CN102195089B

CN102195089B - Nonaqueous electrolyte and nonaqueous electrolyte battery

Info

Publication number: CN102195089B
Application number: CN201110044358.0A
Authority: CN
Inventors: 山田郎; 山田一郎; 齐藤俊介; 渡边春夫; 洼田忠彦
Original assignee: Sony Corp
Current assignee: Murata Northeast China; Murata Manufacturing Co Ltd
Priority date: 2010-03-02
Filing date: 2011-02-23
Publication date: 2016-09-14
Anticipated expiration: 2031-02-23
Also published as: CN102195089A; CN106099191B; CN106099191A

Abstract

The invention provides a kind of nonaqueous electrolyte and nonaqueous electrolyte battery.This nonaqueous electrolyte includes: solvent；Electrolytic salt；And at least one in the heteropolyacid salt compound represented by lower formula (I) and (II): H_xA_y[BD₁₂O₄₀]·zH₂O (I)H_pA_q[B₅D₃₀O₁₁₀]·rH₂Wherein, A represents Li, Na, K, Rb, Cs, Mg, Ca, Al, NH to O (II)₄, or ammonium salt or salt；B represents P, Si, As or Ge；D represents at least one element in Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Tc, Rh, Cd, In, Sn, Ta, W, Re and Tl；X, y and z are the value in the range of 0≤x≤1,2≤y≤4 and 0≤z≤5 that falls respectively；And p, q and r are the value in the range of 0≤p≤5,10≤q≤15 and 0≤r≤15 that falls respectively.

Description

Nonaqueous electrolyte and nonaqueous electrolyte battery

Technical field

The present invention relates to a kind of nonaqueous electrolyte and nonaqueous electrolyte battery.In more detail, the present invention relates to one comprise Organic solvent and the nonaqueous electrolyte of electrolytic salt and use the nonaqueous electrolyte battery of this nonaqueous electrolyte.

Background technology

In recent years, portable electric appts, the integrated VTR (magnetic tape video recorder) of such as video camera, mobile phone and above-knee Type personal computer is the most widely available, and is strongly required to realize their miniaturization, lightweight and long-life.Companion as it does so, Advance the battery as the compact power for electronic equipment, especially lightweight and high-energy-density can be obtained from it The exploitation of secondary cell.

Especially, the embedding and the deintercalation that utilize lithium (Li) are used for secondary cell (the so-called lithium ion that charge/discharge reacts Secondary cell) extensively put into reality application, because electric with traditional lead battery and the NI-G as nonaqueous electrolytic solution secondary battery Pond is compared, and can obtain high-energy-density.Such lithium rechargeable battery is provided with electrolyte and positive pole and negative pole.

Especially, aluminium lamination press mold is used to have bigger energy for the laminated-type battery of package due to its weight amount Metric density.Further, in laminated-type battery, when nonaqueous electrolytic solution expand in polymer, can be with inhibition layer die mould battery Deformation, and therefore, laminated-type polymer battery is also widely used.

But, in laminated-type battery, owing to package is the softest, therefore relate to such problem, i.e. owing to initially filling Gas during electricity and also produced in the inside of battery when High temperature storage, it is easy to cause cell expansion (bubbling, blister). In response to this problem, as described in patent documentation 1 (JP-A-2006-86058), by by all for halogenated cyclic carbonic ester Such as fluoroethylene carbonate or there is the cyclic carbonate such as vinylene carbonate of carbon-to-carbon Multiple Bonds join nonaqueous electrolytic solution In, the reaction of negative electrode active material and nonaqueous electrolytic solution etc. can be suppressed, thus can suppress cell expansion during initial charge. But, such reactive cyclic carbonate can not suppress cell expansion when at high temperature using.

Use heteropolyacid salt as electrode active material additionally, patent documentation 2 (JP-A-2002-289188) proposes, be somebody's turn to do Heteropolyacid salt is the compound that can embed with deintercalate lithium ions and obtains metastable structure.

Summary of the invention

But, patent documentation 1 is without result in obtaining enough battery behavior, this is because miscellaneous many as reductant-oxidant The reactivity of acid self.There is no the following reason that reason for this is that of enough characteristics: heteropoly acid itself is Strong oxdiative reducing agent And it is strong acid；Heteropoly acid comprises water of crystallization etc. in its structure.Therefore, it is added in advance when such heteropoly compound Time in electrode mixture or nonaqueous electrolytic solution, there is the heteropoly acid of the highest redox ability and be derived from water of crystallization Free acid, such as, the corrosion collector body such as oxolane (hydrofuran) or binding agent, thus cause the electricity that such as resistance causes Pond deterioration in characteristics.

Further, patent documentation 2 is directed to use with heteropoly acid for active substance itself, but without reference to miscellaneous many by using Acid improves safety.

Accordingly, it is desired to provide a kind of nonaqueous electrolyte and nonaqueous electrolyte battery, it each can suppress in initial charge Time and the gas that also produces in the inside of battery when High temperature storage, and cause cell expansion hardly.

According to an embodiment of the invention, it is provided that one includes solvent；Electrolytic salt and by lower formula (I) and (II) nonaqueous electrolyte of at least one in the heteropolyacid salt compound represented.

According to another implementation of the invention, it is provided that a kind of include the non-of positive pole, negative pole and nonaqueous electrolyte Water-Electrolyte battery, the gel wherein comprising the amorphous polyacid containing one or more multielements and/or polyacid compound is coated with Layer is arranged at least one of surface of negative pole, and this coating source freely descends the heteropolyacid salt chemical combination that formula (I) and (II) represent At least one in thing.

H_xA_y[BD₁₂O₄₀]·zH₂O (I)

In formula (I), A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminum (Al), ammonium (NH₄), ammonium salt or salt (microcosmic salt)；B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge)；D represents that choosing is freely Titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), Niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), stannum (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and thallium (Tl) At least one element in the group of composition；And x, y and z are to fall in the range of 0≤x≤1,2≤y≤4 and 0≤z≤5 respectively Value.

