CN103975474A - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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Publication number
CN103975474A
CN103975474A CN201280059747.3A CN201280059747A CN103975474A CN 103975474 A CN103975474 A CN 103975474A CN 201280059747 A CN201280059747 A CN 201280059747A CN 103975474 A CN103975474 A CN 103975474A
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secondary battery
lithium secondary
nonaqueous electrolyte
aforementioned
battery
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中村佑介
上剃春树
木部昌明
山田将之
御书至
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Maxell Holdings Ltd
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Hitachi Maxell Ltd
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Priority to CN201810161796.7A priority Critical patent/CN108199035B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

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

Abstract

Provided is a lithium secondary battery which can be stably used even if the lithium secondary battery is continuously charged at a high voltage of 4.3 V or more. The above-mentioned problem is solved by a lithium secondary battery which is provided with: a positive electrode which contains a lithium nickel complex oxide that is represented by general composition formula Li1+yNi1-a-b-cCoaMnbM1 cO2 (wherein M1 represents at least one element that is selected from the group consisting of Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, W, B, P and Bi; -0.15 <= y <= 0.15; 0.05 <= a <= 0.3; 0.05 <= b <= 0.3; 0 <= c <= 0.03 and a + b + c <= 0.5); a negative electrode which contains a material that contains Si and O as constituent elements (provided that if x is the atomic ratio of O to Si, x satisfies 0.5 <= x <= 1.5); a nonaqueous electrolyte which contains a compound that has a nitrile group in each molecule; and a separator.

Description

Lithium secondary battery
Technical field
Carry out constantly trickle charge, the lithium secondary battery that also can stably use even if the present invention relates to high voltage more than 4.3V.
Background technology
In recent years, practical etc. along with the development of the portable electronic device such as portable phone, subnotebook PC, electric automobile, it is essential that the lithium secondary battery of small-size light-weight and high power capacity has become.
In lithium secondary battery, conventionally in positive active material, use LiCoO 2, LiMnO 2deng lithium-contained composite oxide, and then, taking the high capacity of lithium secondary battery as object, in negative electrode active material, except graphite matter material with carbon element etc., also use and have at SiO in research 2the SiO of the structure of the ultramicron of middle dispersion Si x(for example patent documentation 1～3).
In the high capacity of lithium secondary battery, except using active material capacious, it is also conceivable that the method that improves charging voltage.For example, be widely used now with LiCoO 2in lithium secondary battery for positive active material, generally the higher limit of charging voltage is made as to 4.2V left and right, thereby preceding method is to make charging voltage than the high method that realizes further high capacity of aforementioned value.
In addition, also in the characteristic improvement of carrying out realizing by contain various additives in nonaqueous electrolyte lithium secondary battery.For example, in patent documentation 4, the compound in molecule by containing in nonaqueous electrolyte with more than 2 itrile group disclosed improved the lithium secondary battery of charge/discharge cycle characteristics etc.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-047404 communique
Patent documentation 2: TOHKEMY 2005-259697 communique
Patent documentation 3: TOHKEMY 2008-210618 communique
Patent documentation 4: TOHKEMY 2008-108586 communique
Summary of the invention
Invent problem to be solved
And in portable electronic device, when actual use, sometimes carry out constantly trickle charge, for example, in, placing for a long time, charging use equipment etc. under the state charging.
Under this behaviour in service of carrying out constantly trickle charge, the ion of the transition metal such as Co, Mn from the lithium-contained composite oxide stripping as positive active material to nonaqueous electrolyte, thereby there is the deteriorated of positive active material, damage battery behavior, if the ionic weight of stripping is very many, can there is the internal short-circuit of battery.
According to inventor's etc. research, show that the deteriorated caused problem of these positive active materials that caused by the trickle charge of battery is used SiO in negative electrode active material xthe material of such high power capacity, while making charging voltage higher than charging voltage in the past, can significantly occur.
So, especially in the lithium secondary battery of power supply purposes that is applied to portable electronic device, by with negative electrode active material capacious, when improving charging voltage and realizing high capacity, need to improve the stability while carrying out trickle charge constantly.
The present invention In view of the foregoing makes, and carries out constantly trickle charge, the lithium secondary battery that also can stably use even if its object is to provide with high voltage more than 4.3V.
For solving the method for problem
The lithium secondary battery of the present invention that can realize aforementioned object is characterised in that, possess at the one or both sides of collector body and have the positive pole of the anode mixture layer that contains positive active material, have at the one or both sides of collector body negative pole, nonaqueous electrolyte and the barrier film of the anode mixture layer that contains negative electrode active material, the anode mixture layer of aforementioned positive pole contains composition general formula Li 1+yni 1-a-b-cco amn bm 1 co 2(wherein, M 1for selecting free Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, Sr, W, B, at least a kind of element of the group of P and Bi composition,-0.15≤y≤0.15, 0.05≤a≤0.3, 0.05≤b≤0.3, 0≤c≤0.03 and a+b+c≤0.5) represented lithium nickel composite oxide is as positive active material, the anode mixture layer of aforementioned negative pole contain in component, comprise Si and O material (wherein, O is 0.5≤x≤1.5 with respect to the atomic ratio x of Si) as negative electrode active material, aforementioned nonaqueous electrolyte contains the compound in molecule with itrile group.
The effect of invention
According to the present invention, carry out constantly trickle charge, the lithium secondary battery that also can stably use even if can provide with high voltage more than 4.3V.
Brief description of the drawings
Fig. 1 is the figure that schematically shows an example of lithium secondary battery of the present invention, (a) is its vertical view, is (b) its part sectional arrangement drawing.
Fig. 2 is the stereogram of lithium secondary battery shown in Fig. 1.
Embodiment
As previously mentioned, if use SiO by negative electrode active material in lithium secondary battery x, and by charging voltage be set in 4.3V with on realize high capacity, foregoing carry out trickle charge constantly in the situation that, because the ion of the transition metal from positive active material is to stripping in nonaqueous electrolyte, significantly damage battery behavior.This be considered to due to: negative terminal surface, there is SiO from the ion of the transition metal of positive active material stripping xregioselectivity separate out, thereby caused the most SiO in the capacity of burden negative pole xdeteriorated.
In lithium secondary battery of the present invention, use SiO at negative electrode active material x, especially charging voltage is set in to 4.3V when above, realized the inhibition to stripping in nonaqueous electrolyte at the ion of the foregoing transition metal from positive active material that can occur carry out trickle charge constantly in the situation that, this realizes by following method: the composition that the lithium-contained composite oxide of composition that is difficult to the stripping that these ions occur is contained to the effect with the stripping that suppresses aforementioned ion for positive active material and at nonaqueous electrolyte.Therefore, lithium secondary battery of the present invention is high power capacity, even and if also can stably use to carry out constantly the such method of trickle charge.
As the nonaqueous electrolyte in lithium secondary battery of the present invention, can enumerate the solution (nonaqueous electrolytic solution) for example lithium salts being dissolved in organic solvent, in aforementioned nonaqueous electrolyte, use and contain the compound in molecule with itrile group.
The compound in molecule with itrile group is adsorbed in anodal surface and forms tunicle in lithium secondary battery, has to be suppressed to charge under high-tension state the function to the stripping of nonaqueous electrolyte from the ion of the transition metal of positive active material.Therefore, lithium secondary battery of the present invention, the aforementioned effect being obtained by the compound in molecule with itrile group acts synergistically with the effect that the use that is difficult to the positive active material that stripping occurs by the ion of transition metal described later obtains, thereby, even if carry out constantly continuous high-voltage charge, also can stably use.
In addition, in molecule, there is the compound of itrile group by forming tunicle on anodal surface, can suppress anodal and contact with the direct of nonaqueous electrolyte, therefore, can suppress the generation that discharges and recharges the gas that nonaqueous electrolyte composition causes in anodal surperficial decomposition, thus along with battery.Therefore, lithium secondary battery charge/discharge cycle characteristics of the present invention is good, in addition, the cell expansion can also suppress to preserve time, therefore storing property is also good.
As the compound in molecule with itrile group, can enumerate in the dinitrile compound in the mono-nitrile compound in molecule such as with 1 itrile group, molecule with 2 itrile groups, molecule and there are three nitrile compounds of 3 itrile groups etc.Wherein, with regard to aspect aforementioned effect (by the inhibitory action of stripping and the inhibitory action of reacting of positive pole and nonaqueous electrolyte composition of ion that forms the transition metal from positive active material that tunicle obtains on anodal surface) is more good, preferably dinitrile compound (being the compound in molecule with 2 itrile groups), more preferably the represented dinitrile compound of general formula NC-R-CN (wherein, R is the hydrocarbon chain of the straight or branched of carbon number 1～10).In addition more preferably alkylidene chain straight chain shape or that there is side chain of carbon number 1～10 of the R in aforementioned formula.
As the object lesson of mono-nitrile compound, can enumerate such as lauronitrile etc.In addition, as the object lesson of the represented dinitrile compound of aforementioned formula, can enumerate for example malononitrile, succinonitrile, glutaronitrile, adiponitrile, 1,4-dicyano heptane, 1,5-dicyano pentane, 1,6-dicyano hexane, 1,7-dicyano heptane, 2,6-dicyano heptane, 1,8-dicyano octane, 2,7-dicyano octane, 1,9-dicyano nonane, 2,8-dicyano nonane, 1,10-dicyano decane, 1,6-dicyano decane, 2,4-dimethyl-penten dintrile etc., can only use a kind in them, also two or more kinds may be used.Among aforementioned illustrative dinitrile compound, the stronger viewpoint of effect from inhibition from the stripping of the ion of the transition metal of positive active material, more preferably adiponitrile.
In the nonaqueous electrolyte using about battery, in molecule, there is the content of the compound of itrile group, from more effectively bringing into play the viewpoint of the effect being obtained by the use of these compounds, more than being preferably 0.1 quality %, more preferably more than 0.2 quality %.But, if it is too much to have the addition of compound of itrile group in molecule, although the storing property of for example battery further improves, the effect that improves charge/discharge cycle characteristics likely diminishes.Therefore, the content in molecule in the nonaqueous electrolyte that battery uses with the compound of itrile group is preferably below 5.0 quality %, more preferably below 4.0 quality %.
In addition, nonaqueous electrolyte preferably uses the nonaqueous electrolyte that contains the represented phosphoryl acetate compounds of following general formula (1).
[changing 1]
In aforementioned formula (1), R 1, R 2and R 3be the alkyl of the carbon number 1～12 that can be replaced by halogen atom independently of one another, the integer that n is 0～6.
Lithium secondary battery of the present invention uses SiO xas negative electrode active material, in such battery, due to the SiO by causing along with the change in volume discharging and recharging xthe pulverizing of particle, highly active Si exposes (about SiO xthe details of structure, aftermentioned), it decomposes nonaqueous electrolyte, therefore, the problem that exists charge/discharge cycle characteristics easily to reduce.
