characteristic.
Specifically, nonaqueous electrolytic solution made of the embodiment 10 of 1~nonaqueous electrolytic solution of embodiment 2 of nonaqueous electrolytic solution 2 Compared with the comparative example 4 of the comparative example 1 of nonaqueous electrolytic solution 2 and nonaqueous electrolytic solution 2 only containing difluorophosphoric acid salt, high temperature dwell Expansion inhibition level when depositing is not a halfpenny the worse, and battery behavior degradation is also below peer-level.On the other hand, also protect Held the performance present invention " at 25 DEG C for liquid and dielectric constant more than 5, viscosity has in below 0.6cP The high load characteristic for the advantages of compound of group (except backbone carbonyl) of the formation containing heteroatomic skeleton " is original.Compared to it Under, only containing " at 25 DEG C for liquid and dielectric constant more than 5, viscosity in below 0.6cP, and with being formed containing miscellaneous The comparative example 2 of nonaqueous electrolytic solution 2 of the compound of the group (except backbone carbonyl) of the skeleton of atom " and nonaqueous electrolytic solution 2 Comparative example 3, battery occur deterioration reaches inoperable degree, difference is apparent.
In addition, the comparative example 7 of 6~nonaqueous electrolytic solution of comparative example 2 from nonaqueous electrolytic solution 2, contain in nonaqueous electrolytic solution It is and non-although battery can also keep certain work when having vinylene carbonate (VC) as one of specific carbonic ester The embodiment 10 of 1~nonaqueous electrolytic solution of embodiment 2 of water electrolysis liquid 2 is compared, and is in very big difference in terms of load characteristic.This be because For：As the embodiment 11 of nonaqueous electrolytic solution 2 and the embodiment 12 of nonaqueous electrolytic solution 2 are showed, deposit at the same time " at 25 DEG C for liquid and dielectric constant more than 5, viscosity in below 0.6cP, and with being formed containing heteroatomic When 3 kinds of compound of the group (except backbone carbonyl) of skeleton ", difluorophosphoric acid and vinylene carbonate substances, it can obtain more preferable Effect.
The embodiment of nonaqueous electrolytic solution 3 and the comparative example of nonaqueous electrolytic solution 3
Nonaqueous electrolyte two obtained in the embodiment of following nonaqueous electrolytic solutions 3 and the comparative example of nonaqueous electrolytic solution 3 Primary cell it is each evaluation method is as follows described.
<The measure of initial stage discharge capacity>
In order to improve interelectrode adaptation, by non-aqueous electrolyte secondary battery with by the state that glass plate clamps at 25 DEG C Under to be equivalent to the constant current charge of 0.2C to 4.2V, 3V is then discharged to the constant current of 0.2C.The cycling is carried out 3 It is secondary, stablize battery, 4.2V is charged under the 4th constant current for circulating in 0.5C, then carried out with the constant voltage of 4.2V Charging is 0.05C up to current value, is discharged to 3V with the constant current of 0.2C, initial stage discharge capacity is obtained.1C mentioned here Represent the current value to be discharged with 1 when small the reference capacity of battery, 0.2C represents its 1/5 current value.
<The evaluation of trickle charge characteristic>
Non-aqueous electrolyte secondary battery after capacity evaluation test is immersed in ethanol bath, after measuring volume, Constant current charge is carried out with the constant current of 0.5C at 60 DEG C, after reaching 4.25V, constant-potential charge is switched to, continuously fills Electricity 1 week.It after cooling down battery, is immersed in ethanol bath, measures volume, generation is obtained by the variation of volume before and after trickle charge The amount of gas, as " gas flow (mL) generated after trickle charge ".Measure generate gas amount after, at 25 DEG C with The constant current of 0.2C is discharged to 3V.Then, with the constant current charge of 0.5C to 4.2V, then with the constant voltage of 4.2V into Row charges until current value is 0.05C, is discharged to 3V with the constant current of 1C, measures the 1C electric discharges after trickle charge experiment and hold Amount.Ratio of the 1C discharge capacities after trickle charge experiment compared with initial stage discharge capacity is obtained, as " after trickle charge 1C discharge capacities (%) ".
The embodiment 1 of nonaqueous electrolytic solution 3
<The making of non-aqueous electrolyte secondary battery>
[making of cathode]
94 mass parts natural graphite powder and 6 mass parts Kynoar are mixed, add in n-methyl-2-pyrrolidone, system Into slurry, the d values of lattice plane (002 face) are 0.336nm during the natural graphite powder X-ray diffraction, crystallite dimension (Lc) is 652nm, ash content be the median particle diameter that 0.07 mass parts, laser diffraction/scattering method acquire be 12 μm, the specific surface that BET method acquires Product is 7.5m2/ g, R the values (=I being obtained by the Raman spectrum analysis that argon laser is used to carry outB/IA) be 0.12, be in 1570~1620cm-1The half width at the peak of scope is 19.9cm-1.The slurry is uniformly coated on to one of copper foil 12 μm thick On face, after dry, carrying out compacting makes the density of negative electrode active material layer be 1.67g/cm3, as cathode.
[making of anode]
By the cobalt acid lithium (LiCoO of 90 mass % as a positive electrode active material2), 4 mass % carbon blacks, 6 mass % gather inclined fluorine Ethylene (Wu Yu chemistry company systems are made, trade name " KF-1000 ") is mixed, and adds in n-methyl-2-pyrrolidone, slurry is made The slurry is coated on the two sides of thick 15 μm of aluminium foil by material, and after dry, carrying out compacting makes the density of positive electrode active material layer be 3.2g/cm3, as anode.
[nonaqueous electrolytic solution]
Under dry argon atmosphere, in the mixture (volume ratio 2 of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate: 4:4) dissolving LiPF fully dried in6, vinylene carbonate, mono-fluor phosphate and/or difluorophosphoric acid salt and " this hair Bright compound A ", makes LiPF6Concentration is 1mol/L, vinylene carbonate ester concentration is 2 mass %, and make mono-fluor phosphate and/ Or the concentration of difluorophosphoric acid salt and " the compound of the present invention A " are respectively the normal concentration recorded in table 10, are made desired Nonaqueous electrolytic solution.
[manufacture of non-aqueous electrolyte secondary battery]
By the partition plate of above-mentioned anode, cathode and polyethylene according to cathode, partition plate, anode, partition plate, cathode order It is laminated, makes cell device.The cell device is inserted into following bags, and is provided projectingly the terminal of anode and cathode, The bag is made of the laminated film that resin bed is coated on the two sides of aluminium (40 μm thick), and above-mentioned electrolyte is then injected into bag, Vacuum sealing is carried out, makes small disc type batteries.Carry out the evaluation of above-mentioned trickle charge characteristic.The results are shown in Table 10.
The embodiment 10 of 2~nonaqueous electrolytic solution of embodiment 3 of nonaqueous electrolytic solution 3, the comparative example 1 of nonaqueous electrolytic solution 3~non- The comparative example 4 of water electrolysis liquid 3
Except " mono-fluor phosphate and/or difluorophosphoric acid salt ", " the compound of the present invention " described in table 10 are changed to table 10 Recorded species and content are carried out beyond use, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 3, prepare institute's phase The nonaqueous electrolytic solution of prestige, after non-aqueous electrolyte secondary battery is made, according to the 1 same method of embodiment with nonaqueous electrolytic solution 3 Carry out trickle charge evaluating characteristics.The results are shown in Table 10.
[table 10]
As shown in table 10, contain " the compound of the present invention A " using in nonaqueous electrolytic solution, while also contain mono-fluor phosphate And/or difluorophosphoric acid salt the present invention nonaqueous electrolytic solution and the manufactured non-aqueous electrolyte secondary battery (reality of nonaqueous electrolytic solution 3 Apply the embodiment 10 of 1~nonaqueous electrolytic solution of example 3), it contains only " the compound of the present invention A " with using or contains only single fluorophosphoric acid The nonaqueous electrolytic solution of salt and/or difluorophosphoric acid salt (comparative example 4 of 2~nonaqueous electrolytic solution of comparative example 3 of nonaqueous electrolytic solution 3) or Using the nonaqueous electrolytic solution (comparative example 1 of nonaqueous electrolytic solution 3) without both compounds, manufactured nonaqueous electrolyte is secondary Battery is compared, the generation of gas and the deterioration of battery behavior when can inhibit trickle charge.
Each evaluation of battery obtained in the embodiment of following nonaqueous electrolytic solutions 4 and the comparative example of nonaqueous electrolytic solution 4 Method is as follows.
[evaluation of initial stage discharge capacity]