H_pA_q[B₅D₃₀O₁₁₀]·rH₂O (II)

In formula (II), A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminum (Al), ammonium (NH4), ammonium salt or salt；B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge)；D represents the free titanium of choosing (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), in the group that technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), stannum (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and thallium (Tl) form At least one element；And p, q and r are the value in the range of 0≤p≤5,10≤q≤15 and 0≤r≤15 that falls respectively.

According to the embodiment of the present invention, comprise, due to nonaqueous electrolytic solution, the heteropoly acid salinization represented by formula (I) and (II) The fact that at least one in compound, therefore can reduce the moisture in nonaqueous electrolyte and acid composition.Then, using this non- In the nonaqueous electrolyte battery of Water-Electrolyte, it is possible not only on negative pole form coating, and can suppress due in electrolyte Moisture and the acid side reaction that causes of composition.

According to the embodiment of the present invention, the decomposition of electrolyte can be suppressed, gas thus can be suppressed to produce.Further, The deterioration of each several part of battery can be suppressed.

Accompanying drawing explanation

Fig. 1 shows the sectional view of the structure example of the nonaqueous electrolyte battery according to embodiment of the present invention.

Fig. 2 is the sectional view of the part showing the rolled electrode bodies in Fig. 1 enlargedly.

Fig. 3 is the SEM photograph of the negative terminal surface according to embodiment of the present invention.

Fig. 4 show by silico-tungstic acid is joined battery system makes deposit (precipitate) deposit (precipitation) By the two of time-of-flight type (time-of-flight) secondary ion mass spectrometry (ToF-SIMS) in negative terminal surface thereon The figure of the example of secondary ion spectrum.

Fig. 5 shows by silico-tungstic acid joins the negative pole table making deposits in battery system thereon Analyzed the radial structure letter of the W-O key obtained by the Fourier transformation of wave spectrum by X-ray absorption fine structure (XAFS) on face The figure of the example of number (radial structure function).

Fig. 6 shows the decomposition diagram of the structure example of the nonaqueous electrolyte battery according to embodiment of the present invention.

Fig. 7 is the sectional view of the I-I line along the rolled electrode bodies shown in Fig. 6.

Fig. 8 shows the sectional view of other structure example of the nonaqueous electrolyte battery according to embodiment of the present invention.

Fig. 9 shows the sectional view of other structure example of the nonaqueous electrolyte battery according to embodiment of the present invention.

Detailed description of the invention

Following by being described with reference to according to the embodiment of the present invention.It is described in the following order.

1. the first embodiment (according to the example of the nonaqueous electrolytic solution comprising heteropolyacid salt compound of the present invention)

2. the second embodiment (using the example of column type nonaqueous electrolyte battery)

3. the 3rd embodiment (using the example of laminated membrane type nonaqueous electrolyte battery)

4. the 4th embodiment (using the example of laminated membrane type nonaqueous electrolyte battery)

5. the 5th embodiment (using the example of square nonaqueous electrolyte battery)

6. the 6th embodiment (using the example of the nonaqueous electrolyte battery of laminated-type electrode body)

7. other embodiment

1. the first embodiment

Nonaqueous electrolytic solution according to first embodiment of the invention is described.According to first embodiment of the invention Nonaqueous electrolytic solution is such as used for the electrochemical appliance of such as battery.This nonaqueous electrolytic solution comprises solvent, electrolytic salt and miscellaneous Multi-acid salt compound.Electrolytic salt and heteropolyacid salt compound are dissolvable in water in solvent.

(1-1) heteropolyacid salt compound

According to the first embodiment of the invention heteropolyacid salt compound is by lower formula (I) and the tool with structure with Keggin At least one in the lower formula (II) of Preyssler structure is had to represent.

H_xA_y[BD₁₂O₄₀]·zH₂O (I)

In formula (I), A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminum (Al), ammonium (NH4), ammonium salt or salt；B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge)；D represents the free titanium of choosing (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), in the group that technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), stannum (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and thallium (Tl) form At least one element；And x, y and z are the value in the range of 0≤x≤1,2≤y≤4 and 0≤z≤5 that falls respectively.

H_pA_q[B₅D₃₀O₁₁₀]·rH₂O (II)

That is, in formula (I) and (II), in heteropolyacid salt compound, the acid composition (H in formula (I)_xOr in formula (II) H_p) salt (A in formula (I) that is not more than in heteropolyacid salt compound of proton_yOr the A in formula (II)_q) half.

When comprising the heteropolyacid salt compound represented by formula (I) and/or formula (II) in nonaqueous electrolytic solution, by using The charge/discharge during initial stage, is formed on electrode surface, particularly negative terminal surface and is referred to as stable SEI (solid electrolyte interface Coating) coating.Due to be derived from the coating that can embed the heteropolyacid salt compound with deintercalation Li have excellence Li ion saturating The property crossed, produces it is understood that the gas when applied at elevated temperature can be reduced, and does not make cycle characteristics deteriorate, press down simultaneously Make the reaction between electrode and nonaqueous electrolytic solution.Further, especially, when using by the formula with Preyssler structure (II) during the heteropolyacid salt compound represented, it is easier to be dissolved in the solvent of battery, and can be steady in the range of wide pH Surely exist.

When acid composition is present in nonaqueous electrolytic solution, its redox ability is stronger so that relate to such problem, I.e., it is possible to cause the decomposition of such as nonaqueous electrolytic solution and the less desirable side reaction of corrosion.Further, it is present in non-water power when moisture When solving in liquid, relate to such problem, i.e. being derived from the free acid of water of crystallization, such as, oxolane etc. corrodes collector body or bonding Agent, and cause the decomposition of electrolytic salt.

Simultaneously as heteropolyacid salt compound according to the first embodiment of the invention has the most some or all matter Son is replaced the structure of (replacement) by alkali metal cation, therefore can not produce free acid.Further, by use, there is higher chemical combination The heteropolyacid salt compound of the anion of valency, even if when it is in the state not having water of crystallization, is similar to heteropoly acid, heteropoly acid Salt compound is also dissolved easily in nonaqueous electrolytic solution, and becomes to obtain stable structure.In the inside of battery, relatively In the range of wide pH, the heteropolyacid salt compound with maximum conjunction valency with stable structure is prone to be reduced, thus is prone to electricity Chemically form coating.