The represented phosphoryl acetate compounds of aforementioned formula (1) has the function that forms tunicle in negative terminal surface, even due to the change in volume SiO along with discharging and recharging xparticle pulverize and produced newborn face, also can be by its coating well.Therefore, utilize this tunicle, can highly suppress reacting of negative electrode active material and nonaqueous electrolyte.
In addition, the represented phosphoryl acetate compounds of aforementioned formula (1) also has the effect of the expansion that suppresses lithium secondary battery.Therefore; also contain the nonaqueous electrolyte of the represented phosphoryl acetate compounds of aforementioned formula (1) in the case of using; this effect and collaborative the having an effect of effect being obtained by the compound in molecule with itrile group, can further improve the storing property of lithium secondary battery.
In aforementioned formula (1), R 1, R 2and R 3be the alkyl (for example, alkyl, thiazolinyl, alkynyl etc.) of the carbon number 1～12 that can be replaced by halogen atom independently of one another, the integer that n is 0～6.Be aforementioned R 1, R 2and R 3can be different, also can be more than 2 identical.
As the object lesson of the represented phosphoryl acetate compounds of aforementioned formula (1), can enumerate for example following compound.
The compound of n=0 in aforementioned formula (1): trimethyl phosphoryl methyl esters, methyl diethyl phosphoryl methyl esters, methyl dipropyl phosphoryl methyl esters, methyl dibutyl phosphoryl methyl esters, triethyl phosphine acyl group methyl esters, ethyl solutions of dimethyl phosphoryl base methyl esters, ethyl dipropyl phosphoryl methyl esters, ethyl dibutyl phosphoryl methyl esters, tripropyl phosphoryl methyl esters, propyl-dimethyl phosphoryl methyl esters, propyl group diethyl phosphoryl methyl esters, propyl group dibutyl phosphoryl methyl esters, tributyl phosphoryl methyl esters, butyl solutions of dimethyl phosphoryl base methyl esters, butyl diethyl phosphoryl methyl esters, butyl dipropyl phosphoryl methyl esters, methyl two (2, 2, 2-trifluoroethyl) phosphoryl methyl esters, ethyl two (2, 2, 2-trifluoroethyl) phosphoryl methyl esters, propyl group two (2, 2, 2-trifluoroethyl) phosphoryl methyl esters, butyl two (2, 2, 2-trifluoroethyl) phosphoryl methyl esters etc.
The compound of n=1 in aforementioned formula (1): trimethyl phosphoryl acetic acid esters, methyl diethyl phosphoryl acetic acid esters, methyl dipropyl phosphoryl acetic acid esters, methyl dibutyl phosphoryl acetic acid esters, triethyl phosphine acyl acetic acid ester, ethyl solutions of dimethyl phosphoryl yl acetate, ethyl dipropyl phosphoryl acetic acid esters, ethyl dibutyl phosphoryl acetic acid esters, tripropyl phosphoryl acetic acid esters, propyl-dimethyl phosphoryl acetic acid esters, propyl group diethyl phosphoryl acetic acid esters, propyl group dibutyl phosphoryl acetic acid esters, tributyl phosphoryl acetic acid esters, butyl solutions of dimethyl phosphoryl yl acetate, butyl diethyl phosphoryl acetic acid esters, butyl dipropyl phosphoryl acetic acid esters, methyl two (2,2,2-trifluoroethyl) phosphoryl acetic acid esters, ethyl two (2,2,2-trifluoroethyl) phosphoryl acetic acid esters, propyl group two (2,2,2-trifluoroethyl) phosphoryl acetic acid esters, butyl two (2,2,2-trifluoroethyl) phosphoryl acetic acid esters, allyl dimethyl base phosphoryl acetic acid esters, pi-allyl diethyl phosphoryl acetic acid esters, 2-propynyl solutions of dimethyl phosphoryl yl acetate, 2-propynyl diethyl phosphoryl acetic acid esters etc.
The compound of n=2 in aforementioned formula (1): trimethyl 3-phosphoryl propionic ester, methyl 3-(diethyl phosphoryl) propionic ester, methyl 3-(dipropyl phosphoryl) propionic ester, methyl 3-(dibutyl phosphoryl) propionic ester, triethyl group 3-phosphoryl propionic ester, ethyl 3-(solutions of dimethyl phosphoryl base) propionic ester, ethyl 3-(dipropyl phosphoryl) propionic ester, ethyl 3-(dibutyl phosphoryl) propionic ester, tripropyl 3-phosphoryl propionic ester, propyl group 3-(solutions of dimethyl phosphoryl base) propionic ester, propyl group 3-(diethyl phosphoryl) propionic ester, propyl group 3-(dibutyl phosphoryl) propionic ester, tributyl 3-phosphoryl propionic ester, butyl 3-(solutions of dimethyl phosphoryl base) propionic ester, butyl 3-(diethyl phosphoryl) propionic ester, butyl 3-(dipropyl phosphoryl) propionic ester, methyl 3-(two (2,2,2-trifluoroethyl) phosphoryl) propionic ester, ethyl 3-(two (2,2,2-trifluoroethyl) phosphoryl) propionic ester, propyl group 3-(two (2,2,2-trifluoroethyl) phosphoryl) propionic ester, butyl 3-(two (2,2,2-trifluoroethyl) phosphoryl) propionic ester etc.
The compound of n=3 in aforementioned formula (1): trimethyl 4-phosphoryl butyrate, methyl 4-(diethyl phosphoryl) butyrate, methyl 4-(dipropyl phosphoryl) butyrate, methyl 4-(dibutyl phosphoryl) butyrate, triethyl group 4-phosphoryl butyrate, ethyl 4-(solutions of dimethyl phosphoryl base) butyrate, ethyl 4-(dipropyl phosphoryl) butyrate, ethyl 4-(dibutyl phosphoryl) butyrate, tripropyl 4-phosphoryl butyrate, propyl group 4-(solutions of dimethyl phosphoryl base) butyrate, propyl group 4-(diethyl phosphoryl) butyrate, propyl group dibutyl phosphoryl) butyrate, tributyl 4-phosphoryl butyrate, butyl 4-(solutions of dimethyl phosphoryl base) butyrate, butyl 4-(diethyl phosphoryl) butyrate, butyl 4-(dipropyl phosphoryl) butyrate etc.
Among aforementioned illustrative phosphoryl acetate compounds, particularly preferably 2-propynyl diethyl phosphoryl acetic acid esters (PDPA), ethyl diethyl phosphoryl acetic acid esters (EDPA).
The content of the represented phosphoryl acetate compounds of aforementioned formula (1) in the nonaqueous electrolyte using about lithium secondary battery; from guaranteeing better to use the viewpoint of its effect of bringing; more than being preferably 0.5 quality %, more preferably more than 1.0 quality %.But, if the content of the represented phosphoryl acetate compounds of aforementioned formula (1) is too much in nonaqueous electrolyte, the effect that improves the charge/discharge cycle characteristics of battery likely diminishes.Therefore, the content of the represented phosphoryl acetate compounds of aforementioned formula in the nonaqueous electrolyte that lithium secondary battery uses (1) is preferably below 30 quality %, more preferably below 5.0 quality %.
Infer the R in the aforementioned formula (1) of the aforementioned phosphoryl acetate compounds of expression 1, R 2and R 3in any situation that comprises unsaturated bond under, in negative terminal surface, occur thereby carbon-to-carbon double bond or carbon-to-carbon triple bond are opened polymerization form epithelium.The ingredient (composition polymer) of the epithelium that formed is in this case taking soft carbon-carbon bond as main chain, and therefore, flexibility is high.In the time that lithium secondary battery is discharged and recharged, follow this to discharge and recharge, negative electrode active material expands, shrinks, and therefore, also there is change in volume in negative pole (anode mixture layer) entirety.; be formed with the epithelium from phosphoryl acetate compounds on negative pole (anode mixture layer) surface; as previously mentioned; this epithelium is rich in flexibility, therefore, follows the change in volume that discharge and recharge of negative pole along with battery; be difficult to rupture, be full of cracks etc.; thereby, even if repeatedly carry out discharging and recharging of battery, also can maintain well the aforementioned effect being obtained by the epithelium from phosphoryl acetate compounds.
In addition, nonaqueous electrolyte preferably uses the nonaqueous electrolyte of the cyclic carbonate that also contains halogen replacement.The cyclic carbonate that halogen replaces plays a role at negative pole, has the effect of reacting that suppresses negative pole and nonaqueous electrolyte composition.Therefore,, by using the nonaqueous electrolyte of the cyclic carbonate that also contains halogen replacement, can make the better lithium secondary battery of charge/discharge cycle characteristics.
The cyclic carbonate replacing as halogen, can use the represented compound of following general formula (2).
[changing 2]
In aforementioned formula (2), R 4, R 5, R 6and R 7the alkyl that represents hydrogen, halogen element or carbon number 1～10, part or all of the hydrogen of alkyl can be replaced by halogen element, R 4, R 5, R 6and R 7in at least 1 be halogen element, R 4, R 5, R 6and R 7can be different, also can be more than 2 identical.R 4, R 5, R 6and R 7in situation for alkyl, its carbon number is more few better.As aforementioned halogen element, particularly preferably fluorine.
Among the cyclic carbonate being replaced by halogen element like this, particularly preferably 4-fluoro-1,3-dioxolan-2-one (FEC).
The content of the cyclic carbonate that in the nonaqueous electrolyte using about lithium secondary battery, halogen replaces, from guaranteeing better to use the viewpoint of its effect of bringing, more than being preferably 0.1 quality %, more preferably more than 0.5 quality %.But, if the content of the cyclic carbonate that in nonaqueous electrolyte, halogen replaces is too much, the effect that improves storing property likely diminishes.Therefore, the content of the cyclic carbonate that in the nonaqueous electrolyte that lithium secondary battery uses, halogen replaces is preferably below 10 quality %, more preferably below 5 quality %.
And then nonaqueous electrolyte preferably uses the nonaqueous electrolyte that also contains vinylene carbonate (VC).VC anticathode (especially using the negative pole of material with carbon element as negative electrode active material) plays a role, and has the effect of reacting that suppresses negative pole and nonaqueous electrolyte composition.Therefore,, by using the nonaqueous electrolyte that also contains VC, can make the better lithium secondary battery of charge/discharge cycle characteristics.
The content of VC in the nonaqueous electrolyte using about lithium secondary battery, from guaranteeing better to use the viewpoint of its effect of bringing, more than being preferably 0.1 quality %, more preferably more than 1.0 quality %.But, if the content of VC is too much in nonaqueous electrolyte, the effect that improves storing property likely diminishes.Therefore, in the nonaqueous electrolyte that lithium secondary battery uses, the content of VC is preferably below 10 quality %, more preferably below 4.0 quality %.