In order to improve interelectrode adaptation, by lithium secondary battery with by the state that glass plate clamps at 25 DEG C with suitable In 0.2C constant current charge to 4.2V, 3V is then discharged to the constant current of 0.2C.The cycling is carried out 3 times, makes electricity Pond is stablized, then the 4th Xun Huan with the constant voltage of 4.2V charge until electricity with the constant current charge of 0.5C to 4.2V Flow valuve is 0.05C, is discharged to 3V with the constant current of 0.2C, initial stage discharge capacity is obtained.1C mentioned here is represented can be with 1 small When the current value that discharges the reference capacity of battery, 2C represents its 2 times of current value, and 0.2C represents its 1/5 current value.
[evaluation of 2C discharge capacities]
Following experiments are carried out with the battery after initial stage discharge capacity evaluation test：With the constant electricity of 0.5C at 25 DEG C Current charge is to 4.2V, then using the constant-potential charge of 4.2V to current value as 0.05C, then is discharged to the constant current of 2C 3V.Discharge capacity (%) when being obtained using the discharge capacity of initial stage discharge capacity experiment as 100.
[evaluation of High temperature storage characteristic]
By the battery after overcapacity evaluation test with the constant current charge of 0.5C to 4.2V, then with the constant of 4.2V Voltage charges to current value as 0.05C.Following experiments are carried out with the battery：When preservation 24 is small at 85 DEG C, after battery is cooled down, 3V is discharged to the constant current of 0.2C at 25 DEG C, with the constant current charge of 0.5C to 4.2V, then with the constant of 4.2V Voltage charges to current value as 0.05C, is then discharged to 3V with the constant current of 2C.Putting with the experiment of initial stage discharge capacity is obtained Discharge capacity (%) when capacitance is 100.
[evaluation of thermal stability]
4.2V is charged to the homeostasis electric current for being equivalent to 0.2C, 3V is then discharged to the constant current of 0.2C.This is followed Ring carries out 3 times, stablizes battery, and the 4th Xun Huan is with the constant current charge of 0.5C to 4.2V, then with the constant voltage of 4.2V Current value is charged to as 0.05C.The rechargeable battery is measured with Callvert formula calorimeter (Calvet ' s calorimeter) to exist Thermal discharge at room temperature to 300 DEG C.
The embodiment 1 of nonaqueous electrolytic solution 4
[making of cathode]
The 100 mass parts conducts of addition in 98 mass parts 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 mass parts conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubbers be 50 mass %) of the SBR styrene butadiene rubbers of adhesive, with point Scattered device is mixed, and slurry is made.Obtained slurry is uniformly coated on to the one side of the copper foil of 10 μm of thickness, and is dried, Then carrying out calendering with press makes its thickness for 75 μm, and the product after calendering is cut into the size of active material layer for width 30mm, long 40mm, and the shape with width 5mm, the uncoated portion of long 9mm, as cathode.
[making of anode]
By the cobalt acid lithium (LiCoO of 90 mass % as a positive electrode active material2), acetylene of the 5 mass % as conductive material Black and 5 mass % are mixed as the Kynoar (PVdF) of binding agent in n-methyl-2-pyrrolidone solvent, are made Slurry.Gained slurry is coated on a face of aluminium foil 15 μm thick, and be dried, then carrying out calendering with press makes Its thickness is 80 μm, and the product after calendering is cut into the size of active material layer for width 30mm, long 40mm, and with width 5mm, length The shape of the uncoated portion of 9mm, as anode.
[preparation of electrolyte]
Under dry argon atmosphere, by sulfolane (SLF) and methyl ethyl carbonate (EMC：Viscosity at 25 DEG C is Mixture (volume ratio 3 0.68mPas):7) 98 mass parts, mix with 2 mass parts vinylene carbonates (VC), then at it Middle dissolving LiPF fully dried6, make LiPF6Ratio for 1.0mol/L, as electrolyte.
[manufacture of nonaqueous electrolyte battery]
The partition plate of above-mentioned anode, cathode and polyethylene according to the order of cathode, partition plate, anode is laminated, is made Make cell device.The cell device is inserted into following bags, and is provided projectingly the terminal of anode and cathode, the bag is by aluminium The laminated film that the two sides of (40 μm thick) is coated with resin bed is made, and above-mentioned electrolyte is then injected into bag, carries out vacuum sealing, Small disc type batteries are made, and are evaluated.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The embodiment 2 of nonaqueous electrolytic solution 4
In the electrolyte of the embodiment 1 of nonaqueous electrolytic solution 4, replace carbonic acid sub- using vinylethylene carbonate (VEC) Vinyl acetate (VC) in addition, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, makes sheet lithium secondary battery, And it is evaluated.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The embodiment 3 of nonaqueous electrolytic solution 4
In the electrolyte of the embodiment 1 of nonaqueous electrolytic solution 4, vinylene carbonate is replaced with fluorine ethylene carbonate (FEC) (VC), in addition, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, sheet lithium secondary battery is made, and is carried out Evaluation.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The embodiment 4 of nonaqueous electrolytic solution 4
In the electrolyte of the embodiment 1 of nonaqueous electrolytic solution 4, with the LiPO of 0.5 mass parts2F2Instead of vinylene carbonate (VC), in addition, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, sheet lithium secondary battery is made, and is carried out Evaluation.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The comparative example 1 of nonaqueous electrolytic solution 4
In the mixture (volume ratio 3 of sulfolane (SLF) and methyl ethyl carbonate (EMC):7) dissolving is fully dried in LiPF6, and make LiPF6Ratio for 1.0mol/L, prepare electrolyte, in addition to the electrolyte is used, according to nonaqueous electrolytic solution 4 The identical method of embodiment 1, make sheet lithium secondary battery, and evaluated.The ingredient and evaluation result of electrolyte are such as Shown in table 11 and table 12.
The comparative example 2 of nonaqueous electrolytic solution 4
By sulfolane (SLF) and gamma-butyrolacton (GBL：Viscosity at 25 DEG C is 1.73mPas) mixture 94 mass parts (volume ratio 3:7), 2 mass parts vinylene carbonates (VC), 2 mass parts vinylethylene carbonates (VEC) and 2 matter Amount part trioctyl phosphate (TOP) is mixed, and then dissolves LiPF fully dried wherein6, and make LiPF6Ratio be 1.0mol/L prepares electrolyte, in addition to the electrolyte is used, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, system Make sheet lithium secondary battery, and evaluated.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The comparative example 3 of nonaqueous electrolytic solution 4
By the mixture 94 mass parts (volume ratio 3 of sulfolane (SLF) and gamma-butyrolacton (GBL):7), 2 mass parts carbonic acid Vinylene (VC), 2 mass parts vinylethylene carbonates (VEC) and 2 mass parts trioctyl phosphates (TOP) are mixed, so Dissolve LiBF fully dried wherein afterwards4, and make LiBF4Ratio for 1.0mol/L, electrolyte is prepared, except using the electricity It solves outside liquid, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, makes sheet lithium secondary battery, and evaluated.Electricity The ingredient and evaluation result of solution liquid are as shown in table 11 and table 12.
The comparative example 4 of nonaqueous electrolytic solution 4
By the mixture (volume ratio 3 of gamma-butyrolacton (GBL) and methyl ethyl carbonate (EMC):7) 98 mass parts and 2 mass parts Vinylene carbonate (VC) is mixed, and then dissolves LiBF fully dried wherein6, and make LiPF6Ratio be 1.0mol/L prepares electrolyte, in addition to the electrolyte is used, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, system Make sheet lithium secondary battery, evaluated.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
The comparative example 5 of nonaqueous electrolytic solution 4
By the mixture (volume ratio 3 of ethylene carbonate (EC) and methyl ethyl carbonate (EMC):7) 98 mass parts and 2 mass parts Vinylene carbonate (VC) is mixed, and then dissolves LiBF fully dried wherein6, and make LiPF6Ratio be 1.0mol/L prepares electrolyte, in addition to the electrolyte is used, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 4, system Make sheet lithium secondary battery, and evaluated.The ingredient and evaluation result of electrolyte are as shown in table 11 and table 12.
[table 11]
No. Electrolyte Solvent
Embodiment 1 LiPF6 SLF+EMC+VC
Embodiment 2 LiPF6 SLF+EMC+VEC
Embodiment 3 LiPF6 SLF+EMC+FEC
Embodiment 4 LiPF6 SLF+EMC+LiPO2F2
Comparative example 1 LiPF6 SLF+EMC
Comparative example 2 LiPF6 SLF+GBL+VC+VEC+top
Comparative example 3 LiBF4 SLF+GBL+VC+VEC+top
Comparative example 4 LiPF6 GBL+EMC+VC
Comparative example 5 LiPF6 EC+EMC+VC
[table 12]
No. 2C discharge capacities (%) before 85 DEG C of preservations 2C discharge capacities (%) after 85 DEG C of preservations
Embodiment 1 83.1 82.6
Embodiment 2 82.5 81.8
Embodiment 3 87.4 80.8
Embodiment 4 89.7 85.5
Comparative example 1 66.1 55.4
Comparative example 2 48.3 3.4
Comparative example 3 26.0 14.1
Comparative example 4 89.8 70.2
Comparative example 5 89.1 84.7
The embodiment 5 of nonaqueous electrolytic solution 4
Come using anode, cathode and the electrolyte obtained according to the 3 same method of embodiment with nonaqueous electrolytic solution 4 Sheet lithium secondary battery is made, the evaluation of thermal stability is carried out by heat analysis.Evaluation result is as shown in table 13.
The comparative example 6 of nonaqueous electrolytic solution 4