Preferably, the least as the content of moisture of the reason of the decomposition etc. of electrolytic salt in nonaqueous electrolytic solution. Specifically, it is preferred that, in nonaqueous electrolytic solution, the amount of moisture is not more than 50ppm.The amount of moisture can such as be had a rest by karr expense Your method etc. is measured.

And, it is preferred that nonaqueous electrolytic solution cause the decomposition of nonaqueous electrolytic solution become with the acid of the corrosion of metal material The content divided is the least.Specifically, it is preferred that, in nonaqueous electrolytic solution, the amount of acid composition is not more than 100ppm.Here, acid becomes Divide and refer to Bronsted acid such as HF.In nonaqueous electrolytic solution, the amount of acid composition can be such as by using acid-base titrations etc. to measure.

According to the first embodiment of the invention heteropolyacid salt compound is by as two or more oxyacid (oxoacid) heteropoly acid of condensation substance is constituted.According to the first embodiment of the invention, it is preferred that heteropoly acid has There is the structure being wherein readily dissolved in the solvent of battery, such as such as the structure with Keggin in formula (I) with as in formula (II) Preyssler structure.Further, wherein acid composition proton not more than salt half have Anderson (Anderson) structure or The heteropoly acid of road gloomy (Dawson) structure is preferred.

The heteropoly acid of heteropolyacid salt compound and composition heteropolyacid salt compound has selected from following elements group (a) Polyatomic heteropolyacid salt compound and heteropoly acid；Or there is the polyatomic heteropoly acid salinization selected from following elements group (a) Compound and heteropoly acid, a portion polyatom is selected from least any element of following elements group (b) and replaces.

Element group (a): Mo, W, Nb, V

Element group (b): Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Tc, Rh, Cd, In, Sn, Ta, Re, Tl, Pb

Further, heteropolyacid salt compound and heteropoly acid are to have the heteroatomic heteropolyacid salt selected from following elements group (c) Compound and heteropoly acid；Or there is the heteroatomic heteropolyacid salt compound selected from following elements group (c) and heteropoly acid, Qi Zhongyi Part hetero atom is selected from least any element of following elements group (d) and replaces.

Element group (c): B, Al, Si, P, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As

Element group (d): H, Be, B, C, Na, Al, Si, P, S, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se、Zr、Rh、Sn、Sb、Te、I、Re、Pt、Bi、Ce、Th、U、Np

It is included in for the example bag according to the heteropoly acid in the heteropolyacid salt compound in first embodiment of the invention Include miscellaneous many wolframic acids, such as phosphotungstic acid and silico-tungstic acid；And heteropoly molybdic acid, such as phosphomolybdic acid and silicomolybdic acid.Further, many as comprising Plant the material of multielement (polyelement), it is possible to use such as phosphovanadomolybdic acid, phosphotungstomolybdic acid, silicon vanadium molybdic acid and silicon tungsten molybdic acid Material.

Preferably, heteropolyacid salt compound has cation, such as, and Li⁺、Na⁺、K⁺、Rb⁺、Cs⁺、R₄N⁺、R₄P⁺Deng, its Middle R is H or the alkyl with not more than 10 carbon atoms.Further, cation is more preferably Li⁺, tetra-n-butyl ammonium or four positive fourths Base.

The example of such heteropolyacid salt compound includes miscellaneous how tungstated compound, such as silicotungstic sodium, Sodium phosphotungstate, phosphorus Ammonium tungstate and silico-tungstic acid four (tetra-n-butyl) salt.Further, the example of heteropoly compound includes heteropoly molybdic acid compound, such as Sodium phosphomolybdate, ammonium phosphomolybdate and phosphomolybdic acid three (tetra-n-butyl ammonium) salt.Additionally, the example of the compound comprising multiple polyacid includes The such as material of phosphotungstomolybdic acid three (four positive ammoniums) salt.Such heteropoly acid or heteropoly compound can with two kinds in them or More kinds of mixture uses.Such heteropoly acid or heteropoly compound are readily dissolved in solvent, are stable in the battery , and it is difficult to have a negative impact, such as with the reaction of other materials.

Further, according to the first embodiment of the invention, it is possible to use polyacid compound.As polyacid compound, Different polyacid compound can be used together with heteropoly compound.Further, compared with heteropoly compound, different polyacid compound exists The effect aspect often adding weight is tended to somewhat deteriorate.But, due to different polyacid compound dissolubility in polar solvent The lowest, therefore when being used in negative or positive electrode, have in such as viscoelasticity and its coating characteristic over time Excellent aspect (situation) so that from the point of view of industrial point, it has serviceability.

Being similar to heteropolyacid salt compound, polyacid compound according to the first embodiment of the invention is to have to be selected from down Polyatomic polyacid compound of column element group (a)；Or there is the polyatomic polyacid compound selected from following elements group (a), A portion polyatom is selected from least any element of following elements group (b) and replaces.

Element group (a): Mo, W, Nb, V

It is included in for including tungsten according to the example of the polyacid in the polyacid compound in first embodiment of the invention (VI) acid and molybdenum (VI) acid.Its instantiation includes tungstic acid anhydride, molybdic acid anhydride and their hydrate.The hydrate that can use Example include as wolframic acid monohydrate (WO₃·H₂O) ortho-tungstic acid (positive wolframic acid) (H₂WO₄), molybdic acid dihydrate (H₄MoO₅、H₂MoO₄·H₂O or MoO₃·2H₂O) and as molybdic acid monohydrate (MoO₃·H₂O) ortho-molybdic acid (H₂MoO₄)。 It is used for the metatungstic acid of different polyacid of above-mentioned hydrate, para-tungstic acid etc. and it is possible to use there is less hydrogen content and There is the tungstic acid anhydride (WO of zero hydrogen content eventually₃)；Than metamolybdic acid, para-molybdic acid etc., there is less hydrogen content and finally there is zero hydrogen Molybdic acid anhydride (the MoO of content₃) etc..

Nonaqueous electrolytic solution comprises at least one in the compound represented by aforementioned formula (I) and (II).And it is possible to use The combination of two or more compounds represented by formula (I) and (II).Wherein remove by adding to have in nonaqueous electrolytic solution The multi-acid salt compound of such structure of deprotonation and moisture, can control the moisture in nonaqueous electrolytic solution and suppress The generation of free acid, no matter the addition of heteropolyacid salt compound how.