As nonaqueous electrolyte lithium salts used, form Li as long as dissociating in solvent +ion and the lithium salts that is difficult to the side reactions such as generation decomposition in the voltage range using as battery, be just not particularly limited.Can use for example LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6deng inorganic lithium salt, LiCF 3sO 3, LiCF 3cO 2, Li 2c 2f 4(SO 3) 2, LiN (CF 3sO 2) 2, LiC (CF 3sO 2) 3, LiC nf 2n+1sO 3(n≤2), LiN (RfOSO 2) 2organic lithium salts such as (here, Rf are fluoroalkyl) etc.
Concentration as this lithium salts in nonaqueous electrolyte, is preferably made as 0.5～1.5mol/l, is more preferably made as 0.9～1.25mol/l.
As nonaqueous electrolyte organic solvent used, as long as making aforementioned lithium salts dissolve and not occur the organic solvent of the side reactions such as decomposition in the voltage range using as battery, be just not particularly limited.For example can enumerate: the cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, the linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, the chain esters such as methyl propionate, the cyclic esters such as gamma-butyrolacton, dimethoxy-ethane, ether, 1, the cyclic ethers such as chain ether diox, oxolane, 2-methyltetrahydrofuran such as 3-dioxolanes, diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether, the sulfurous esters such as glycol sulfite ester etc., they also can mix two or more and use.In addition, in order to make the better battery of characteristic, the mixed solvent of preferred compositions use ethylene carbonate and linear carbonate etc. can obtain the solvent of high conductivity.
In addition, for further improving charge/discharge cycle characteristics, improving the object of high-temperature storage, the fail safes such as preventing of overcharging, in the nonaqueous electrolyte using at lithium secondary battery, also can suitably add the acid of acid anhydrides (No water), the additive (also comprising their derivative) such as sulphonic acid ester, PS, diphenyl sulfide, cyclohexyl benzene, biphenyl, fluorobenzene, tert-butyl benzene.
And then in the nonaqueous electrolyte of lithium secondary battery, aforementioned nonaqueous electrolyte (nonaqueous electrolytic solution) also can use known gelating agents such as adding polymer and the nonaqueous electrolyte (gel-like electrolyte) of gelation.
Positive pole in lithium secondary battery of the present invention uses the electrode of following structure: have the anode mixture layer that contains positive active material, adhesive and conductive auxiliary agent etc. at the one or both sides of collector body.
Positive active material uses composition general formula Li 1+yni 1-a-b-cco amn bm 1 co 2(wherein, M 1for selecting at least a kind of element of group of free Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, W, B, P and Bi composition ,-0.15≤y≤0.15,0.05≤a≤0.3,0.05≤b≤0.3,0≤c≤0.03 and a+b+c≤0.5) represented lithium nickel composite oxide (a).
Lithium nickel composite oxide (a), except being high power capacity, is also difficult to occur the stripping of metal ion in nonaqueous electrolyte in battery, and in addition, thermal stability is also high.Therefore, in the molecule that the effect being obtained by lithium nickel composite oxide (a) and nonaqueous electrolyte comprise, there is collaborative the having an effect of effect of the compound of itrile group, thereby lithium secondary battery of the present invention is high power capacity, even and if by carrying out constantly the such method of trickle charge, also can stably use.In addition,, by the use of lithium nickel composite oxide (a), can also improve charge/discharge cycle characteristics, high-temperature storage characteristic, part throttle characteristics, the fail safe of battery.
In lithium nickel composite oxide (a), Ni is the composition that contributes to the capacity that improves lithium nickel composite oxide (b).
In lithium nickel composite oxide (a), Co contributes to improve the capacity of lithium nickel composite oxide (a), meanwhile, contributes to improve the packed density of lithium nickel composite oxide in anode mixture layer (a).In addition, Co has suppressed the valence mumber that discharges and recharges middle Mn at battery along with the doping of Li and the variation of dedoping, makes the average valence mumber of Mn be stabilized near the value 4 valencys, also has reversible effect that further raising discharges and recharges.Therefore, from bringing into play better the viewpoint of the aforementioned effect being obtained by Co, represent in the aforementioned component general formula of lithium nickel composite oxide (a), represent that a of the amount of Co more than 0.05, is preferably more than 0.1.
But, if the amount of Co is too much in lithium nickel composite oxide (a), the quantitative change of other elements is few, likely cannot give full play to the effect being obtained by these other elements.Therefore, represent in the aforementioned component general formula of lithium nickel composite oxide (a), represent that a of the amount of Co, below 0.3, is preferably below 0.2.
In lithium nickel composite oxide (a), Mn has the effect of the thermal stability of raising lithium nickel composite oxide (a).Therefore, from bringing into play better the viewpoint of the aforementioned effect being obtained by Mn, represent in the aforementioned component general formula of lithium nickel composite oxide (a), represent that the b of the amount of Mn more than 0.05, is preferably more than 0.1.
But, if the amount of Mn is too much in lithium nickel composite oxide (a), the quantitative change of other elements is few, likely cannot give full play to the effect being obtained by these other elements.Therefore, represent in the aforementioned component formula of lithium nickel composite oxide (a), represent that the b of the amount of Mn, below 0.3, is preferably below 0.2.
About lithium nickel composite oxide (a), except Li, O, Ni, Co and Mn, can also contain at least a kind of element M of the group of selecting free Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, W, B, P and Bi composition 1.But, if the middle element M of lithium nickel composite oxide (a) 1amount too much, the quantitative change of Ni, Co, Mn is few, likely cannot give full play to by they obtain effect.Therefore, represent, in the aforementioned component general formula of lithium nickel composite oxide (a), to represent element M 1the c of amount below 0.03, be preferably below 0.01.In addition, lithium nickel composite oxide (a) can not contain element M 1, in aforementioned component general formula, represent element M 1the c of amount be more than 0.
In addition, represent in the aforementioned component general formula of lithium nickel composite oxide (a), if represent b and the expression element M of the amount of a, the expression Mn of the amount of Co 1the total amount " a+b+c " of c of amount too much, the quantitative change of Ni is few, the capacity of lithium nickel composite oxide (a) likely diminishes.Therefore, aforementioned " a+b+c ", below 0.5, is preferably below 0.3.
That is, represent in the aforementioned component general formula of lithium nickel composite oxide (a), represent that " 1-a-b-c " of the amount of Ni is more than 0.5, be preferably more than 0.6, in addition, from guaranteeing well the viewpoint of the effect being obtained by the interpolation of Co, Mn etc., be, below 0.9, to be preferably below 0.8.
Lithium nickel composite oxide (a) is especially when approaching the composition of stoichiometric proportion, it is large that its real density becomes, become the material with higher energy bulk density, particularly, in aforementioned component formula, preferably be made as-0.15≤y≤0.15, regulate by the value to y by this way, the invertibity when can improving real density and discharging and recharging.
Lithium nickel composite oxide (a) can be manufactured by following method: will containing Li compound (lithium hydroxide etc.), containing Ni compound (nickelous sulfate etc.), containing Co compound (cobaltous sulfate etc.), containing Mn compound (manganese sulfate etc.) and as required contain element M 1compound (oxide, hydroxide, sulfate etc.) mix and this raw mixture burnt till etc.In addition, for the synthetic lithium nickel composite oxide (a) of the purity with higher, preferably will contain Ni, Co, Mn and contain as required element M 1in complex chemical compound (hydroxide, oxide etc.) and other starting compounds (containing Li compound etc.) of multiple element mix and this raw mixture burnt till.
About the firing condition of the raw mixture for the synthesis of lithium nickel composite oxide (a), for example, can be made as 800～1050 DEG C, 1～24 hour, preferably for example,, by being temporarily heated to the temperature lower than firing temperature (250～850 DEG C) and keeping preheating in this temperature, be then warming up to firing temperature reaction is carried out.Be not particularly limited for the pre-warmed time, conventionally, be made as about 0.5～30 hour.In addition, atmosphere while burning till can be made as mixed atmosphere, the oxygen atmosphere etc. of oxygen-containing atmosphere (in atmosphere), non-active gas (argon gas, helium, nitrogen etc.) and oxygen, oxygen concentration (volume reference) is now preferably more than 15%, is preferably more than 18%.
In positive active material, except lithium nickel composite oxide (a), following substances can also be used together with lithium nickel composite oxide (a): LiCoO 2deng lithium and cobalt oxides, LiMnO 2, Li 2mnO 3deng lithium manganese oxide, LiNiO 2deng lithium nickel oxide, LiCo 1-xniO 2etc. the lithium-contained composite oxide of layer structure, LiMn 2o 4, Li 4/3ti 5/3o 4deng the lithium-contained composite oxide of spinel structure, LiFePO 4deng the lithium-contained composite oxide of olivine structural, the oxide (but, except lithium nickel composite oxide (a)) being replaced by various elements taking aforesaid oxides as basic composition etc.
In addition, following substances also can be used together with lithium nickel composite oxide (a): composition general formula Li 1+oco 1-p-qmg pm 2 qo 2(wherein, M 2for selecting at least a kind of element of group of free Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, Sr, W, B, P and Bi composition ,-0.3≤o≤0.3,0.001≤p≤0.1 and 0≤q≤0.1) represented lithium cobalt composite oxide (b).Lithium cobalt composite oxide (b) contains Mg, utilizes its effect, for example, and the LiCoO being widely used with positive active material as lithium secondary battery 2compare, the stability of high-voltage region is high, is difficult to occur metal (being mainly Co) ion to the stripping in nonaqueous electrolyte in battery, and in addition, thermal stability is also high.Therefore, by lithium cobalt composite oxide (b) and lithium nickel composite oxide (a) use in the situation that, even charge with high voltage, stability is also high, can make charge/discharge cycle characteristics, high-temperature storage characteristic, part throttle characteristics, the better lithium secondary battery of fail safe.
In lithium cobalt composite oxide (b), Co is the composition that contributes to the capacity that improves lithium cobalt composite oxide (b).As shown in aforementioned component general formula, lithium cobalt composite oxide (b), except Li, O and Co, also contains Mg and element M 2(also can not contain element M 2), amount p and the element M of Mg for the amount of Co 2amount q represent with " 1-p-q ".About the amount " 1-p-q " of Co in lithium cobalt composite oxide (b), particularly, from improving the viewpoint of its capacity, be preferably more than 0.9, more preferably more than 0.95, in addition, from guaranteeing well the viewpoint of the effect being obtained by the interpolation of Mg etc., be preferably below 0.999, more preferably below 0.05.
In lithium cobalt composite oxide (b), Mg improves the stability of lithium cobalt composite oxide (b) at high-voltage region, there is the effect of the stripping that suppresses metal ion, in addition, also there is the effect of the thermal stability that improves lithium cobalt composite oxide (b).Therefore, from bringing into play better the viewpoint of the aforementioned effect being obtained by Mg, represent in the aforementioned component general formula of lithium cobalt composite oxide (b), represent that the p of the amount of Mg is preferably more than 0.001, more preferably more than 0.002.