Anode, cathode and the electrolyte obtained using the 4 same method of comparative example of nonaqueous electrolytic solution 4 makes sheet Lithium secondary battery carries out the evaluation of thermal stability by heat analysis.Evaluation result is as shown in table 13.
[table 13]
Thermal discharge (J)
Embodiment 5 382
Comparative example 6 605
From 11~table of table 13, the battery (embodiment of nonaqueous electrolytic solution 4 made using the nonaqueous electrolytic solution of the present invention 1~4) charge-discharge characteristic at higher current densities, High temperature storage characteristic are excellent, and can by the embodiment 5 of nonaqueous electrolytic solution 4 Know, it is safe since battery thermal discharge is low.And battery (the ratio of nonaqueous electrolytic solution 4 of the nonaqueous electrolytic solution of the present invention is not used Compared with the comparative example 5 of 1~nonaqueous electrolytic solution of example 4) charge-discharge characteristic, High temperature storage characteristic it is poor, such as the comparative example of nonaqueous electrolytic solution 4 6 like that, and battery thermal discharge is high.
[making of anode]
Mix the lithium-transition metal composite oxide (LiNi that 92 mass parts contain nickel, manganese and cobalt0.33Mn0.33Co0.33O2)、4 Mass parts Kynoar (following, to be properly termed as " PVdF ") and 4 mass parts acetylene blacks, add in N-Methyl pyrrolidone, are made The slurry is coated on the two sides of collector made of aluminum by slurry, and dry, obtains anode.
[making of cathode]
92 mass parts powdered graphites and 8 mass parts PVdF are mixed, N-Methyl pyrrolidone is added in, slurry is made, this is starched Material is coated on a face of the collector being made of copper, and dry, obtains cathode.
[manufacture of non-aqueous electrolyte secondary battery]
By the partition plate of above-mentioned anode, cathode and polyethylene according to cathode, partition plate, anode, partition plate, cathode order It is laminated, makes cell device.The cell device of above-mentioned acquisition is wrapped up with tubular aluminium press mold, after injecting aftermentioned electrolyte, very Sky sealing, makes sheet non-aqueous electrolyte secondary battery.In addition, in order to improve interelectrode adaptation, with glass plate clamping piece Shape battery pressurizes.
[capacity evaluation]
In 25 DEG C of thermostats, sheet non-aqueous electrolyte secondary battery is subjected to constant current-constant voltage with 0.2C and is filled Electricity (following, to be properly termed as " CCCV chargings "), until voltage is 4.4V, is then discharged to 2.75V with 0.2C.Repeat the operation 3 It is secondary, after being adjusted, CCCV is carried out with 0.2C again and charges to 4.4V, 2.75V is discharged to 1C again, initial stage electric discharge is obtained and holds Amount.Cut-out electric current during charging is 0.05C.In addition, 1C refer to available 1 it is small when electric current when all told of battery being made to discharge Value.
[4.4V trickle charges evaluating characteristics]
Battery after overcapacity evaluation test is put into 60 DEG C of thermostat, carrying out constant current with 0.2C fills Electricity, voltage are switched to constant-potential charge when reaching 4.4V.It carries out 7 days after charging, battery is cooled to 25 DEG C.Then by battery It is immersed in ethanol bath, measures buoyancy (Archimedes principle), the growing amount of gas is obtained by buoyancy.It is further, since right The degradation of capacity is evaluated after trickle charge, is discharged to 3V first with 0.2C, and then carrying out CCCV with 0.2C charges directly It is 4.4V to voltage, then 2.75V is discharged to 1C, measures discharge capacity (recovery capacity) at this time, according to following calculating formulas, ask Go out the capacity retention ratio after trickle charge.The numerical value is bigger, shows that the degradation of battery is lower.
Capacity retention ratio (%) after trickle charge 7 days
=(trickle charge 7 days after recovery capacity/initial stage discharge capacity) × 100
The embodiment 1 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 2:8, weight ratio 24.7:75.3) with the ratio dissolving electrolyte LiPF of 1mol/L in6, by gained electricity Electrolyte (I) based on solution liquid, the addition Isosorbide-5-Nitrae into the basic electrolyte (I), 8,11- tetraazacyclododecane tetradecanes and carbonic acid are sub- Vinyl acetate (VC) prepares nonaqueous electrolytic solution, and makes Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes and vinylene carbonate (VC) compared with The concentration of nonaqueous electrolytic solution is respectively 0.1 mass % and 1 mass %, is made according to the method described above using the nonaqueous electrolytic solution non- Water-Electrolyte secondary cell carries out capacity evaluation and 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The embodiment 2 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 8,11- tetra- azepines The ring tetradecane and fluorine ethylene carbonate (FEC), and they are respectively 0.1 mass % and 1 matter compared with the concentration of nonaqueous electrolytic solution Measure the nonaqueous electrolytic solution of %.As a result as shown in table 14.
The embodiment 3 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 8,11- tetra- azepines The ring tetradecane and difluorophosphate (LiPO2F2), and they are respectively 0.1 mass % and 0.5 compared with the concentration of nonaqueous electrolytic solution The nonaqueous electrolytic solution of quality %.As a result as shown in table 14.
The embodiment 4 of nonaqueous electrolytic solution 5
Addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes make it compared with the dense of nonaqueous electrolytic solution in basic electrolyte (I) It spends for 0.02 mass %, prepares nonaqueous electrolytic solution.Nonaqueous electrolytic solution obtained by use makes nonaqueous electrolyte two according to the method described above Primary cell carries out capacity evaluation and 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The embodiment 5 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 8,11- tetra- azepines The ring tetradecane, and it is the nonaqueous electrolytic solution of 0.05 mass % compared with the concentration of nonaqueous electrolytic solution.As a result as shown in table 14.
The embodiment 6 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 8,11- tetra- azepines The ring tetradecane, and it is the nonaqueous electrolytic solution of 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.As a result as shown in table 14.
The embodiment 7 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 7,10- tetra- azepines Cyclododecane, and it is the nonaqueous electrolytic solution of 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.As a result as shown in table 14.
The embodiment 8 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae, 8,11- tetramethyls are with the addition of in basic electrolyte (I) Base-Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes, and it is the nonaqueous electrolytic solution of 0.1 mass % compared with the concentration of nonaqueous electrolytic solution. As a result as shown in table 14.
The embodiment 9 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that Isosorbide-5-Nitrae is with the addition of in basic electrolyte (I), 8,11- tetra- azepines Ring tetradecane -5,7- diketone, and it is the nonaqueous electrolytic solution of 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.As a result such as table Shown in 14.
The embodiment 10 of nonaqueous electrolytic solution 5
Using following nonaqueous electrolytic solutions, make non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation with And 4.4V trickle charge evaluating characteristics, the nonaqueous electrolytic solution are that ring (the sweet ammonia of β-alanyl is with the addition of in basic electrolyte (I) Acyl-β-alanyl glycyl), and it is the nonaqueous electrolytic solution of 0.02 mass % compared with the concentration of nonaqueous electrolytic solution.As a result such as Shown in table 14.
The embodiment 11 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 1:9, weight ratio 12.7:87.3) with the ratio dissolving electrolyte LiPF of 1mol/L in6, by what is obtained Electrolyte (II) based on electrolyte, the addition Isosorbide-5-Nitrae into the basic electrolyte (II), 8,11- tetraazacyclododecane tetradecanes, as Nonaqueous electrolytic solution, and make Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.It uses Gained nonaqueous electrolytic solution makes non-aqueous electrolyte secondary battery according to the method described above, carries out capacity evaluation and 4.4V continuously fills Electrical characteristics are evaluated.As a result as shown in table 14.
The embodiment 12 of nonaqueous electrolytic solution 5
In the fluorine ethylene carbonate (FEC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Mixed solvent (mixed volume ratio 1:9th, weight ratio 14.2:85.8) with the ratio dissolving electrolyte LiPF of 1mol/L in6, will Electrolyte (III) based on the electrolyte arrived, addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecanes 14 into the basic electrolyte (III) Alkane as nonaqueous electrolytic solution, and makes Isosorbide-5-Nitrae, and 8,11- tetraazacyclododecane tetradecanes are 0.1 matter compared with the concentration of nonaqueous electrolytic solution Measure %.Nonaqueous electrolytic solution obtained by use makes non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation and 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The embodiment 13 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 3:7, weight ratio 36.0:64.0) with the ratio dissolving electrolyte LiPF of 1mol/L in6, by what is obtained Electrolyte (IV) based on electrolyte, the addition Isosorbide-5-Nitrae into the basic electrolyte (IV), 8,11- tetraazacyclododecane tetradecanes, as Nonaqueous electrolytic solution, and make Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.It uses Gained nonaqueous electrolytic solution makes non-aqueous electrolyte secondary battery according to the method described above, carries out capacity evaluation and 4.4V continuously fills Electrical characteristics are evaluated.As a result as shown in table 14.