Further, at least one heteropolyacid salt constituted in the compound represented by formula (I) and (II) in nonaqueous electrolytic solution The content of compound, is preferably by weight more than 0.01% and is not more than from the viewpoint of the cell expansion after initial charge By weight 3%, and after each operation of initial charge and High temperature storage from the viewpoint of cell expansion, more preferably press Weight meter more than 1.0% and no more than by weight 3.0%.When the content of heteropolyacid salt compound is the least, the formation of SEI is Insufficient so that it is little to obtain by adding the effect that heteropolyacid salt compound causes.Further, heteropolyacid salt compound Content be the most very much not preferably as by reaction irreversible capacity become excessive so that battery capacity reduce.

Furthermore, it is possible to such as lithium hexafluoro phosphate (LiPF is used in combination₆) and LiBF4 (LiBF₄) lithium fluoride salt, And join in nonaqueous electrolytic solution.Accordingly, owing to creating the aluminium fluoride etc. being derived from lithium salts, therefore can more effectively prevent The generation of the corrosion only caused due to the moisture in such as heteropolyacid salt compound and acid composition.

In heteropolyacid salt compound according to the first embodiment of the invention, as by shown by formula (I) and (II), Acid composition (the H in formula (I)_xOr the H in formula (II)_p) can be with the salt (A in formula (I)_yOr the A in formula (II)_q) be present in together In compound.Further, such as, as previously described, preferably the amount of moisture and the amount of acid composition are the most little in nonaqueous electrolytic solution In 50ppm and no more than 100ppm.As long as the amount of the amount of moisture and acid composition falls within the above range, it is possible to use not saliferous Heteropoly acid and the mixture according to the heteropolyacid salt compound of first embodiment of the invention.

(1-2) synthetic method of heteropolyacid salt compound

Although the synthetic method of the heteropolyacid salt compound according to first embodiment of the invention is not particularly limited, but The method that the example of synthetic method includes making heteropoly acid mix with acid salt, hydroxide etc.；And make tungsten oxide, molybdenum oxide and The method of acid salt mixing.Heteropolyacid salt is separated by such as Crystallization Separation and vacuum drying method.And it is possible to by The structure of the heteropolyacid salt compound of synthesis is confirmed in X-ray diffraction or UV or IR measurement.

Further, the nonaqueous electrolytic solution comprising the heteropolyacid salt compound according to first embodiment of the invention can be by mixed Close and be ready to use in solvent and the heteropoly acid of nonaqueous electrolytic solution, then pass through azeotropic mixture or utilize desiccant dehydration, exchanged by ion Sour composition minimizing technology, or prepared by other method.(1-3) wherein there was added the nonaqueous electrolytic solution of heteropolyacid salt compound Constitute

[electrolytic salt]

Electrolytic salt can such as comprise one or both or more kinds of light metal salt such as lithium salts.The example bag of this lithium salts Include lithium hexafluoro phosphate (LiPF₆), LiBF4 (LiBF₄), lithium perchlorate (LiClO₄), hexafluoroarsenate lithium (LiAsF₆), four benzene Ylboronic acid lithium (LiB (C₆H₅)₄), Loprazolam lithium (LiCH₃SO₃), trifluoromethayl sulfonic acid lithium (LiCF₃SO₃), tetrachloro-lithium aluminate (LiAlCl₄), hexafluorosilicic acid two lithium (Li₂SiF₆), lithium chloride (LiCl) and lithium bromide (LiBr).Especially, free hexafluoro phosphorus is selected Acid lithium (LiPF₆), LiBF4 (LiBF₄), lithium perchlorate (LiClO₄) and hexafluoroarsenate lithium (LiAsF₆) in the group that forms At least one member is preferred, and lithium hexafluoro phosphate (LiPF₆) it is preferred.This is because the resistance of nonaqueous electrolyte Reduce.In particular it is preferred to lithium hexafluoro phosphate (LiPF₆) it is used together LiBF4 (LiBF₄).This is because can obtain High effect.

[nonaqueous solvent]

The example of the nonaqueous solvent that can use includes ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), γ-Ding Nei Ester, gamma-valerolactone, 1,2-dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, Pentamethylene oxide., DOX, 4-methyl isophthalic acid, 3-dioxolanes, 1,3-dioxane, Isosorbide-5-Nitrae-dioxane, methyl acetate, ethyl acetate, methyl propionate, propanoic acid second Ester, methyl butyrate, methyl isobutyrate, methyl trimethylacetate, tri-methyl ethyl acetate, acetonitrile, glutaronitrile, adiponitrile, methoxy Base acetonitrile, 3-methoxypropionitrile, DMF, N-Methyl pyrrolidone, N-methyloxazolidinone, N, N '-diformazan Base imidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate and dimethyl sulfoxide.This is because it is non-aqueous being provided with Electrolyte electrochemical device such as battery can obtain capacity, cycle characteristics and the preservation characteristics of excellence.These materials can Individually or to use with the multiple mixture in them.

The free ethylene carbonate of choosing (EC), propylene carbonate (PC), dimethyl carbonate is comprised it is particularly preferred to use (DMC), molten as solvent of at least one member in the group that diethyl carbonate (DEC) and Ethyl methyl carbonate (EMC) form Agent.This is because sufficient effect can be obtained.In this case, it is particularly preferred to use comprises it, each is all high viscous The ethylene carbonate of degree (high-k) solvent (such as, than DIELECTRIC CONSTANT ε >=30) or propylene carbonate and its each It it is all the mixture of dimethyl carbonate, diethyl carbonate or the Ethyl methyl carbonate of low viscosity solvent (such as, viscosity≤1mPa s) Solvent.This is because the dissociation properties of electrolytic salt and the mobility of ion can be improved so that higher effect can be obtained Really.

Preferably electrolyte comprises the cyclic carbonate represented by lower formula (III) or (IV).Can also use and select free style (III) combination of two or more and in (IV) compound of representing.

In formula (III), each in R1 to R4 represents hydrogen group, halogen group, alkyl or haloalkyl, and condition is At least one in R1 to R4 represents halogen group or haloalkyl.