But, Mg can not make contributions to the capacity that improves lithium cobalt composite oxide (b), if Mg amount is too much in lithium cobalt composite oxide (b), and the amount of for example Co minimizing, capacity likely can reduce.Therefore, represent in the aforementioned component general formula of lithium cobalt composite oxide (b), represent that the p of the amount of Mg is preferably below 0.1, more preferably below 0.05.
Lithium cobalt composite oxide (b), except Li, O, Co and Mg, can also contain at least a kind of element M of the group of selecting free Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, Sr, W, B, P and Bi composition 2.But, if the middle element M of lithium cobalt composite oxide (b) 2amount too much, the quantitative change of Co, Mg is few, likely cannot give full play to by they obtain effect.Therefore, represent, in the aforementioned component general formula of lithium cobalt composite oxide (b), to represent element M 2the q of amount be preferably below 0.1, more preferably below 0.05.In addition, as previously mentioned, lithium cobalt composite oxide (b) can not contain element M 2, in aforementioned component general formula, represent element M 2the q of amount be more than 0.
Lithium cobalt composite oxide (b) is especially when approaching the composition of stoichiometric proportion, it is large that its real density becomes, become the material with higher energy bulk density, particularly, in aforementioned component formula, preferably be made as-0.3≤o≤0.3, regulate by the value to o by this way, the invertibity when can improving real density and discharging and recharging.
Lithium cobalt composite oxide (b) can be synthetic by following method: will containing Li compound (lithium hydroxide etc.), containing Co compound (cobaltous sulfate etc.), contain Mg compound (magnesium sulfate etc.) and as required contain element M 2compound (oxide, hydroxide, sulfate etc.) mix and this raw mixture burnt till etc.In addition, for the synthetic lithium cobalt composite oxide (b) of the purity with higher, preferably will contain Co and Mg, further contain as required element M 2complex chemical compound (hydroxide, oxide etc.) with mix and this raw mixture burnt till containing Li compound etc.
About the firing condition of the raw mixture for the synthesis of lithium cobalt composite oxide (b), also with the situation of lithium nickel composite oxide (a) similarly, for example, can be made as 800～1050 DEG C, 1～24 hour, preferably for example,, by being temporarily heated to the temperature lower than firing temperature (250～850 DEG C) and keeping preheating in this temperature, be then warming up to firing temperature reaction is carried out.Be not particularly limited for the pre-warmed time, conventionally, be made as about 0.5～30 hour.In addition, atmosphere while burning till can be made as mixed atmosphere, the oxygen atmosphere etc. of oxygen-containing atmosphere (in atmosphere), non-active gas (argon gas, helium, nitrogen etc.) and oxygen, oxygen concentration (volume reference) is now preferably more than 15%, is preferably more than 18%.
The in the situation that of at positive active material and with lithium nickel composite oxide (a) and other positive active materials, other positive active materials more preferably use lithium cobalt composite oxide (b).
The in the situation that of at positive active material and for example, with lithium nickel composite oxide (a) and other positive active materials (lithium cobalt composite oxide (b)), from guaranteeing better to use the viewpoint of the effect that lithium nickel composite oxide (a) obtains, more than preferably the content of lithium nickel composite oxide (a) in positive active material total amount being made as to 10 quality %.
In addition, the in the situation that of at positive active material and with lithium nickel composite oxide (a) and lithium cobalt composite oxide (b), preferably the content of lithium nickel composite oxide (a) in positive active material total amount is made as to 80 quality % following (, more than the content of lithium cobalt composite oxide (b) in positive active material total amount is made as to 20 quality %).
Adhesive in anode mixture layer can suitably use such as Kynoar (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc.In addition, as the conductive auxiliary agent in anode mixture layer, can enumerate following material with carbon element etc.: the graphite (graphite matter material with carbon element) such as such as native graphite (flaky graphite etc.), Delanium, the carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, dim, thermal black, carbon fiber etc.
Positive pole can be manufactured through following operation: for example, the composition that contains anode mixture that positive active material, adhesive and conductive auxiliary agent etc. are dispersed in pasty state in METHYLPYRROLIDONE (NMP) equal solvent, pulpous state by modulation (wherein, adhesive also can be dissolved in solvent), after being coated on the one or both sides of collector body and making it dry, implement as required calender process.But, positive pole should not be understood to be defined in the electrode of manufacturing by aforementioned manufacture method, can be the electrode of manufacturing by additive method yet.
In addition, also can on positive pole, be formed for as required the lead-in wire body that is electrically connected with the miscellaneous part in lithium secondary battery according to conventional method.
The thickness of anode mixture layer is for example preferably every 10～100 μ m of collector body.
In addition, as the composition of anode mixture layer, for example, the amount of positive active material is preferably 60～95 quality %, and the amount of adhesive is preferably 1～15 quality %, and the amount of conductive auxiliary agent is preferably 3～20 quality %.
Anodal collector body can use the same collector body of collector body using with the positive pole of in the past known lithium secondary battery, for example, is preferably the aluminium foil of thickness 10～30 μ m.
Negative pole in lithium secondary battery of the present invention for example uses the electrode at the one or both sides of collector body with the structure of the anode mixture layer that contains negative electrode active material, adhesive etc.And the negative electrode active material in negative pole uses SiO x.
SiO xcan comprise crystallite or the amorphous phase of Si, in this case, the atomic ratio of Si and O becomes the ratio that comprises the crystallite of Si or the Si of amorphous phase.Be SiO xbe included in amorphous SiO 2in matrix, be dispersed with the material of the structure of Si (for example crystallite Si), this amorphous SiO 2be scattered in Si wherein and add up that to meet aforementioned atomic ratio x be 0.5≤x≤1.5.For example,, with amorphous SiO 2in matrix, be dispersed with structure, the SiO of Si 2in the situation of the mol ratio of the Si material that is 1:1, x=1, as structural formula, represents with SiO.In the case of the material of this structure, for example, sometimes in X-ray diffraction analysis, do not observe the peak being caused by the existence of Si (crystallite Si), if but observe with transmission electron microscope, can confirm the existence of fine Si.
And, SiO xbe preferably and the complex of material with carbon element Composite, for example, preferably SiO xsurface by material with carbon element coating.As previously mentioned, SiO xlack conductivity, therefore, in the time using using this as negative electrode active material, from guaranteeing the viewpoint of good battery behavior, need to use conductive material (conductive auxiliary agent), make SiO in negative pole xwith the mixing of conductive material, good dispersion, thereby form excellent conductive network.If by SiO xwith the complex of material with carbon element Composite, for example, with use only by SiO xcompared with the situation of the material being obtained by mixing with conductive materials such as material with carbon elements, in negative pole, form better conductive network.
As SiO xwith the complex of material with carbon element, except aforementioned that SiO xsurface by beyond the complex of material with carbon element coating, can also enumerate SiO xwith granulation body of material with carbon element etc.
In addition, SiO aforesaid by making, xsurface further used with conductive material (material with carbon element etc.) Composite by the complex of material with carbon element coating, can in negative pole, form better conductive network, therefore, can realize more high power capacity and the more excellent lithium secondary battery of battery behavior (for example charge/discharge cycle characteristics).As by the SiO of material with carbon element coating xwith the complex of material with carbon element, for example can enumerate by the SiO of material with carbon element coating xthe granulation body obtaining with the further granulation of mixture of material with carbon element etc.
In addition, as surface by the SiO of material with carbon element coating x, can preferably use SiO xthe material for example, further being formed by material with carbon element coating than the surface of the complex of its little material with carbon element (granulation body) with resistivity.If aforementioned granulation body inside is SiO xstate with material with carbon element disperses, can form better conductive network, therefore, has the SiO of containing xin lithium secondary battery as the negative pole of negative electrode active material, can further improve the battery behaviors such as heavy load flash-over characteristic.
As can for SiO xform the aforementioned material with carbon element of complex, can enumerate the material with carbon elements such as such as low-crystalline carbon, carbon nano-tube, gas-phase growth of carbon fibre as preferred material.
As the details of aforementioned material with carbon element, be preferably at least a kind of material of the choosing group that freely fibrous or spiral helicine material with carbon element, carbon black (comprising acetylene black, Ketjen black), Delanium, easy graphitized carbon and difficult graphitized carbon form.Fibrous or spiral helicine material with carbon element is preferred from easy formation conductive network and surface area broad aspect.Carbon black (comprising acetylene black, Ketjen black), easily graphitized carbon and difficult graphitized carbon have high conductivity, the high fluidity of protecting, even and if then also have a SiO xparticle dilation also easily keeps the character contacting with this particle, is preferred with regard to this respect.
In addition, details as described later, in the present invention preferably using graphite matter material with carbon element and SiO as negative electrode active material xuse together, also can be using this graphite matter material with carbon element as SiO xuse with the material with carbon element in the complex of material with carbon element.Graphite matter material with carbon element also with carbon black etc. similarly, there is high conductivity, the high fluidity of protecting, even and if then also there is SiO xparticle dilation also easily keeps and the character contacting of this particle, therefore, can with SiO xthe formation of complex in preferably use.
Among aforementioned illustrative material with carbon element, as with SiO xcomplex be material with carbon element used in the situation of granulation body, particularly preferably fibrous material with carbon element.This be because, fibrous material with carbon element is because it is shaped as filament shape, flexibility is high, therefore can follow SiO xalong with the dilation discharging and recharging of battery, in addition, bulk density is large, therefore, can with SiO xparticle has more junction point.As fibrous carbon, can enumerate such as polyacrylonitrile (PAN) based carbon fiber, pitch-based carbon fiber, gas-phase growth of carbon fibre, carbon nano-tube etc., can use the arbitrary substance in them.
In addition, about fibrous material with carbon element, for example, can also utilize vapor phase method at SiO xthe surface of particle forms.
SiO xresistivity be generally 10 3～10 7k Ω cm, and the resistivity of aforementioned illustrative material with carbon element is generally 10 -5～10k Ω cm.
In addition SiO, xcan also further there is with the complex of material with carbon element the material layer (material layer that comprises difficult graphitized carbon) of material with carbon element coating that covers particle surface.
Use SiO at negative pole xin the situation of the complex of material with carbon element, about SiO xwith the ratio of material with carbon element, from bringing into play well the viewpoint by the effect obtaining with the Composite of material with carbon element, with respect to SiO x100 mass parts, more than material with carbon element is preferably 5 mass parts, more preferably more than 10 mass parts.In addition, in aforementioned complex, and if SiO xthe ratio of the material with carbon element of Composite is too much, can cause SiO in anode mixture layer xthe reduction of amount, the effect of high capacity likely diminishes, therefore, with respect to SiO x100 mass parts, material with carbon element is preferably below 50 mass parts, more preferably below 40 mass parts.