The embodiment 14 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 4:6th, weight ratio 46.7:53.4) with the ratio dissolving electrolyte LiPF of 1mol/L in6, by what is obtained Electrolyte (V) based on electrolyte, addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes -5,7- bis- into the basic electrolyte (V) Ketone as nonaqueous electrolytic solution, and makes Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecane -5,7- diketone compared with nonaqueous electrolytic solution concentration For 0.1 mass %.Nonaqueous electrolytic solution obtained by use makes non-aqueous electrolyte secondary battery according to the method described above, carries out capacity and comments Valency and 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The embodiment 15 of nonaqueous electrolytic solution 5
In the ethylene carbonate (EC) and the mixed solvent (mixed volume ratio of propylene carbonate (PC) as cyclic carbonate 5:5, weight ratio 52.4:47.6) with the ratio dissolving electrolyte LiPF of 1mol/L in6, will be electric based on obtained electrolyte Liquid (VI) is solved, addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecane -5,7- diketone, as non-water power into the basic electrolyte (VI) Liquid is solved, and makes Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecane -5,7- diketone are 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.Make With gained nonaqueous electrolytic solution, non-aqueous electrolyte secondary battery is made according to the method described above, carries out capacity evaluation and 4.4V is continuous Charge characteristic is evaluated.As a result as shown in table 14.It understands in the case where being with the addition of Cyclic polyamides compound, it is molten to that can be used as There is no limit for the weight ratio for the cyclic carbonate that agent uses.
The comparative example 1 of nonaqueous electrolytic solution 5
Using basic electrolyte (I) itself, non-aqueous electrolyte secondary battery is made according to the method described above, carries out capacity evaluation And 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The comparative example 2 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 35:65, weight ratio 41.4:58.6) in, with the ratio dissolving electrolyte LiPF of 1mol/L6, will Electrolyte (VII) based on the electrolyte arrived, addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecanes 14 into the basic electrolyte (VII) Alkane as nonaqueous electrolytic solution, and makes Isosorbide-5-Nitrae, and 8,11- tetraazacyclododecane tetradecanes are 0.1 matter compared with the concentration of nonaqueous electrolytic solution Measure %.Nonaqueous electrolytic solution obtained by use makes non-aqueous electrolyte secondary battery according to the method described above, carry out capacity evaluation and 4.4V trickle charge evaluating characteristics.As a result as shown in table 14.
The comparative example 3 of nonaqueous electrolytic solution 5
In the mixed of the ethylene carbonate (EC) as cyclic carbonate and the methyl ethyl carbonate (EMC) as linear carbonate Bonding solvent (mixed volume ratio 4:6, weight ratio 46.7:53.4) with the ratio dissolving electrolyte LiPF of 1mol/L in6, by what is obtained Electrolyte (V) based on electrolyte, addition Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes, as non-into the basic electrolyte (V) Water electrolysis liquid, and make Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.1 mass % compared with the concentration of nonaqueous electrolytic solution.Using institute Nonaqueous electrolytic solution is obtained, makes non-aqueous electrolyte secondary battery according to the method described above, carries out capacity evaluation and 4.4V trickle charges Evaluating characteristics.As a result as shown in table 14.
Cyclic polyamine compounds or the mark of Cyclic polyamides compound are as described below in table 14.
cyclam：1,4,8,11- tetraazacyclododecane tetradecanes
cyclen：Cyclen
TM-cyclam：1,4,8,11- tetramethyl -1,4,8,11- tetraazacyclododecane tetradecanes
DO-cyclam：1,4,8,11- tetraazacyclododecane tetradecane -5,7- diketone
TetO-cyclam：Ring (β-alanyl glycyl-β-alanyl glycyl)
In table 14, " in unsaturated carbon acid ester, fluorine-containing carbonic ester, mono-fluor phosphate and difluorophosphoric acid salt extremely Few a kind of compound " refers to " specific compound ", and the mark of " specific compound " is as described below.
VC：Vinylene carbonate
FEC：Fluorine ethylene carbonate
LiPO2F2：Difluorophosphate
If above-mentioned table 14 is understood, using the nonaqueous electrolytic solution of the present invention, trickle charge characteristic (nonaqueous electrolytic solution 5 can be improved Embodiment 1~15).On the other hand, (embodiment 5-1, reality are not met in the case of the nonaqueous electrolytic solution that the present invention is not used Apply the nonaqueous electrolytic solution of any condition in mode 5-2, embodiment 5-3), trickle charge characteristic it is very poor (nonaqueous electrolytic solution 5 Comparative example 1~3).In addition, as described in the comparative example 2 of nonaqueous electrolytic solution 5 and the comparative example 3 of nonaqueous electrolytic solution 5, in non-water system Organic solvent contains cyclic polyamine compounds, and containing in the case of the cyclic carbonate for having more than 40 mass %, trickle charge Characteristic is also very poor.
<The making of secondary cell>
[making of anode]
It is made according to [making of anode] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method.
[making of cathode]
It is made according to [making of cathode] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method.
[nonaqueous electrolytic solution]
The embodiment 1 of nonaqueous electrolytic solution 6
Under dry argon atmosphere, in the mixture of ethylene carbonate and methyl ethyl carbonate (volume ratio 3:7) dissolving is through filling in Divide dry LiPF6, table 15 record the annular 1,2- perfluors second di-sulfonyl imides lithium as ring-type di-sulfonyl imides salt with And difluorophosphate, and its concentration is made to be respectively 1mol/L, 0.05mol/L, 0.5 mass %, desired non-aqueous solution electrolysis is made Liquid.
[assembling of battery]
It is made according to [assembling of battery] of the embodiment 1 with nonaqueous electrolytic solution 1 identical method.
[evaluation of battery]
In order to improve interelectrode adaptation, by above-mentioned small disc type batteries with by the state that glass plate clamps at 25 DEG C with phase When the constant current in 0.2C carries out charge and discharge, end of charge voltage 4.2V, final discharging voltage 3V carry out 3 Xun Huans Charge and discharge stabilize it, the 4th circulates in be equivalent under the electric current of 0.5C and charges to end of charge voltage 4.4V, be further continued for into Row charging becomes being equivalent to 0.05C up to charging current value, that is, carries out 4.4V- constant-current constant-voltages charging (CCCV chargings) (0.05C cut-outs) then carries out 3V electric discharges to be equivalent to the constant current value of 0.2C, measures the discharge capacity before High temperature storage. It carries out 4.4V-CCCV (0.05C cut-outs) again to charge, then when High temperature storage 24 is small under conditions of 85 DEG C.
Before and after the High temperature storage, small disc type batteries are immersed in ethanol bath, the gas of generation is obtained by volume change Amount.Battery after preservation is discharged to final discharging voltage 3V at 25 DEG C with the constant current of 0.2C, after obtaining food preservation test Remaining capacity.4.4V-CCCV (0.05C cut-outs) is carried out again to charge, and 3V is discharged to the current value for being equivalent to 0.2C, is measured 0.2C capacity obtains the 0.2C capacity after food preservation test, as recovery capacity.It here, can be fully charged when 1C expressions 1 are small Current value.Residual capacity and recovery capacity (%) during by using the discharge capacity before High temperature storage as 100 are shown in table 15.
The embodiment 2 of nonaqueous electrolytic solution 6
Using ring-type 1, the 2- perfluor second di-sulfonyl imides lithiums as ring-type di-sulfonyl imides salt of 0.1mol/L, except this Outside, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The embodiment 3 of nonaqueous electrolytic solution 6
Using ring-type 1, the 2- perfluor second di-sulfonyl imides lithiums as ring-type di-sulfonyl imides salt of 0.01mol/L, remove Outside this, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The embodiment 4 of nonaqueous electrolytic solution 6
Using ring-type 1,2- perfluor the third di-sulfonyl imides lithiums as ring-type di-sulfonyl imides salt of 0.05mol/L, remove Outside this, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The embodiment 5 of nonaqueous electrolytic solution 6
Using ring-type 1, the 2- perfluor second di-sulfonyl imides sodium as ring-type di-sulfonyl imides salt of 0.05mol/L, remove Outside this, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The embodiment 6 of nonaqueous electrolytic solution 6