In formula (IV), each in R5 and R6 represents hydrogen group or alkyl.

The example of the cyclic carbonate with halogen represented by formula (III) include 4-fluoro-1,3-dioxolan-2-one, 4-chlorine-1,3-dioxolane-2-ketone, 4,5-bis-fluoro-DOX-2-ketone, four fluoro-DOX-2-ketone, 4- Chloro-5-fluoro-1,3-dioxolan-2-one, 4,5-bis-chloro-DOX-2-ketone, four chloro-DOX-2-ketone, 4,5-bis trifluoromethyls-DOX-2-ketone, 4-Trifluoromethyl-1,3-dioxolan-2-one, 4,5-bis-fluoro-4,5-bis- Methyl isophthalic acid, 3-dioxolan-2-one, 4,4-bis-fluoro-5-methyl isophthalic acid, 3-dioxolan-2-one, 4-ethyl-5,5-bis-fluoro-1,3- Dioxolan-2-one, 4-fluoro-5-Trifluoromethyl-1,3-dioxolan-2-one, 4-methyl-5-Trifluoromethyl-1,3-dioxy penta Ring-2-ketone, 4-fluoro-4,5-dimethyl-DOX-2-ketone, 5-(1,1-bis-fluoro ethyl)-4,4-bis-fluoro-1,3-dioxy Penta ring-2-ketone, 4,5-bis-chloro-4,5-dimethyl-DOX-2-ketone, 4-ethyl-5-fluoro-DOX-2- Ketone, 4-ethyl-4,5-bis-fluoro-DOX-2-ketone, 4-ethyl-4,5,5-tri-fluoro-DOX-2-ketone and 4- Fluoro-4-methyl isophthalic acid, 3-dioxolan-2-one.These materials can individually or use with the multiple mixture in them. Wherein, 4-fluoro-1,3-dioxolan-2-one and 4,5-bis-fluoro-DOX-2-ketone is preferred.This is because not only These materials are easily obtained, but also can obtain the highest effect.

The example of the cyclic carbonate with unsaturated bond represented by formula (IV) includes vinylene carbonate (1,3-dioxy Heterocyclic pentene-2-ketone), methyl vinylene (4-methyl isophthalic acid, 3-dioxole-2-ketone), carbonic acid ethyl Asia ethylene Ester (4-ethyl-1,3-dioxole-2-ketone), 4,5-dimethyl-1,3-dioxole-2-ketone, 4,5-diethyl- 1,3-dioxole-2-ketone, 4-fluoro-1,3-dioxole-2-ketone and 4-Trifluoromethyl-1,3-dioxane penta Alkene-2-ketone.These materials can individually or use with the multiple mixture in them.Wherein, vinylene carbonate is Preferably.This is because not only this material is easily obtained, but also high effect can be obtained.

[macromolecular compound]

According to the first embodiment of the invention, there is nonaqueous solvent and non-water power that electrolytic salt is mixed therein Solution liquid can comprise the holding material containing macromolecular compound thus form so-called gel.

The material of gelation macromolecular compound can be can be used as wherein after adsorption solvent.The example includes that fluorocarbon radical is high Molecular compound such as Kynoar and vinylidene fluoride and the copolymer of hexafluoropropene；Ether macromolecular compound is such as Poly(ethylene oxide) and the cross-linked material comprising poly(ethylene oxide)；And comprise polyacrylonitrile, poly(propylene oxide) or polymethyl Acid methyl ester is as the compound of repetitive.This macromolecular compound can be individually or with two or more in them Mixture uses.

Especially, from the viewpoint of oxidation-reduction stability, fluorocarbon radical macromolecular compound is desired；And especially It is that it is preferred for comprising vinylidene fluoride and hexafluoropropene as the copolymer of component.And, this copolymer can comprise insatiable hunger With the monoesters such as monomethyl maleate of binary acid, vinyl halides such as CTFE, the cyclic carbonate of unsaturated compound Ester such as vinylene carbonate, acryloyl group vinyl monomer (acryl vinyl monomer) containing epoxy radicals etc. is as group Point.This is because higher characteristic can be obtained.

Method for forming gel-like electrolyte layer is described below.

According to the first embodiment of the invention, comprise in nonaqueous electrolytic solution by formula (I) and (II) at least One heteropolyacid salt compound represented.Accordingly, moisture and the amount of acid composition in nonaqueous electrolytic solution can be reduced.Then, pass through Use such nonaqueous electrolytic solution for nonaqueous electrolyte battery, coating can be formed in negative terminal surface, thus can obtain For suppressing the effect of the side reaction of nonaqueous electrolytic solution.

2. the second embodiment

Nonaqueous electrolyte battery according to second embodiment of the invention is described.Implementing according to the present invention second Nonaqueous electrolyte battery in mode is column type nonaqueous electrolyte battery.

(2-1) structure of nonaqueous electrolyte battery

Fig. 1 shows the cross-sectional configuration of the nonaqueous electrolyte battery according to second embodiment of the invention.Fig. 2 shows enlargedly Go out a part for the rolled electrode bodies 20 shown in Fig. 1.This nonaqueous electrolyte battery is that the capacity of wherein negative pole is based on work The lithium rechargeable battery expressed for the embedding of lithium and the deintercalation of electrode reaction thing.

[the whole structure of nonaqueous electrolyte battery]

In this nonaqueous electrolyte battery, the rolled electrode that wherein positive pole 21 and negative pole 22 are laminated via barrier film 23 and wind Body 20 and a pair insulation board 12 and 13 are mostly held in the inside of substantially hollow column-shaped battery case 11.Use this cylinder The battery structure of shape battery case 11 is referred to as column type.

Battery case 11 is made up of the ferrum (Fe) being such as coated with nickel (Ni), and one end seal is closed, and the other end is unlimited.? The inside of battery case 11, a pair insulation board 12 and 13 is respectively perpendicular to wind side face and arranges, in order to be placed in by rolled electrode bodies 20 Therebetween.

At the opening of battery case 11, battery cover 14 is by with being arranged on the relief valve mechanism 15 in this battery cover 14 and just PTC device (PTC device) 16 is installed via packing ring 17 caulked, and the inside of battery case 11 is hermetically sealed.