Aforesaid SiO xcan obtain as described below by example with the complex of material with carbon element.
First, to making SiO xmanufacture method in the situation of Composite describes.Prepare SiO xthe dispersion liquid disperseing in decentralized medium and sprayed dry, thereby make the compound particle that contains multiple particles.As decentralized medium, can use such as ethanol etc.The spraying of dispersion liquid is suitable conventionally in the atmosphere of 50～300 DEG C.Except preceding method, use in the prilling process of mechanical methods of ball mill, the rod mill etc. of oscillating mode, planet-shaped in utilization, also can make same compound particle.
In addition, manufacturing SiO xcompare SiO with resistivity xin the situation of the granulation body of little material with carbon element, at SiO xin the dispersion liquid disperseing, add aforementioned material with carbon element in decentralized medium, use this dispersion liquid, by with make SiO xthe same method of situation of Composite is made compound particle (granulation body).In addition, utilize the prilling process using with aforementioned same mechanical methods, also can make SiO xgranulation body with material with carbon element.
Then, by SiO xparticle (SiO xcompound particle or SiO xgranulation body with material with carbon element) surface make with material with carbon element coating in the situation of complex, for example, by SiO xparticle and hydrocarbon system gas heat in gas phase, thereby make the coke build-up being produced by the thermal decomposition of hydrocarbon system gas on the surface of particle.In this way, utilize vapor phase growth (CVD) method, hydrocarbon system gas spreads all over each corner of compound particle, can in the emptying aperture on the surface of particle, surface, form to comprise and there is material with carbon element thin of conductivity and uniform epithelium (material with carbon element coating), therefore, can utilize a small amount of material with carbon element have good uniformity to SiO xparticle is given conductivity.
By the SiO of material with carbon element coating xmanufacture in, the treatment temperature (atmosphere temperature) of vapor phase growth (CVD) method is according to the difference of hydrocarbon system gaseous species and difference, common 600～1200 DEG C is suitable, wherein, is preferably more than 700 DEG C, more preferably more than 800 DEG C.This is because treatment temperature height can form the coating that comprises the less residual and carbon that conductivity is high of impurity.
As the fluid supply of hydrocarbon system gas, can use toluene, benzene, dimethylbenzene, mesitylene etc., particularly preferably maneuverable toluene.For example, by being vaporized (, with nitrogen foam), can obtain hydrocarbon system gas.In addition, also can use methane gas, acetylene gas etc.
In addition, also can utilize vapor phase growth (CVD) method by SiO xparticle (SiO xcompound particle or SiO xgranulation body with material with carbon element) surface with material with carbon element cover after, making to select free petroleum pitch, coal is that at least a kind of organic compound of the group of the condensation product composition of pitch, thermosetting resin and naphthalene sulfonate and aldehydes is attached on the coating that comprises material with carbon element, then, the aforementioned particle that is attached with organic compound is burnt till.
Particularly, prepare by the SiO of material with carbon element coating xparticle (SiO xcompound particle or SiO xgranulation body with material with carbon element) and the dispersion liquid that disperses in decentralized medium of aforementioned organic compound by dry this dispersion liquid spraying, thereby form by the particle of organic compound coating, this particle by organic compound coating is burnt till.
As aforementioned pitch, can use isotropic pitch, as thermosetting resin, can use phenolic resins, furane resins, furfural resin etc.As the condensation product of naphthalene sulfonate and aldehydes, can use naphthalene sulfonic acid-formaldehyde condensation product.
As for making by the SiO of material with carbon element coating xthe decentralized medium that particle and aforementioned organic compound disperse, can use such as water, alcohols (ethanol etc.).The spraying of dispersion liquid is suitable conventionally under the atmosphere of 50～300 DEG C.Common 600～1200 DEG C of firing temperature is suitable, wherein, is preferably more than 700 DEG C, more preferably more than 800 DEG C.This is because treatment temperature height can form the coating that comprises the less residual and material with carbon element that conductivity is high, quality is good of impurity.But, treatment temperature need to be at SiO xfusing point below.
The related negative electrode active material of lithium secondary battery of the present invention is preferably by graphite matter material with carbon element and SiO xuse together.Thereby by using graphite matter material with carbon element to reduce SiO in negative electrode active material xratio, suppressed as much as possible by SiO xthe reduction of the high capacity effect that causes of minimizing, and suppressed the change in volume that discharge and recharge of negative pole (anode mixture layer) along with battery, thereby can suppress the reduction of the battery behavior that can occur because of this change in volume.
As with SiO xthe graphite matter material with carbon element using as negative electrode active material together, can enumerate: the native graphites such as such as flaky graphite, by RESEARCH OF PYROCARBON class, carbonaceous mesophase spherules (MCMB), carbon fiber etc. easily graphitized carbon 2800 DEG C carry out graphitization processing above and Delaniums etc.
In addition, in negative pole in the present invention, from guaranteeing well by using SiO xthe viewpoint of the effect of the high capacity obtaining is set out, SiO in negative electrode active material xcontent be preferably 0.01 quality % more than, more preferably more than 3 quality %.In addition, from avoiding better the viewpoint of negative pole along with the problem of the change in volume discharging and recharging, SiO in negative electrode active material xcontent be preferably below 30 quality %, more preferably below 20 quality %.
Adhesive in anode mixture layer can suitably use such as Kynoar (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc.And then, in anode mixture layer, can also add various carbon blacks, carbon nano-tube, the carbon fibers etc. such as acetylene black as conductive auxiliary agent.
Negative pole can be manufactured through following operation: for example, modulation makes negative electrode active material and adhesive, further conductive auxiliary agent is as required dispersed in the composition that contains cathode agent in NMP, water equal solvent (wherein, adhesive also can be dissolved in solvent), after being coated on the one or both sides of collector body and making it dry, implement as required calender process.But, negative pole should not be understood to be defined in the electrode of manufacturing by aforementioned manufacture method, can be the electrode of manufacturing by additive method yet.
About the thickness of anode mixture layer, be preferably every 10～100 μ m of collector body, the density (quality and thickness by the anode mixture layer that is layered in the per unit area on collector body calculate) of anode mixture layer is preferably 1.0～1.9g/cm 3.In addition, as the composition of anode mixture layer, for example, the amount of negative electrode active material is preferably 80～95 quality %, and the amount of adhesive is preferably 1～20 quality %, and in the situation that using conductive auxiliary agent, its amount is preferably 1～10 quality %.
As the collector body of negative pole, can use the paper tinsel of copper, nickel system, die-cut metal, net, extruded metal etc., conventionally use Copper Foil.About this negative electrode collector, make the thin thickness of negative pole entirety at the battery in order to obtain high-energy-density, the upper limit of thickness is preferably 30 μ m, and in order to ensure mechanical strength, lower limit is preferably 5 μ m.
The related barrier film of lithium secondary battery of the present invention preferably has the character (being shut-down function) of its bore closure of (more preferably more than 100 DEG C) (more preferably below 150 DEG C) below 170 DEG C more than 80 DEG C, can use the barrier film using in common lithium secondary battery etc., for example, the micro-porous film of the polyolefin system such as polyethylene (PE), polypropylene (PP).The micro-porous film that forms barrier film can be the micro-porous film that for example only uses the micro-porous film of PE, only uses PP, in addition, can be also the duplexer of the micro-porous film of PE system and the micro-porous film of PP system.
In addition, barrier film in lithium secondary battery of the present invention preferably uses cascade type barrier film, described cascade type barrier film there is the porous layer (I) using fusing point as the resin below 140 DEG C as main body and be included at the temperature below 150 DEG C not can melting resin or the porous layer (II) of heat resisting temperature as more than 150 DEG C inorganic fillers as main body.Herein, " fusing point " meaning is according to the regulation of JIS K7121, the melting temperature of measuring with differential scanning calorimeter (DSC).In addition, " can not melt at the temperature below 150 DEG C " meaning is according to the regulation of JIS K7121, has exceeded at 150 DEG C of grades, temperature in the time measuring aforementioned melting temperature below 150 DEG C and has not shown melting behavior by the melting temperature that DSC measures.And then " heat resisting temperature is more than 150 DEG C " meaning is at least to have no the softening distortion that waits in the time of 150 DEG C.
Porous layer (I) in aforementioned cascade type barrier film is the layer that is mainly used in guaranteeing shut-down function, in the time that lithium secondary battery reaches above as the fusing point of resin of composition of main body that becomes porous layer (I), porous layer (I) thus in resin melting stopped up the emptying aperture of barrier film, there is the shut-down of the carrying out that suppresses electrochemical reaction.
Fusing point as the main body that becomes porous layer (I) is 140 DEG C of following resins, can enumerate for example PE, as its form, can be set forth in the dispersion liquid of the particle that on the aforementioned lithium secondary battery base material such as micro-porous film, nonwoven fabrics used, coating contains PE and make its object dry etc. and that obtain.Herein, in whole constituents of porous layer (I), the fusing point that becomes main body is that the volume of 140 DEG C of following resins is more than 50 volume %, more preferably more than 70 volume %.In addition, for example, in the case of porous layer (I) is formed with the micro-porous film of aforementioned PE, fusing point is that the volume of 140 DEG C of following resins is 100 volume %.
Porous layer (II) in aforementioned cascade type barrier film also can prevent by the direct function that contacts the short circuit causing anodal and negative pole even if possess in the time that the internal temperature of lithium secondary battery rises, utilize at temperature below 150 DEG C not can melting resin or heat resisting temperature be more than 150 DEG C inorganic fillers, guaranteed this function.; in the situation that battery becomes high temperature; even if porous layer (I) shrinks, utilize and be difficult to the porous layer (II) that shrinks, the short circuit that the direct contact by both positive and negative polarity that also can prevent from can having occurred in the situation that thermal contraction has occurred barrier film causes.In addition, this thermal endurance porous layer (II) plays a role as the skeleton of barrier film, therefore, also can suppress the thermal contraction of porous layer (I), i.e. the thermal contraction of barrier film entirety itself.
Form in the situation of porous layer (II) as more than 150 DEG C resins as main body taking fusing point, for example can enumerate: for example, with micro-porous film (the battery micro-porous film of aforementioned PP system) that resin that can melting at the temperature by below 150 DEG C is formed in the upper stacked form of porous layer (I); The dispersion liquid of the particle of resin that can melting at the temperature containing below 150 DEG C etc. is coated on to porous layer (I) and goes up and make it dry, thereby form the form of the coating cascade type of porous layer (II) on the surface of porous layer (I).
As resin that can melting at the temperature below 150 DEG C, can enumerate: PP, the various cross-linked polymer particulates such as crosslinked polymethylmethacrylaparticles, crosslinked polystyrene, crosslinked polydivinylbenezene, styrene diethylene benzene copoly mer cross-linking agent, polyimides, melmac, phenolic resins, benzoguanamine-formaldehyde condensation products, polysulfones, polyether sulfone, polyphenylene sulfide, polytetrafluoroethylene, polyacrylonitrile, aramid fiber, polyacetals etc.