In addition to using the difluorophosphate of 0.1 mass %, according to the side identical with the embodiment 1 of nonaqueous electrolytic solution 6 Method makes non-aqueous electrolyte secondary battery, and carries out the evaluation of battery.As a result as shown in Table 15.
The embodiment 7 of nonaqueous electrolytic solution 6
In addition to using the difluorophosphate of 1.0 mass %, according to the side identical with the embodiment 1 of nonaqueous electrolytic solution 6 Method makes non-aqueous electrolyte secondary battery, and carries out the evaluation of battery.As a result as shown in Table 15.
The embodiment 8 of nonaqueous electrolytic solution 6
In addition to using the difluorophosphoric acid sodium of 0.5 mass %, according to the side identical with the embodiment 1 of nonaqueous electrolytic solution 6 Method makes non-aqueous electrolyte secondary battery, and carries out the evaluation of battery.As a result as shown in Table 15.
The embodiment 9 of nonaqueous electrolytic solution 6
In addition to two lithium of single fluorophosphoric acid for using 0.5 mass %, according to identical with the embodiment 1 of nonaqueous electrolytic solution 6 Method makes non-aqueous electrolyte secondary battery, and carries out the evaluation of battery.As a result as shown in Table 15.
The embodiment 10 of nonaqueous electrolytic solution 6
Under dry argon atmosphere, in the mixture of ethylene carbonate and methyl ethyl carbonate (volume ratio 3:7) dissolving is through filling in Divide dry LiPF6, recorded in table 15 as ring-type di-sulfonyl imides salt annular 1,2- perfluors second di-sulfonyl imides lithium, Difluorophosphate and 1 mass parts vinylene carbonate, make LiPF6Concentration is 1mol/L, ring-type 1,2- perfluor second disulfonyl is sub- The concentration of amination lithium is 0.05mol/L, the concentration of difluorophosphate is 0.5 mass %, prepares desired nonaqueous electrolytic solution, removes Outside this, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The comparative example 1 of nonaqueous electrolytic solution 6
Under dry argon atmosphere, in the mixture of ethylene carbonate and methyl ethyl carbonate (volume ratio 3:7) dissolving is through filling in Divide dry LiPF6, and its concentration is made to prepare nonaqueous electrolytic solution for 1mol/L, in addition, according to nonaqueous electrolytic solution 6 The identical method of embodiment 1 makes non-aqueous electrolyte secondary battery, and carries out the evaluation of battery.As a result as shown in Table 15.
The comparative example 2 of nonaqueous electrolytic solution 6
In addition to the difluorophosphate of 0.5 mass % is not used, according to identical with the embodiment 1 of nonaqueous electrolytic solution 6 Method makes non-aqueous electrolyte secondary battery, carries out the evaluation of battery.As a result as shown in Table 15.
The comparative example 3 of nonaqueous electrolytic solution 6
The annular 1,2- perfluors second di-sulfonyl imides as ring-type di-sulfonyl imides salt except 0.05mol/L is not used Beyond lithium, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
The comparative example 4 of nonaqueous electrolytic solution 6
Under dry argon atmosphere, in the mixture of ethylene carbonate and methyl ethyl carbonate (volume ratio 3:7) dissolving is through filling in Divide dry LiPF6With 1 mass parts vinylene carbonate, and make LiPF6Concentration for 1mol/L, nonaqueous electrolytic solution is prepared, except this Outside, according to the method identical with the embodiment 1 of nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery is made, and carries out battery Evaluation.As a result as shown in Table 15.
[table 15]
If table 15 is understood, contain using the annular di-sulfonyl imides salt represented by containing at least one kind of general formula (8) and also The nonaqueous electrolytic solution of the present invention of mono-fluor phosphate and/or difluorophosphoric acid salt and manufactured non-aqueous electrolyte secondary battery is (non-aqueous The embodiment 10 of 1~nonaqueous electrolytic solution of embodiment 6 of electrolyte 6), with using only containing ring-type two shown at least one kind of general formula (8) Sulfimide salt or manufactured non-aqueous electrolyte secondary battery (the non-water power only containing mono-fluor phosphate and/or difluorophosphoric acid salt Solve the comparative example 2 of liquid 6 and the comparative example 3 of nonaqueous electrolytic solution 6) it compares or is free of both compound (non-water power with using Solve liquid 6 comparative example 1) nonaqueous electrolytic solution and manufactured non-aqueous electrolyte secondary battery is compared, not only can inhibit High temperature storage When expansion, and can inhibit residual capacity and recover the deterioration of battery behavior that capacity is characterized.
In addition, with only contain annular di-sulfonyl imides salt represented by general formula (8) or only containing mono-fluor phosphate and/or The comparative example 2 of the nonaqueous electrolytic solution 6 of difluorophosphoric acid salt and the comparative example 3 of nonaqueous electrolytic solution 6 are compared, and contain above two chemical combination Expansion and inhibition electricity of the embodiment 10 of 1~nonaqueous electrolytic solution of embodiment 6 of the nonaqueous electrolytic solution 6 of object when inhibiting High temperature storage Two aspect of deterioration of pond characteristic is respectively provided with improvement result.In addition, by the embodiment 10 of nonaqueous electrolytic solution 6 and nonaqueous electrolytic solution 6 Comparative example 4 understand, in nonaqueous electrolytic solution during vinylene carbonate containing one of specific carbonic ester, also confirm same Effect.
Industrial applicibility
<Nonaqueous electrolytic solution 1,2, non-aqueous electrolyte secondary battery 1,2>
Nonaqueous electrolytic solution 1,2 using the present invention can inhibit the decomposition of the electrolyte of non-aqueous electrolyte secondary battery, inhibit The deterioration of battery when using battery in high temperature environments, and it is excellent to manufacture preservation characteristics, cycle characteristics with high power capacity The non-aqueous electrolyte secondary battery of high-energy density.Therefore, it is applicable to the electronic equipment using non-aqueous electrolyte secondary battery Etc. in various fields.
<Nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>
Nonaqueous electrolytic solution 3 using the present invention, inhibits gas when can manufacture cycle characteristics, preservation characteristics, trickle charge Generation, the excellent nonaqueous electrolytic solution and non-aqueous electrolyte secondary battery of battery behavior.Therefore, it is applicable to using non-aqueous In the various fields such as the electronic equipment of electrolyte secondary battery.
<Nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>
Using the nonaqueous electrolyte battery 4 of the nonaqueous electrolytic solution 4 of the present invention, since high electricity and security etc. can be kept Also it is excellent, therefore can be used in well known various uses.
<Nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>
Using the non-aqueous electrolyte secondary battery 5 of the nonaqueous electrolytic solution 5 of the present invention, due to that can keep high power capacity, continuously fill Electrical characteristics etc. are also excellent, therefore can be used in well known various uses.
<Nonaqueous electrolytic solution 6, non-aqueous electrolyte secondary battery 6>
Nonaqueous electrolytic solution 6 using the present invention can inhibit decomposition, the suppression of the nonaqueous electrolytic solution of non-aqueous electrolyte secondary battery The deterioration of battery when system uses battery in high temperature environments, and it is excellent to manufacture preservation characteristics, cycle characteristics with high power capacity High-energy density non-aqueous electrolyte secondary battery.Therefore, it is applicable to set using the electronics of non-aqueous electrolyte secondary battery In the various fields such as standby.
The non-aqueous electrolyte for secondary battery 1~6 of the present invention, the purposes of non-aqueous electrolyte secondary battery 1~6 be not special It limits, available for well known various uses.As concrete example, can enumerate, it is laptop, pen control type PC, portable Formula PC, e-book player, mobile phone, portable facsimile printer, portable copier, portable printer, stereo ear Machine, video camera, LCD TV, portable type cleaner, portable CD, minidisk, portable wireless walkie-talkie, electronic recording Sheet, calculator, storage card, portable recorder, radio, stand-by power supply, motor, automobile, motorcycle, electric bicycle, from Driving, ligthing paraphernalia, toy, game machine, table, lathe, flash lamp, camera etc..
The application is hereby incorporated the full content of following applications based on following Japanese patent applications, is incorporated into this In the prospectus of invention.
Nonaqueous electrolytic solution 1：Japanese Patent Application 2007-116442 (the applyings date:On April 26th, 2007)
Nonaqueous electrolytic solution 2：Japanese Patent Application 2007-116445 (the applyings date:On April 26th, 2007)
Nonaqueous electrolytic solution 3：Japanese Patent Application 2007-116450 (the applyings date:On April 26th, 2007)
Nonaqueous electrolytic solution 4：Japanese Patent Application 2007-111961 (the applyings date:On April 20th, 2007)
Nonaqueous electrolytic solution 5：Japanese Patent Application 2007-099274 (the applyings date:On April 5th, 2007)
Nonaqueous electrolytic solution 6：Japanese Patent Application 2007-111931 (the applyings date:On April 20th, 2007)