Battery cover 14 is made up of such as identical with battery case 11 material.Relief valve mechanism 15 is via ptc device 16 are electrically connected to battery cover 14.In this relief valve mechanism 15, when making electricity due to internal short-circuit or from outside heating etc. When the interior pressure in pond reaches more than certain value, discoid plate 15A overturns, and thus cuts off between battery cover 14 and rolled electrode bodies 20 Electrical connection.

When the temperature increases, ptc device 16 controls electric current by increasing resistance value, thus prevents by big electricity The abnormal delivery in hot weather that stream causes is raw.Packing ring 17 is made up of such as insulant, and coats Colophonium in its surface.

Such as, centrepin 24 is inserted into the center of rolled electrode bodies 20.In rolled electrode bodies 20, make aluminum (Al) etc. The positive wire 25 become is connected to positive pole 21；And the negative wire 26 being made up of nickel (Ni) etc. is connected to negative pole 22.Positive pole draws Line 25 is electrically connected to battery cover 14 by being soldered to relief valve mechanism 15；And negative wire 26 is electrically connected to by welding Battery case 11.

[positive pole]

Positive pole 21 is the most such positive pole, wherein positive electrode active material layer 21B be arranged on have a pair relative to each other On two surfaces of the positive electrode collector 21A on surface.But, positive electrode active material layer 21B can be arranged on positive electrode collector 21A Only one surface on.In the heteropolyacid salt compound that formation source free style (I) and (II) represents on positive electrode surface at least A kind of coating.The coating formed comprises and is deposited by the electrolysis of heteropolyacid salt compound by precharge or charging Deposit.This deposit comprises polyacid and/or polyacid compound.On positive pole, the deposit of deposition depends on to be added to battery The amount of the heteropolyacid salt compound in system is formed.

Positive electrode collector 21A is made up of such as metal material such as aluminum, nickel and rustless steel.

Positive electrode active material layer 21B comprises one or both or more kinds of positive electrode conduct that can embed with removal lithium embedded Positive active material, and if so desired, other material, such as binding agent and conductive agent can be comprised further.

As the positive electrode that can embed with removal lithium embedded, such as, lithium-containing compound is preferred.This is because can obtain Obtain high energy density.The example of this lithium-containing compound includes containing lithium and the composite oxides of transition metal and contains Lithium and the phosphate compounds of transition metal.Wherein, at least in the group selecting free cobalt, nickel, manganese and ferrum composition is comprised Kind member is preferred as the compound of transition metal.This is because higher voltage can be obtained.

Example containing lithium and the composite oxides of transition metal includes lithium cobalt composite oxide (Li_xCoO₂), lithium nickel Composite oxides (Li_xNiO₂), lithium/nickel/cobalt composite oxide (Li_xNi_1-zCo_zO₂(z ＜ 1)), lithium nickel cobalt manganese oxide (Li_xNi_(1-v-w)Co_vMn_wO₂(v+w ＜ 1)) and it is respectively provided with the complex Li-Mn-oxide (LiMn of spinel structure₂O₄) or Li-mn-ni compound oxide (LiMn_2-tNi_tO₄(t ＜ 2)).Wherein, the composite oxides containing cobalt are preferred.This is because not only High power capacity can be obtained, but also the cycle characteristics of excellence can be obtained.Additionally, containing lithium and the phosphate of transition metal The example of compound includes lithium iron phosphate compound (LiFePO₄) and ithium iron manganese phosphate compounds (LiFe_1-uMn_uPO₄(u ＜ 1))。

And, from the viewpoint of can obtaining higher electrode filling capacity and cycle characteristics, it is possible to embed and deintercalation The positive electrode of lithium can be formed through coating by upper with by any one fine grained constituted in other lithium-containing compound State the surface of nuclear particle that any one in lithium-containing compound is constituted and the composite particles obtained.

Furthermore it is possible to the example embedding the positive electrode with removal lithium embedded includes oxide, such as titanium oxide, vanadium oxide and two Manganese oxide；Disulphide, such as titanium disulfide and molybdenum sulfide；Chalcogenide, such as selenizing niobium；Sulfur；And conducting polymer, Such as polyaniline and polythiophene.Much less, it is possible to embed and the positive electrode of removal lithium embedded can be in addition to described above those Outside other material.Further, above-named a series of positive electrode can be that two or more in them are with arbitrarily The mixture of combination.

[negative pole]

Negative pole 22 is the most such negative pole, wherein, negative electrode active material layer 22B be arranged on have a pair relative to each other On two surfaces of the negative electrode collector 22A on surface.But, negative electrode active material layer 22B can be arranged on negative electrode collector 22A Only one surface on.In the heteropolyacid salt compound that formation source free style (I) and (II) represents in negative terminal surface at least A kind of coating.The coating formed comprises to be tied with three-dimensional network after heteropolyacid salt compound is electrolysed by precharge or charging The deposit of structure deposition.This coating is formed at least one of surface of negative pole, and comprises containing one or more many The amorphous polyacid of element and/or polyacid compound, and this amorphous polyacid and/or polyacid compound comprise electrolyte and employing is solidifying Glue form.

The gel coating formed in negative terminal surface according to second embodiment of the invention can such as pass through SEM (scanning electron microscope) confirms, as it is shown on figure 3, wherein this coating to comprise the amorphous being made up of one or more multielements many Acid and/or polyacid compound.Fig. 3 is the SEM image of the negative terminal surface after charging, and is to rinse electrolyte to obtain the most after drying The photo taken.

And, the deposition of amorphous polyacid and/or polyacid compound can be based on by X-ray absorption fine structure (XAFS) Analyze the structural analysis of the coating formed in negative terminal surface and by time-of-flight type secondary ion mass spectrometry (ToF-SIMS) Molecular chemistry information confirm.

Fig. 4 shows in the negative terminal surface of nonaqueous electrolyte battery by time-of-flight type secondary ion mass spectrometry (ToF-SIMS) example of the secondary ion spectrum carried out, negative pole coating the most second embodiment of the invention is passed through will Silico-tungstic acid joins in battery system and is charged battery and is formed.It is noted that exist and comprise tungsten (W) from Fig. 4 With oxygen (O) as the molecule of constitution element.