Use at temperature below 150 DEG C not can the resin particle of melting, more than its particle diameter is for example preferably 0.01 μ m in average grain diameter, more preferably more than 0.1 μ m, in addition, be preferably below 10 μ m, more preferably below 2 μ m.In addition, the average grain diameter of the alleged various particles of this specification is: for example, and the average grain diameter D50% for example, in the medium that can not make resin dissolves, these microparticulate being measured with laser light scattering Particle Size Analyzer (hole field makes made " LA-920 ").
In the case of forming porous layer (II) as more than 150 DEG C inorganic fillers as main body taking heat resisting temperature, for example can enumerate by contain heat resisting temperature be the dispersion liquid of 150 DEG C of above inorganic fillers etc. be coated on porous layer (I) thus go up and make the form of the coating cascade type of its dry formation porous layer (II).
Inorganic filler in porous layer (II) as long as nonaqueous electrolyte battery being had for when more than 150 DEG C at heat resisting temperature stable, further in the operating voltage range of battery, be difficult to the inorganic filler of the electrochemical stability of oxidized reduction, from aspects such as dispersions, be preferably particulate, in addition, be preferably aluminium oxide, silicon dioxide, boehmite.Aluminium oxide, silicon dioxide, boehmite oxidative resistance are high, can be by particle diameter, Adjusting Shape to the numerical value of expecting etc., therefore, easily precision is controlled the void content of porous layer (II) well.In addition, heat resisting temperature is that 150 DEG C of above inorganic fillers for example can be used separately a kind of aforementioned illustrative inorganic filler, and also two or more kinds may be used.In addition, by heat resisting temperature be can melting at the inorganic filler of 150 DEG C and aforementioned temperature below 150 DEG C resin and with also harmless.
The shape that is 150 DEG C of above inorganic fillers for the heat resisting temperature in porous layer (II) is not particularly limited, and can use spherical (comprising proper sphere shape) substantially, the inorganic filler of ellipsoid shaped (comprising ellipsoid shaped), the various shapes such as tabular substantially.
In addition, too small if the heat resisting temperature in porous layer (II) is the average grain diameter of 150 DEG C of above inorganic fillers, the permeability of ion can reduce, therefore, and more than being preferably 0.3 μ m, more preferably more than 0.5 μ m.In addition, if heat resisting temperature is that 150 DEG C of above inorganic fillers are excessive, electrical characteristics become easily deteriorated, and therefore, its average grain diameter is preferably below 5 μ m, more preferably below 2 μ m.
In porous layer (II), resin that can melting at temperature below 150 DEG C and heat resisting temperature are that more than 150 DEG C inorganic fillers contains as main body in porous layer (II), therefore, their amounts in porous layer (II) (porous layer (II) only contain at the temperature below 150 DEG C not can melting resin and heat resisting temperature be any one in more than 150 DEG C inorganic fillers, for its amount, in the situation that containing both, it is their total amount.Be the more than 150 DEG C inorganic filler amount in porous layer (II) for resin that can melting at the temperature below 150 DEG C and heat resisting temperature, identical below) in the whole volume of the constituent of porous layer (II), be more than 50 volume %, more than being preferably 70 volume %, more preferably more than 80 volume %, more preferably more than 90 volume %.By the inorganic filler in porous layer (II) is made as to foregoing high-load, even in the time that lithium secondary battery becomes high temperature, also can suppress well the thermal contraction of barrier film entirety, can suppress better by the direct generation that contacts the short circuit causing anodal and negative pole.
In addition, as described later, preferably in porous layer (II), also contain organic bond, therefore, resin that can melting at temperature below 150 DEG C and heat resisting temperature be the more than 150 DEG C inorganic filler amount in porous layer (II) in the whole volume of the constituent of porous layer (II), be preferably below 99.5 volume %.
In porous layer (II), for resin that can melting at the temperature below 150 DEG C or heat resisting temperature, to be bonding each other of more than 150 DEG C inorganic filler, porous layer (II) with porous layer (I) integrated etc., preferably contains organic bond.As organic bond, can enumerate ethylene-vinyl acetate copolymer (EVA, be 20～35 % by mole from the construction unit of vinylacetate), ethylene-acrylic acid copolymer, the fluorine such as ethylene-ethyl acrylate copolymer be rubber, SBR, CMC, carboxyethyl cellulose (HEC), polyvinyl alcohol (PVA), polyvinyl butyral resin (PVB), PVP (PVP), crosslinked acrylic resin, polyurethane, epoxy resin etc., especially preferably uses the thermal endurance adhesive with 150 DEG C of above heat resisting temperatures.Organic bond can use separately a kind of aforementioned illustrative adhesive, and also two or more kinds may be used.
Among aforementioned illustrative organic bond, preferably EVA, ethylene-acrylic acid copolymer, fluorine are the adhesive that the flexibility such as rubber, SBR is high.As the object lesson of the high organic bond of such flexibility, there is " EVAFLEX series (EVA) ", the EVA of Uni-Charm Co., Ltd., " EVAFLEX-EEA series (ethylene-acrylic acid copolymer) ", the EEA of Uni-Charm Co., Ltd., " DAI-EL LATEX series (fluorubber) ", " TRD-2001 (SBR) ", " BM-400B (SBR) " of Nippon Zeon Co., Ltd. etc. of JSR company of Daikin Industries company of polymeric chemical company of Mitsui Du Pont of polymeric chemical company of Mitsui Du Pont.
In addition, by aforementioned organic bond for the porous layer (II) in the situation that, the form that can form the emulsion of the form of dissolving with composition or dispersion in solvent with aftermentioned porous layer (II) is used.
Aforementioned coating cascade type barrier film can be manufactured by following method: for example, the porous layer (II) that is more than 150 DEG C inorganic filler etc. by particle, the heat resisting temperature of resin that can melting at the temperature containing below 150 DEG C forms and is coated on the surface of the micro-porous film for forming porous layer (I) and is dried at the temperature specifying with composition fluid compositions such as (etc.) slurries, thus formation porous layer (II).
Particle and/or heat resisting temperature that porous layer (II) forms resin that can melting under containing the temperature below 150 DEG C with composition are more than 150 DEG C inorganic fillers, also contain as required organic bond etc., they are dispersed in solvent and (comprise decentralized medium.Identical below) in.In addition, organic bond can also be dissolved in solvent.Porous layer (II) can make at the temperature below 150 DEG C not particle, the inorganic filler etc. of resin that can melting disperse equably as long as form with composition solvent used, in addition can make organic bond dissolve equably or disperse, can suitably use the general organic solvents such as ketone such as the furans such as aromatic hydrocarbon, oxolane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) such as such as toluene.In addition, for the object of control surface tension force, in these solvents, also can suitably add the various expoxy propane such as alcohol (ethylene glycol, propylene glycol etc.) or methyl ether acetate is alcohol ether etc.In addition, be in water miscible situation, inferior as the situation of emulsion use at organic bond, can be using water as solvent, now also can suitably add alcohols (methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol etc.) and carry out effects on surface tension force and control.
Porous layer (II) forms and is preferably 150 DEG C of above inorganic fillers by being included at 150 DEG C of following temperature not the particle of resin that can melting and/or heat resisting temperature, further comprises that the solid component content of organic bond etc. is made as for example 10～80 quality % with composition.
In addition, in aforementioned cascade type barrier film, it is respectively 1 layer respectively that porous layer (I) and porous layer (II) there is no need, and also can have multiple layers in barrier film.The two sides that for example, also can be formed in porous layer (II) disposes the formation of porous layer (I) or disposes the formation of porous layer (II) on the two sides of porous layer (I).But, the thickness of barrier film increases along with the increase of the number of plies, likely cause the increase of the internal resistance of battery, the reduction of energy density, thereby preferably not making the number of plies too much, in aforementioned cascade type barrier film, porous layer (I) is preferably below 5 layers with the total number of plies of porous layer (II).
The thickness of the barrier film (barrier film being formed by the micro-porous film of polyolefin system, aforementioned cascade type barrier film) in lithium secondary battery of the present invention is for example preferably 10～30 μ m.
In addition, in aforementioned cascade type barrier film, from more effectively bringing into play the viewpoint of the aforementioned each effect being obtained by porous layer (II), more than the thickness of porous layer (II) (being its gross thickness in the situation that barrier film has multi-layer porous matter layer (II)) is preferably 3 μ m.But, if porous layer (II) is blocked up, likely cause the reduction of the energy density of battery etc., therefore, the thickness of porous layer (II) is preferably below 8 μ m.
And then, in aforementioned cascade type barrier film, from more effectively bringing into play the viewpoint of the aforementioned effect (especially shut-down effect) being obtained by the use of porous layer (I), the thickness of porous layer (I) (is its gross thickness in the situation that barrier film has multi-layer porous matter layer (I).Identical below) be preferably 6 μ m more than, more preferably more than 10 μ m.But, if porous layer (I) is blocked up, likely cause the reduction of the energy density of battery, in addition, cause the power of porous layer (I) thermal contraction to become large, the effect that suppresses the thermal contraction of barrier film entirety likely diminishes.Therefore, the thickness of porous layer (I) is preferably below 25 μ m, more preferably below 20 μ m, more preferably below 14 μ m.
As the void content of barrier film entirety, in order to ensure guarantor's liquid measure of electrolyte and make ion permeability good, under drying regime, be preferably more than 30%.On the other hand, from guaranteeing barrier film intensity and the viewpoint that prevents internal short-circuit, under drying regime, the void content of barrier film is preferably below 70%.In addition, the void content P (%) of barrier film can be by the density of the quality of the thickness of barrier film, unit are, constituent, and following by using (3) formula is obtained about the summation of each component i and calculated.
P＝{1-(m/t)/(Σa i·ρ i)}×100 (3)
Herein, in aforementioned (3) formula, a ifor the quality using overall is as the ratio of 1 o'clock component i, ρ ifor the density (g/cm of component i 3), the quality (g/cm of the per unit area that m is barrier film 2), the thickness (cm) that t is barrier film.
In addition, the in the situation that of aforementioned cascade type barrier film, in aforementioned (3) formula, by m being made as to the quality (g/cm of per unit area of porous layer (I) 2), t is made as to the thickness (cm) of porous layer (I), can also use aforementioned (3) formula to obtain the void content P (%) of porous layer (I).The void content of the porous layer (I) of trying to achieve by the method is preferably 30～70%.
And then, the in the situation that of aforementioned cascade type barrier film, in aforementioned (3) formula, by m being made as to the quality (g/cm of per unit area of porous layer (II) 2), t is made as to the thickness (cm) of porous layer (II), can also use aforementioned (3) formula to obtain the void content P (%) of porous layer (II).The void content of the porous layer (II) of trying to achieve by the method is preferably 20～60%.