Claims (3)

1. a kind of nonaqueous electrolytic solution, is used for non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery has non-aqueous Electrolyte and the cathode and anode that can occlude and release ion, wherein, the nonaqueous electrolytic solution has electrolyte and non-aqueous Agent, the nonaqueous solvents contain the carbonic ester with halogen atom and contain mono-fluor phosphate and/or difluorophosphoric acid salt.
2. a kind of nonaqueous electrolytic solution, which is mainly made of electrolyte with the nonaqueous solvents for dissolving the electrolyte, In, the nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, also containing following compounds：The compound exists It is liquid at 25 DEG C, and dielectric constant is more than 5, viscosity is in below 0.6cP, and with formation containing heteroatomic skeleton Group, it is described not include backbone carbonyl containing heteroatomic skeleton.
3. a kind of non-aqueous electrolyte secondary battery, which contains nonaqueous electrolytic solution and can occlude and put Go out the cathode and anode of lithium ion, wherein, which is the nonaqueous electrolytic solution described in claim 1 or 2.
CN201810132906.7A 2007-04-05 2008-04-04 Non-aqueous electrolyte for secondary battery and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution Pending CN108091826A (en)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
JP2007099274A JP2008258013A (en) 2007-04-05 2007-04-05 Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same
JP099274/07 2007-04-05
JP2007111931A JP2008269979A (en) 2007-04-20 2007-04-20 Nonaqueous electrolyte for secondary battery, and nonaqueous electrolyte secondary battery using the same
JP111961/07 2007-04-20
JP111931/07 2007-04-20
JP2007111961A JP5374827B2 (en) 2007-04-20 2007-04-20 Non-aqueous electrolyte and non-aqueous electrolyte battery
JP116442/07 2007-04-26
JP2007116442A JP5628469B2 (en) 2007-04-26 2007-04-26 Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same
JP2007116445A JP5268016B2 (en) 2007-04-26 2007-04-26 Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same
JP116445/07 2007-04-26
JP116450/07 2007-04-26
JP2007116450A JP5418955B2 (en) 2007-04-26 2007-04-26 Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same
CN200880011461A CN101652894A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte for rechargeable battery, and rechargeable battery with nonaqueous electrolyte