Further, Fig. 5 shows in the negative terminal surface of nonaqueous electrolyte battery by X-ray absorption fine structure (XAFS) Analyze the example of the radial structure function of W-O key obtained by the Fourier transformation of wave spectrum, wherein according to the of the present invention The negative pole coating of two embodiments is formed by joining in battery system by silico-tungstic acid and be charged battery.And, Fig. 5 together illustrates as the tungsten that may be used for the polyacid according to second embodiment of the invention with the analysis result of negative pole coating Acid (WO₃Or WO₂) and as the silico-tungstic acid (H that may be used for according to the heteropoly acid in second embodiment of the invention₄ (SiW₁₂O₄₀)·26H₂The example of the radial structure function of the W-O key each of in O).

The peak L1 of the deposit from Fig. 5 it is noted that in negative terminal surface have be in respectively with silico-tungstic acid (H₄ (SiW₁₂O₄₀)·26H₂O), tungsten dioxide (WO₂) and Tungstic anhydride. (WO₃) the peak of peak L2, L3 position different with L4, and There is different structures.It is the Tungstic anhydride. (WO of typical tungsten oxide in both of which₃) and tungsten dioxide (WO₂) and conduct Raw-material silico-tungstic acid (H according to second embodiment of the invention₄(SiW₁₂O₄₀)·26H₂O) in, it is contemplated that radial structure letter Number, main peak is present in the range of 1.0 to 2.0 angstroms, and also can confirm that peak is in the range of 2.0 to 4.0 angstroms.

On the other hand, main according to deposit on the positive pole in second embodiment of the invention and each in negative pole The W-O bond length of the polyacid being made up of wolframic acid from distribution in, although peak is proved in the range of 1.0 to 2.0 angstroms, but upper The different peaks suitable from those in peak L1 are not found outside stating scope.That is, substantially do not have in the range of more than 3.0 angstroms Observe peak.In this case, it can be verified that the deposit in negative terminal surface is amorphous.

Negative electrode collector 22A is such as made up of metal material such as copper, nickel and rustless steel.

Negative electrode active material layer 22B comprises one or both or more kinds of negative material conduct that can embed with removal lithium embedded Negative electrode active material, and if so desired, other material such as binding agent and conductive agent can be comprised further.In this situation Under, it is preferably able to the rechargeable capacity embedding the negative material with the removal lithium embedded discharge capacity more than positive pole.About binding agent Identical with those in positive pole with the details of conductive agent.

The example that can embed the negative material with removal lithium embedded includes material with carbon element.The example of such material with carbon element includes Yi Shi Inkization carbon, (002) interplanar distance are the graphite that the difficult graphitized carbon of more than 0.37nm and (002) interplanar distance are not more than 0.34nm. More specifically, pyrolytic carbon, coke, vitreous carbon fiber, organic high molecular compound sintered body, activated carbon and charcoal are listed Black.Wherein, the example of coke includes pitch coke, needle coke and petroleum coke.Organic high molecular compound as referred to herein burns Adult is by burning till the material that phenolic resin, furane resins etc. obtain via carbonization at a proper temperature.Material with carbon element is Preferably as the change of the crystal structure of the embedding of adjoint lithium and deintercalation is the least, and it is close therefore can to obtain high-energy Spend, it is possible to obtain excellent cycle characteristics, and material with carbon element also plays the effect of conductive agent.The shape of material with carbon element can be fiber Any one in shape, spherical, granular or laminar (squamous).

In addition to above-mentioned material with carbon element, it is possible to the example embedding the negative material with removal lithium embedded also includes can embedding and deintercalation Lithium and comprise the material as constitution element of at least one member in the group selecting free metallic element and semimetallic elements to form Material.This is because high-energy-density can be obtained.Such negative material can be metallic element or the simple substance of semimetallic elements, Alloy or compound, or can be, in it is at least some of, there is one or both or the material of more kinds of phase.Except by Outside the alloy that two or more metallic elements are constituted, " alloy " as referred to herein also includes comprising one or more metals Element and the alloy of one or more semimetallic elements.Further, " alloy " can comprise nonmetalloid.The example of its structure Including solid solution, eutectic (eutectic mixture), intermetallic compound and wherein two or more in them coexist Structure.

The example of metallic element or semimetallic elements includes metallic element or the semimetal that can form alloy together with lithium Element.Its instantiation includes magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), stannum (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) and platinum (Pt).Wherein, it is selected from At least one member in silicon and stannum is preferred, and silicon is preferred.This is because silicon and stannum have bigger embedding Ability with removal lithium embedded so that high-energy-density can be obtained.

The example of the negative material comprising at least one member in silicon and stannum includes the simple substance of silicon, alloy or chemical combination Thing；The simple substance of stannum, alloy or compound；And in it is at least some of, there is one or both or the material of more kinds of phase.

The example of the alloy of silicon includes containing selecting free stannum (Sn), nickel (Ni), copper (Cu), ferrum (Fe), cobalt (Co), manganese (Mn), in the group that zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) form at least A kind of member is as the alloy of the second constitution element in addition to silicon.The example of the alloy of stannum includes containing selecting free silicon (Si), nickel (Ni), copper (Cu), ferrum (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), at least one member in the group that antimony (Sb) and chromium (Cr) form is as the second constitution element in addition to stannum (Sn) Alloy.

The example of the compound of stannum or the compound of silicon includes comprising oxygen (O) or the compound of carbon (C), and these chemical combination Thing can comprise above-mentioned second constitution element in addition to stannum (Sn) or silicon (Si) further.

As the negative material of at least one member comprised in silicon (Si) and stannum (Sn), such as, stannum (Sn) is comprised As the first constitution element, and the material of the second constitution element in addition to this stannum (Sn) and the 3rd constitution element is special Preferably.Much less, this negative material can be used together with above-mentioned negative material.Second constitution element is to select free cobalt (Co), ferrum (Fe), magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), indium (In), cerium (Ce), hafnium (Hf), tantalum (Ta), tungsten (W), bismuth (Bi) and silicon (Si) group At least one member in the group become.3rd constitution element is the group selecting free boron (B), carbon (C), aluminum (Al) and phosphorus (P) to form In at least one member.This is because when comprising the second constitution element and three constitution elements, cycle characteristics can be improved.