As aforementioned barrier film, the barrier film that preferred mechanical intensity is high, for example, more than the intensity that punctures is preferably 3N.For example, alloy, the oxide etc. of Si, Sn contributes to the high capacity of battery as negative electrode active material capacious, but follows the change in volume discharging and recharging large.Therefore,, in the case of having used such negative electrode active material, by repeated charge, flexible due to negative pole entirety, can cause mechanical injuries to aspectant barrier film with it.If the puncture intensity of barrier film is more than 3N, guarantee good mechanical strength, can relax the suffered mechanical damage of barrier film.
Be barrier film more than 3N as puncture intensity, can enumerate aforementioned cascade type barrier film, especially preferably on the porous layer using fusing point as the resin below 140 DEG C as main body (I), be laminated with the barrier film that contains the porous layer (II) of heat resisting temperature as more than 150 DEG C inorganic fillers as main body.This be considered to due to: the mechanical strength of aforementioned inorganic filler is high, therefore, has compensated the mechanical strength of porous layer (I), thereby can improve the mechanical strength of barrier film entirety.
Aforementioned puncture intensity can be measured by the following method.On the plate in hole that has 2 inches diameter, barrier film is fixed in the mode that there is no fold, deflection, making most advanced and sophisticated diameter is that the spherical metal needle of the semicircle of 1.0mm drops on and measures on sample with the speed of 120mm/min, and the power when producing hole in barrier film is carried out 5 times and measured.And, average for the mensuration of 3 times except maximum and minimum value in the measured value of aforementioned 5 times, set it as the puncture intensity of barrier film.
Aforementioned positive pole, aforementioned negative pole and aforementioned barrier film can use with following form in lithium secondary battery of the present invention: between positive pole and negative pole across barrier film and overlapping cascade type electrode body is further wound into spiral helicine rolled electrode body.
In aforementioned cascade type electrode body, rolled electrode body, use and especially on the porous layer using fusing point as the resin below 140 DEG C as main body (I), be laminated with the barrier film that contains the porous layer (II) of heat resisting temperature as more than 150 DEG C inorganic fillers as main body at aforementioned cascade type barrier film, be preferably at least configured towards anodal mode with porous layer (II).In addition, in this case, by contain heat resisting temperature be 150 DEG C of above inorganic fillers as porous layer main body, that oxidative resistance is more excellent (II) towards positive pole, can suppress better the oxidation of the barrier film being caused by positive pole, therefore preservation characteristics, charge/discharge cycle characteristics, can also improve the high temperature of battery time.In addition, the in the situation that of being added with the additive such as VC, cyclohexyl benzene in nonaqueous electrolyte, stop up the pore of barrier film thereby form epithelium at side of the positive electrode, also likely caused the reduction of battery behavior.Here by making the porous layer (II) of relative porous towards positive pole, can also expect the effect of the obstruction that suppresses pore.
On the other hand, be porous layer (I) on a surface of aforementioned cascade type barrier film, preferably be made as porous layer (I) towards negative pole, in this way, for example, while having suppressed shut-down, absorbed by the mixture layer of electrode from the thermoplastic resin of porous layer (I) melting, thereby can utilize efficiently the obturation of barrier film emptying aperture.
As the form of lithium secondary battery of the present invention, can enumerate and use cylinder of steel, aluminium pot etc. as the tubular (square tube shape, cylindrical shape etc.) of outer package jar etc.In addition, can also make taking evaporation and have the lamination mould of metal as the flexible-packed battery of external packing body.
Upper voltage limit when lithium secondary battery of the present invention can be by charging before using is made as the 4.2V left and right that common lithium secondary battery adopts, even but the method for charging to high voltage more than 4.3V with height also can stably use.
Embodiment
Below, based on embodiment, the present invention is at length described.But, following embodiment is not limitation of the present invention.
Embodiment 1
Anodal making: by Li 1.0ni 0.5co 0.2mn 0.3o 2(lithium nickel composite oxide (a)) and Li 1.036co 0.991al 0.004mg 0.002sr 0.001ti 0.002zr 0.001o 2(lithium cobalt composite oxide (b)) in the ratio of 3:7 (mass ratio) mix positive active material 100 mass parts, contain as nmp solution 20 mass parts of the PVDF of binding agent, carry out mixing as Delanium 1 mass parts and the Ketjen black 1 mass parts twin-screw mixer machine of conductive auxiliary agent using the concentration of 10 quality %, further add NMP to regulate viscosity, thereby be modulated into the paste that contains anode mixture.
The aforementioned paste that contains anode mixture is coated on to the two sides of the aluminium foil that thickness is 15 μ m (positive electrode collector), then, carries out vacuumize in 12 hours at 120 DEG C, thereby form anode mixture layer on the two sides of aluminium foil.Afterwards, carry out pressurized treatments, thereby thickness and density to anode mixture layer regulate, weld the lead-in wire body of nickel system at the exposed division of aluminium foil, thereby make the band shape positive pole of length 375mm, width 43mm.In the positive pole obtaining, the thickness of every, anode mixture layer is 55 μ m.
The making of negative pole: using as negative electrode active material, average grain diameter D50% is that graphite that the SiO surface of 8 μ m is 16 μ m by the complex of material with carbon element coating (in complex, the amount of material with carbon element is 10 quality %) with average grain diameter D50% is mixture 97.5 mass parts that are obtained by mixing of the amount of 3.75 quality % by the amount of the complex of material with carbon element coating by SiO surface, adds water and mix as the SBR1.5 mass parts of binding agent and in the CMC1 mass parts of thickener, is modulated into the paste that contains cathode agent.
The aforementioned paste that contains cathode agent is coated on to the two sides of the Copper Foil that thickness is 8 μ m (negative electrode collector), then, carries out vacuumize in 12 hours at 120 DEG C, thereby form anode mixture layer on the two sides of Copper Foil.Afterwards, carry out pressurized treatments, thereby thickness and the density of anticathode mixture layer regulate, weld the lead-in wire body of nickel system at the exposed division of Copper Foil, thereby make the banded negative pole of length 380mm, width 44mm.In the negative pole obtaining, the thickness of every of anode mixture layer is 65 μ m.
The modulation of nonaqueous electrolyte: in the mixed solvent that is 3:7 in ethylene carbonate (EC) and the volumetric ratio of diethyl carbonate (DEC), by LiPF 6dissolve with the concentration of 1.1mol/L, amount, the FEC that amount, the EDPA that further becomes 0.1 quality % with adiponitrile respectively becomes 1.25 quality % becomes the amount of 2.0 quality % and VC and becomes the amount of 2.0 quality % and add, thus modulation nonaqueous electrolyte.
The assembling of battery: by aforementioned banded anodal be that barrier film shown below and the aforementioned banded negative pole of 16 μ m is overlapping across thickness, be wound into after helical form, pressurize to become flat, thereby make the electrode coiling body of flat winding-structure, this electrode coiling body is fixed with the insulating tape of polypropylene system.Then, former electrodes coiling body is inserted to the prismatic battery case that external dimensions is the aluminium alloy system of thickness 4.0mm, width 34mm, height 50mm, the welding of the body that goes between, meanwhile, is connected on the bridge welding of aluminium alloy system the open end of battery case.Thereafter, from cover plate, set inlet injects aforementioned nonaqueous electrolyte, leaves standstill after 1 hour, by inlet sealing, thereby obtains the lithium secondary battery of outward appearance shown in structure, Fig. 2 shown in Fig. 1.
The making of barrier film: add ion exchange water 5kg and dispersant (water system polybasic carboxylic acid ammonium salt in 5kg average grain diameter D50% is the boehmite of 1 μ m, solid component concentration 40 quality %) 0.5kg, carry out 10 hours pulverization process with the ball mill of 40 beats/min of internal volume 20L, revolution, thus modulation dispersion liquid.Make dispersion liquid after treatment 120 DEG C of vacuumizes, observe with scanning electron microscope (SEM), result, the shape of boehmite is roughly tabular.
In aforementioned dispersion liquid 500g, add as the xanthans 0.5g of tackifier, as resin binder dispersion (the modified polypropene acid butyl ester of adhesive, solid component content 45 quality %) 17g, with Three-OneMotor stirring 3 hours, thereby be modulated into uniform slurry (porous layer (II) forms with slurry, solid constituent ratio 50 quality %).
The one side of the micro-porous barrier film of secondary lithium batteries PE system (porous layer (I): 135 DEG C of the fusing points of thickness 12 μ m, void content 40%, average pore size 0.08 μ m, PE) is implemented to Corona discharge Treatment (discharge capacity 40Wmin/m 2), form with starching and being dried with miniature intaglio plate coating machine applying porous matter layer (II) on this treated side, forming thickness is the porous layer (II) of 4 μ m, thereby obtains cascade type barrier film.The quality of the per unit area of porous layer in this barrier film (II) is 5.5g/m 2, the volume containing ratio of boehmite is 95 volume %, void content is 45%.
Here battery shown in Fig. 1 and Fig. 2 is described, (a) of Fig. 1 is that vertical view, (b) are its fragmentary cross-sectional view, as shown in Fig. 1 (b), anodal 1 is wound into after helical form across barrier film 3 with negative pole 2, pressurize, to become flat, be contained in together with nonaqueous electrolyte in square (square tube shape) battery case 4 as the electrode coiling body 6 of flat.But, in Fig. 1, for fear of complicated, and metal forming, the nonaqueous electrolyte etc. of the collector body using when not shown, negative pole 2 anodal 1 as making.
Battery case 4 is aluminium alloy system, forms the exterior body of battery, and this battery case 4 is held concurrently as positive terminal.And, dispose the insulator 5 being formed by PE sheet material in the bottom of battery case 4, lead to positive wire body 7 and the negative wire body 8 of the one end that is connected in separately positive pole 1 and negative pole 2 from the flat electrode coiling body 6 being formed by positive pole 1, negative pole 2 and barrier film 3.In addition, the sealing of the aluminium alloy system of the peristome sealing of battery case 4 is used on cover plate 9, the terminal 11 of stainless steel is installed across the insulation spacer 10 of polypropylene system, on this terminal 11, the lead plate 13 of stainless steel is installed by insulator 12.
And this cover plate 9 inserts the peristome of battery case 4, by both junction surfaces are welded, the peristome of battery case 4 is sealed, and inside battery is sealed.In addition, in the battery of Fig. 1, cover plate 9 is provided with nonaqueous electrolyte inlet 14, to have inserted the state of seal member in this nonaqueous electrolyte inlet 14, by such as laser welding etc. and soldered sealing, thereby guarantee the sealing of battery (therefore, in the battery of Fig. 1 and Fig. 2, in fact, nonaqueous electrolyte inlet 14 is nonaqueous electrolyte inlet and seal member, but for ease of explanation, show as nonaqueous electrolyte inlet 14).And then, on cover plate 9, as inner gas being expelled to outside mechanism when the temperature rise of battery, be provided with venting 15.