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN200880011461A Division CN101652894A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte for rechargeable battery, and rechargeable battery with nonaqueous electrolyte

Publications (1)

Publication Number Publication Date
CN108091826A true CN108091826A (en) 2018-05-29

Family

ID=39981371

Family Applications (4)

Application Number Title Priority Date Filing Date
CN201710201105.7A Active CN106848406B (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery
CN201911353774.1A Pending CN111048841A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery using same
CN200880011461A Pending CN101652894A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte for rechargeable battery, and rechargeable battery with nonaqueous electrolyte
CN201810132906.7A Pending CN108091826A (en) 2007-04-05 2008-04-04 Non-aqueous electrolyte for secondary battery and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CN201710201105.7A Active CN106848406B (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery
CN201911353774.1A Pending CN111048841A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery using same
CN200880011461A Pending CN101652894A (en) 2007-04-05 2008-04-04 Nonaqueous electrolyte for rechargeable battery, and rechargeable battery with nonaqueous electrolyte

Country Status (2)

Country Link
JP (1) JP2008258013A (en)
CN (4) CN106848406B (en)

Families Citing this family (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5463957B2 (en) * 2010-03-02 2014-04-09 ソニー株式会社 Non-aqueous electrolyte and battery
WO2011136189A1 (en) * 2010-04-26 2011-11-03 三井化学株式会社 Nonaqueous electrolyte solution containing cyclic sulfone compound, and lithium secondary battery
JP5842379B2 (en) * 2010-05-12 2016-01-13 三菱化学株式会社 Non-aqueous electrolyte secondary battery
JP6003036B2 (en) * 2010-09-28 2016-10-05 三菱化学株式会社 Non-aqueous electrolyte secondary battery
CN103608962B (en) * 2011-01-31 2016-10-26 三菱化学株式会社 Non-aqueous electrolyte and the nonaqueous electrolyte secondary battery of this non-aqueous electrolyte of use
WO2012105404A1 (en) * 2011-01-31 2012-08-09 三菱化学株式会社 Non-aqueous electrolytic solution, and non-aqueous electrolyte secondary battery using same
CN105576282B (en) * 2011-02-10 2018-11-06 三菱化学株式会社 Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution
JP5668929B2 (en) * 2011-03-23 2015-02-12 ソニー株式会社 Secondary battery, electronic device, electric tool, electric vehicle and power storage system
EP2755272B1 (en) * 2011-11-16 2018-04-18 LG Chem, Ltd. Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same
CN102569887B (en) * 2012-01-04 2015-05-13 华南师范大学 Non-water system high-voltage electrolyte additive and preparation method of electrolyte
US9130246B2 (en) * 2012-01-11 2015-09-08 Samsung Sdi Co., Ltd. Rechargeable lithium battery having lithium difluorophosphate and a sultone-based compound
US9212290B2 (en) 2012-01-27 2015-12-15 Celanese Acetate Llc Substituted cellulose acetates and uses thereof
US9167830B2 (en) 2012-01-27 2015-10-27 Celanese Acetate Llc Substituted cellulose acetates and uses thereof
US9023757B2 (en) 2012-01-27 2015-05-05 Celanese Acetate Llc Substituted cellulose acetates and uses thereof
CN104737354A (en) * 2012-06-19 2015-06-24 A123系统有限责任公司 Electrolytes including fluorinated solvents for use in electrochemical cells
KR101857930B1 (en) * 2012-06-29 2018-05-14 미쯔비시 케미컬 주식회사 Nonaqueous electrolytic solution and nonaqueous electrolytic solution cell using same
JP2014049294A (en) * 2012-08-31 2014-03-17 Tdk Corp Nonaqueous electrolyte for lithium ion secondary battery and lithium ion secondary battery
JP5678936B2 (en) 2012-09-07 2015-03-04 トヨタ自動車株式会社 Method for producing lithium ion secondary battery
US9090045B2 (en) 2012-09-24 2015-07-28 Celanese Acetate Llc Engineered wood produced with substituted cellulose ester adhesives and methods relating thereto
US9138967B2 (en) 2012-09-24 2015-09-22 Celanese Acetate Llc Wood laminate articles comprising substituted cellulose ester adhesives and methods relating thereto
CN104124470B (en) * 2013-04-25 2017-05-03 中国科学院宁波材料技术与工程研究所 High safety battery electrolyte solution
EP2824750B1 (en) * 2013-07-08 2019-01-30 Samsung SDI Co., Ltd. Silicon-containing compound used in electrolytes for lithium secondary batteries
CN104009255B (en) * 2014-06-24 2017-06-23 东莞市凯欣电池材料有限公司 A kind of nonaqueous electrolytic solution and preparation method thereof and a kind of lithium ion battery
CN106163806B (en) 2014-08-29 2018-01-16 住友化学株式会社 Layered product, distance piece and non-aqueous secondary batteries
CN104617333B (en) * 2015-01-05 2017-10-24 深圳新宙邦科技股份有限公司 A kind of nonaqueous electrolytic solution and lithium rechargeable battery
US9490503B1 (en) * 2015-06-22 2016-11-08 Wildcat Discovery Technologies, Inc. Electrolyte formulations for lithium ion batteries
HUE053993T2 (en) * 2015-10-22 2021-08-30 Daikin Ind Ltd Electrolytic solution, electrochemical device, lithium-ion secondary cell, and module
CN105742710A (en) * 2016-05-03 2016-07-06 深圳市沃特玛电池有限公司 Lithium ion battery electrolyte and lithium ion battery
CN107346831A (en) * 2016-05-04 2017-11-14 上海奇谋能源技术开发有限公司 A kind of method for improving lithium ion battery service life
CN107403958A (en) * 2016-05-19 2017-11-28 宁德新能源科技有限公司 Electrolyte and lithium ion battery
CN107634265A (en) * 2016-07-18 2018-01-26 万向二三股份公司 A kind of high pressure resistant lithium-ion battery electrolytes
JP7003394B2 (en) * 2016-09-06 2022-01-20 株式会社村田製作所 Batteries for secondary batteries, secondary batteries, battery packs, electric vehicles, power storage systems, power tools and electronic devices
CN106252639A (en) * 2016-10-17 2016-12-21 广州天赐高新材料股份有限公司 A kind of high-capacity lithium ion cell electrolyte, preparation method and lithium ion battery taking into account high temperature performance
CN106450170A (en) * 2016-10-25 2017-02-22 东莞市联洲知识产权运营管理有限公司 Production method of low-cost and high-quality lithium-ion battery
CN107146911A (en) * 2017-04-10 2017-09-08 珠海市赛纬电子材料股份有限公司 The application of lithium ion battery, nonaqueous lithium ion battery electrolyte and flurosulphonic acid acid anhydride in nonaqueous lithium ion battery electrolyte is prepared
CN107394267B (en) * 2017-07-27 2021-06-25 湛江市金灿灿科技有限公司 Electrolyte and lithium ion battery
FR3070532A1 (en) * 2017-08-22 2019-03-01 Commissariat A L'energie Atomique Et Aux Energies Alternatives ELECTROLYTIC COMPOSITION COMPRISING A PHOSPHAZEN FAMILY ADDITIVE USEFUL FOR SUPERCONDENSATORS
CN113381072A (en) * 2017-12-06 2021-09-10 宁德新能源科技有限公司 Electrolyte and battery containing the same
CN109920978A (en) * 2017-12-13 2019-06-21 上海杉杉科技有限公司 A kind of high-capacity battery of the electrode of silica-base film containing rock-steady structure
CN109935902B (en) * 2017-12-19 2021-10-19 成都大超科技有限公司 Solid electrolyte, lithium battery cell and lithium battery
CN109994778B (en) * 2017-12-29 2021-07-13 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN109994780B (en) * 2017-12-29 2020-12-11 宁德时代新能源科技股份有限公司 Electrolyte and lithium ion battery
CN108808085B (en) * 2018-07-12 2020-09-04 合肥国轩高科动力能源有限公司 Electrolyte for improving heat-resistant uncontrol performance of lithium ion battery
JP2020102309A (en) * 2018-12-20 2020-07-02 古河電池株式会社 Lithium ion secondary battery
CN110336076B (en) * 2019-06-19 2021-08-06 东莞东阳光科研发有限公司 Lithium ion battery electrolyte and lithium ion battery
CN112563572B (en) * 2019-09-26 2022-05-20 杉杉新材料（衢州）有限公司 High-nickel lithium ion battery electrolyte used under high voltage and lithium ion battery
CN112090357A (en) * 2020-11-10 2020-12-18 佛山市兴炬烨科技研究有限公司 Nano-slurry preparation device and preparation method
CN113328140B (en) * 2021-04-30 2022-07-29 惠州锂威新能源科技有限公司 Electrolyte and lithium ion battery containing same
CN113451651A (en) * 2021-07-09 2021-09-28 湖南豪曼新能源科技有限公司 Lithium ion battery electrolyte and lithium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1167270A (en) * 1997-08-21 1999-03-09 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
WO2006043538A1 (en) * 2004-10-19 2006-04-27 Mitsubishi Chemical Corporation Method for producing difluorophosphate, nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery
US20060134528A1 (en) * 2004-12-10 2006-06-22 Masayuki Ihara Battery
WO2006137177A1 (en) * 2005-06-20 2006-12-28 Mitsubishi Chemical Corporation Method for producing difluorophosphate, non-aqueous electrolyte for secondary cell and non-aqueous electrolyte secondary cell

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4000603B2 (en) * 1995-03-07 2007-10-31 旭硝子株式会社 Electric double layer capacitor
JPH08250378A (en) * 1995-03-08 1996-09-27 Mitsubishi Chem Corp Nonaqueous electrolyte for electrochemical capacitor
JPH09245832A (en) * 1996-03-07 1997-09-19 Fuji Elelctrochem Co Ltd Non-aqueous electrolytic liquid
JP4236390B2 (en) * 2001-04-19 2009-03-11 三洋電機株式会社 Lithium secondary battery
JP2002324578A (en) * 2001-04-25 2002-11-08 Mitsubishi Chemicals Corp Nonaqueous electrolyte secondary battery and nonaqueous electrolyte used for it
WO2003077350A1 (en) * 2002-03-08 2003-09-18 Mitsubishi Chemical Corporation Nonaqueous electrolyte and lithium-ion secondary battery containing the same
JP2004139743A (en) * 2002-08-21 2004-05-13 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
US7740986B2 (en) * 2002-09-03 2010-06-22 Quallion Llc Battery having electrolyte with organoborate additive
JP4698126B2 (en) * 2003-02-10 2011-06-08 日本電気株式会社 Non-aqueous electrolyte secondary battery
JP4167103B2 (en) * 2003-03-28 2008-10-15 松下電器産業株式会社 Nonaqueous electrolyte secondary battery
JP2005251738A (en) * 2004-02-03 2005-09-15 Toshiba Corp Nonaqueous electrolyte secondary battery and manufacturing method for nonaqueous electrolyte secondary battery
JP4284541B2 (en) * 2004-12-14 2009-06-24 ソニー株式会社 Secondary battery
KR101213286B1 (en) * 2004-12-16 2012-12-17 유시카고 아르곤, 엘엘씨 Long life lithium batteries with stabilized electrodes
JP2006286351A (en) * 2005-03-31 2006-10-19 Sumitomo Bakelite Co Ltd Lithium ion conductive electrolyte, composition for the same, its manufacturing method, and secondary battery
JP5055710B2 (en) * 2005-04-13 2012-10-24 ソニー株式会社 Secondary battery electrolyte, secondary battery and electronic equipment
JP2006351337A (en) * 2005-06-15 2006-12-28 Mitsubishi Chemicals Corp Lithium secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1167270A (en) * 1997-08-21 1999-03-09 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
WO2006043538A1 (en) * 2004-10-19 2006-04-27 Mitsubishi Chemical Corporation Method for producing difluorophosphate, nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery
US20060134528A1 (en) * 2004-12-10 2006-06-22 Masayuki Ihara Battery
WO2006137177A1 (en) * 2005-06-20 2006-12-28 Mitsubishi Chemical Corporation Method for producing difluorophosphate, non-aqueous electrolyte for secondary cell and non-aqueous electrolyte secondary cell

Also Published As

Publication number Publication date
CN106848406B (en) 2020-09-11
CN106848406A (en) 2017-06-13
CN111048841A (en) 2020-04-21
CN101652894A (en) 2010-02-17
JP2008258013A (en) 2008-10-23

Similar Documents

Publication Publication Date Title
CN102569893B (en) Non-aqueous electrolyte for secondary battery and use the rechargeable nonaqueous electrolytic battery of this nonaqueous electrolytic solution
CN108091826A (en) Non-aqueous electrolyte for secondary battery and the non-aqueous electrolyte secondary battery using the nonaqueous electrolytic solution
CN104167564B (en) Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery
CN105580189B (en) Nonaqueous electrolytic solution and the nonaqueous electrolyte battery using the nonaqueous electrolytic solution
CN104966849B (en) Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution
CN105576282B (en) Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution
CN102036912B (en) Method for producing difluorophosphate, nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery
CN104584309B (en) Non-aqueous electrolyte and the nonaqueous electrolyte secondary battery using the non-aqueous electrolyte
KR101690843B1 (en) Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery employing the same
CN110233290A (en) Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution
US11302966B2 (en) Amine borate compound containing nonaqueous electrolytic solution and power storage device
CN107658494A (en) Non-aqueous electrolyte and nonaqueous electrolyte secondary battery
CN107210486B (en) Non-aqueous electrolyte and the nonaqueous electrolyte secondary battery for using the electrolyte
CN104025366A (en) Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery
CN110495042A (en) Electrolyte solution for lithium ion secondary battery, lithium ion secondary battery and component
CN104221205B (en) Nonaqueous electrolytic solution and nonaqueous electrolyte battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20210107

Address after: Tokyo, Japan

Applicant after: MITSUBISHI CHEMICAL Corp.

Applicant after: Mu electrolyte Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: MITSUBISHI CHEMICAL Corp.

TA01 Transfer of patent application right
RJ01 Rejection of invention patent application after publication

Application publication date: 20180529

RJ01 Rejection of invention patent application after publication