In the battery of this embodiment 1, by directly positive wire body 7 being welded on cover plate 9, outer package jar 5 and cover plate 9 are as positive terminal performance function, by negative wire body 8 being welded in to lead plate 13 and making negative wire body 8 and terminal 11 conductings by this lead plate 13, terminal 11 is as negative terminal performance function, but according to material of battery case 4 etc., its positive and negative meeting is contrary sometimes.
Fig. 2 is the stereogram that schematically shows the outward appearance of battery shown in earlier figures 1, and this Fig. 2 shows that aforementioned battery is that rectangular cell is that object is carried out illustrated figure, in this Fig. 1, has substantially shown battery, has only shown specific parts in the building block of battery.In addition, in Fig. 1 the part of the inner circumferential side of electrode body also not in section.
Embodiment 2
The addition of adiponitrile is changed to 0.25 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 3
The addition of adiponitrile is changed to 0.5 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 4
The addition of adiponitrile is changed to 1.0 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 5
The addition of adiponitrile is changed to 2.5 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 6
The addition of adiponitrile is changed to 5.0 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 7
The addition of adiponitrile is changed to 0.5 quality %, do not add EPDA, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 8
The addition of adiponitrile is changed to 7.5 quality %, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
Embodiment 9
Adiponitrile is changed to succinonitrile, in addition, operation similarly to Example 4, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operates similarly to Example 4, makes lithium secondary battery.
Embodiment 10
EDPA is changed to PDPA, in addition, operation similarly to Example 4, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operates similarly to Example 4, makes lithium secondary battery.
Comparative example 1
Do not add adiponitrile, in addition, operation similarly to Example 1, modulation nonaqueous electrolyte, except using this nonaqueous electrolyte, operation similarly to Example 1, makes lithium secondary battery.
50 DEG C of DOD5% tests: for the battery of embodiment and comparative example, carry out constant-current charge until reach 4.35V with the current value of 1.0C, then, carry out constant-voltage charge with the voltage of 4.35V.In addition, the total charging time of constant-current charge and constant-voltage charge is made as 2.5 hours.,, discharge with the current value of 0.2C until reach 3.0V, thereby initial capacity is measured thereafter.
Then, each battery of measuring after initial capacity is charged to the electric state that is full of to measure same condition with initial capacity.And, for the each battery that is full of electric state, be discharged to 5% (DOD5%) of about rated capacity at 50 DEG C of current values with 1.0C, again charge with the current value of 1.0C until reach the electric state that is full of, using above-mentioned sequence of operations as 1 circulation, repeatedly carry out discharging and recharging of 800 circulations.For each battery thereafter, discharge and recharge to measure same condition with initial capacity, the capacity of the each battery after 800 circulations is measured, this capacity is represented with percentage divided by the value of initial capacity, try to achieve capacity dimension holdup.
This 50 DEG C of DOD5% test is following test: for the battery that is full of electric state, a fraction of electric discharge of repeatedly carrying out capacity only with until be full of the charging of electric state, thereby be assumed to be the using method of carrying out constantly trickle charge.Therefore, in this test, capacity dimension holdup is higher, even if mean that the method to carry out constantly trickle charge is used battery, stability is also high.
Short circuit test after trickle charge: for each battery (not being the battery that has carried out 50 DEG C of DOD5% tests) of embodiment and comparative example, continue to carry out determining electric current-constant-voltage charge, investigate the having or not of short circuit of each battery after 500 hours, describedly determine electric current-constant-voltage charge and be: charge until the constant-current charge of 4.4V at 45 DEG C of current values with 1.0C, then, carry out constant-voltage charge with the voltage of 4.4V.
This test is also assumed to be the using method of carrying out constantly trickle charge, even the battery to short circuit unconfirmed means that the method to carry out constantly trickle charge is used after this test, stability is also high.
Charge/discharge cycle characteristics: for each battery (not being the battery that has carried out aforementioned each evaluation) of embodiment and comparative example, discharge and recharge to measure same condition with the initial capacity of 50 DEG C of DOD5% tests, initial capacity is measured.
Then, for each battery of measuring after initial capacity, current value with 1C carries out constant-current charge until 4.35V, then, carry out the charging (total charging time of constant-current charge and constant-voltage charge was as 2.5 hours) of constant-voltage charge taking the voltage of 4.35V, thereafter, discharge until 3.0V with the current value of 1C, using above-mentioned sequence of operations as 1 circulation, repeatedly carry out discharging and recharging of 500 circulations.For each battery thereafter, same condition is carried out charging and discharging when measuring with initial capacity, discharge capacity to the each battery after 500 circulations is measured, and by representing divided by the percentage of the value with initial capacity with this capacity, tries to achieve capacity dimension holdup.Can say, this capacity dimension holdup Gao Yuegao, the charge/discharge cycle characteristics of battery is better.
Storage test: for the battery (not being the battery that has carried out aforementioned each evaluation) of embodiment and comparative example, charge to measure same condition with the initial capacity of 50 DEG C of DOD5% tests.Each battery after charging is put into thermostat, temperature in groove is made as to 85 DEG C, place 24 hours., each battery from thermostat taken out, place cooling until reach after room temperature, thickness is measured, calculate poor with initial stage thickness (4.0mm), try to achieve the swell increment of battery after storage test thereafter.
Part throttle characteristics: for the battery (not being the battery that has carried out aforementioned each evaluation) of embodiment and comparative example, discharge and recharge to measure same condition with the initial capacity of 50 DEG C of DOD5% tests, thereby discharge capacity (0.2C discharge capacity) is measured.In addition, the each battery after measuring for 0.2C discharge capacity, same condition is charged when measuring with 0.2C discharge capacity, discharges until 3.0V, thereby discharge capacity (1.5C discharge capacity) is measured with the current value of 1.5C.And, for each battery, by representing divided by the value percentage of 0.2C discharge capacity by 1.5C discharge capacity, try to achieve capacity dimension holdup.Can say, this capacity dimension holdup Gao Yuegao, the part throttle characteristics of battery is better.
In the nonaqueous electrolyte that the lithium secondary battery of embodiment and comparative example is used, the content of each additive is shown in table 1, and aforementioned each evaluation result is shown in to table 2.
Table 1
Table 2
As shown in Table 1 and Table 2, by lithium nickel composite oxide (a) for positive active material, SiO is used for to negative electrode active material, and use the lithium secondary battery of the embodiment 1～10 that contains the nonaqueous electrolyte in molecule with the compound of itrile group compared with having used the battery that does not contain the comparative example 1 in molecule with the nonaqueous electrolyte of the compound of itrile group, in 50 DEG C of DOD5% tests, capacity dimension holdup is high, in addition after trickle charge, be not short-circuited, yet.Therefore, even if carrying out the such method of trickle charge constantly with high voltage more than 4.3V, the lithium secondary battery of embodiment 1～10 also can stably use.And then the lithium secondary battery part throttle characteristics of embodiment 1～10 is also good.
In addition; used the nonaqueous electrolyte that also contains the represented phosphoryl acetate compounds of aforementioned formula (1) embodiment 1～6,8,9,10 lithium secondary battery with used not containing compared with the battery of the embodiment 7 of the nonaqueous electrolyte of this compound; swell increment after storage test is little, and storing property is also excellent.
In addition, used the nonaqueous electrolyte that the content of the compound in molecule with itrile group is suitable embodiment 1～7,9,10 lithium secondary battery with used this compounds content very compared with the lithium secondary battery of the embodiment 8 of many nonaqueous electrolytes, capacity dimension holdup when charge/discharge cycle characteristics is evaluated is high, and charge/discharge cycle characteristics is also excellent.
Not departing from the scope of its aim, the present invention can also implement as the form beyond aforementioned.The disclosed execution mode of the application is an example, and the present invention is not limited to these execution modes.Compared with the record of aforementioned specification, scope of the present invention preferentially explained by the record of appended claims, is all contained in claims with the whole changes in the scope of claims equalization.
Industry utilizability
Even if carrying out trickle charge constantly, lithium secondary battery of the present invention also can stably use, therefore, except can being suitably applied to the power supply purposes of the portable electronic device that the possibility that in this way uses is high, can also be used for and the application same purposes of the various uses of known lithium secondary battery in the past.
Symbol description
1 positive pole
2 negative poles
3 barrier films

Claims (10)

1. a lithium secondary battery, is characterized in that, possesses positive pole, negative pole, nonaqueous electrolyte and barrier film,
Described positive pole has the anode mixture layer that contains positive active material at the one or both sides of collector body,
Described negative pole has the anode mixture layer that contains negative electrode active material at the one or both sides of collector body,
The anode mixture layer of described positive pole contains by forming general formula Li 1+yni 1-a-b-cco amn bm 1 co 2represented lithium nickel composite oxide is as positive active material, wherein, and M 1for selecting at least a kind of element of group of free Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, W, B, P and Bi composition ,-0.15≤y≤0.15,0.05≤a≤0.3,0.05≤b≤0.3,0≤c≤0.03 and a+b+c≤0.5,
The anode mixture layer of described negative pole contains the material that comprises Si and O in component as negative electrode active material, and wherein, O is 0.5≤x≤1.5 with respect to the atomic ratio x of Si,
Described nonaqueous electrolyte contains the compound in molecule with itrile group.
2. lithium secondary battery according to claim 1, the nonaqueous electrolyte of the represented phosphoryl acetate compounds of following general formula (1) that its use contains 0.5～30 quality %,
In described general formula (1), R 1, R 2and R 3be the alkyl of the carbon number 1～12 that can be replaced by halogen atom independently of one another, the integer that n is 0～6.
3. lithium secondary battery according to claim 1 and 2, the content in its use molecule with the compound of itrile group is the nonaqueous electrolyte of 0.1～5.0 quality %.
4. according to the lithium secondary battery described in any one in claim 1～3, the compound in molecule with itrile group has more than 2 itrile group in molecule.
5. according to the lithium secondary battery described in any one in claim 1～4, the compound in molecule with itrile group is adiponitrile.
6. according to the lithium secondary battery described in any one in claim 1～5, the anode mixture layer of negative pole contains the material that comprises Si and O in component and the complex of material with carbon element.
7. according to the lithium secondary battery described in any one in claim 1～6, the anode mixture layer of negative pole further contains graphite matter material with carbon element as negative electrode active material.
8. according to the lithium secondary battery described in any one in claim 1～7, it uses the nonaqueous electrolyte of the cyclic carbonate that further contains halogen replacement.
9. according to the lithium secondary battery described in any one in claim 1～8, it uses the nonaqueous electrolyte that further contains vinylene carbonate.
10. according to the lithium secondary battery described in any one in claim 1～9, more than the upper voltage limit of its charging is set in 4.3V.
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