Especially, negative material is preferably the material Han SnCoC, and this contains SnCoC material and comprises stannum (Sn), cobalt (Co) and carbon (C) as constitution element, and the content of the carbon (C) having by mass more than 9.9% and is not more than by mass In the range of 29.7%, and the ratio (Co/ (Sn+Co)) of cobalt (Co) and stannum (Sn) and cobalt (Co) summation is by mass 30% Above and be not more than in the range of by mass 70%.This is because in above-mentioned compositing range, be possible not only to obtain high-energy Density, and the cycle characteristics of excellence can be obtained.

If so desired, this contains SnCoC material can comprise other constitution element further.As other constitution element, example As, silicon (Si), ferrum (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), molybdenum (Mo), aluminum (Al), phosphorus (P), gallium (Ga) and bismuth (Bi) are preferred.This contains SnCoC material can comprise two or more in these elements.This is Because capacity characteristic or cycle characteristics can be greatly improved.

This contains SnCoC material has containing stannum (Sn), cobalt (Co) and the phase of carbon (C), and preferably this phase has low crystallization Property structure or non crystalline structure (impalpable structure).And, at this containing in SnCoC material, preferably as constitution element carbon extremely A few part is combined with metallic element or the semimetallic elements as other constitution element.Be because while it is believed that due to Stannum (Sn) etc. assemble or crystallization and cause the reduction of cycle characteristics, but when carbon is combined with other element, can be suppressed this The gathering of sample or crystallization.

For checking that the example of the measuring method of the bonding state of element includes x-ray photoelectron power spectrum (XPS).At this In XPS, for graphite, making to obtain the energy correction device at the peak of the 4f track (Au4f) of gold atom at 84.0eV In, the peak of the 1s track (C1s) of carbon occurs in 284.5eV.Further, for surface contamination carbon, the peak of the 1s track (C1s) of carbon Occur in 284.8eV.On the contrary, when the charge density of carbon is the highest, such as, when carbon and metallic element or semimetallic elements knot During conjunction, the peak of C1s occurs in less than the region of 284.5eV.That is, when the composite wave about the C1s obtained containing SnCoC material Peak occurs in less than time in the region of 284.5eV, the carbon (C) comprised in containing SnCoC material at least some of with as it The metallic element of its constitution element or semimetallic elements combine.

In XPS measuring, such as, the peak of C1s is used to correct for the energy axes of spectrum.Exist generally, due to surface contamination carbon On surface, therefore the peak of the C1s of surface contamination carbon is fixed on 284.8eV, and this peak is used as energy reference.At XPS In measurement, due to C1s peak waveform as include surface contamination carbon peak and in containing SnCoC material the form at the peak of carbon And obtain, therefore surface contamination carbon peak and containing the peak of carbon in SnCoC material by utilizing the analysis being such as purchased software program And it is separated from one another.In the analysis of waveform, the position being present in the main peak on minimum combination energy side is used as energy reference (284.8eV)。

Further, it is possible to the example embedding the negative material with removal lithium embedded includes it, each can embed the gold with removal lithium embedded Belong to oxide and macromolecular compound.The example of metal-oxide includes ferrum oxide, ruthenium-oxide and molybdenum oxide；And producing high-molecular The example of compound includes polyacetylene, polyaniline and polypyrrole.

Other material that the negative material with removal lithium embedded can be in addition to outside those described above can be embedded.Further, arrange above The negative material lifted can be the mixture in any combination of two or more in them.

Negative electrode active material layer 22B can such as pass through in vapor phase method, liquid phase method, spraying process, sintering method or cladding process Any one, or the combined method of two or more in these methods and formed.When negative electrode active material layer 22B is by using The combined method of two or more in vapor phase method, liquid phase method, spraying process, sintering method or these methods and when being formed, preferably Negative electrode active material layer 22B and negative electrode collector 22A is alloyed at least some of interface betwixt.And specifically, it is preferable to , in interface, the constitution element of negative electrode collector 22A is diffused in negative electrode active material layer 22B, negative electrode active material layer The constitution element of 22B is diffused in negative electrode collector 22A, or these constitution elements can inter-diffuse among each other.This is Because being possible not only to suppress owing to rupturing of causing with the expansion of negative electrode active material layer 22B of charge/discharge and contraction is (broken Bad), and the electronic conductivity between negative electrode active material layer 22B and negative electrode collector 22A can be improved.

The example of vapor phase method includes physical deposition methods and chemical deposition, specifically, vaccum gas phase sedimentation method, sputtering method, Ion plating method, laser ablation (melting) method, thermal chemical vapor deposition (CVD) method and plasma chemical vapor deposition.Make For liquid phase method, such as plating (electrolysis plating) and the known technology of electroless-plating can be used.Sintering method as referred to herein is A kind of such method, wherein after making graininess negative electrode active material mix with binding agent etc., is dispersed in mixture In solvent, and it is coated, then by the material of coating higher than carrying out heat treatment at a temperature of the fusing point of binding agent etc..About Sintering method, it is also possible to utilize known technology, and the example includes that atmosphere sintering method, reaction sintering method and hot pressing are burnt till Method.

[barrier film]

Positive pole 21 is separated from each other by barrier film 23 with negative pole 22, and allows lithium ion to pass through the most simultaneously to prevent due to two The short circuit current that contact between electrode causes.This barrier film 23 is by such as by such as politef, polypropylene and polyethylene The perforated membrane that synthetic resin is made；Perforated membrane being made up of pottery etc. is constituted, and also can use in these perforated membranes The layered product of two or more.Barrier film 23 can be impregnated with the electrolyte of above-mentioned first embodiment according to the present invention.

(2-2) manufacture method of nonaqueous electrolyte battery

Above-mentioned nonaqueous electrolyte battery can be manufactured in the following manner.

[manufacture of positive pole]

First, positive pole 21 is manufactured.Such as, positive electrode, binding agent and conductive agent carry out mix to form positive pole to mix Compound, is then dispersed in organic solvent forming the cathode mix slurry of pasty state.Subsequently, it is coated with by scraper or scraping article Cloth machines etc., are uniformly coated on this cathode mix slurry on two surfaces of positive electrode collector 21A, then make it be dried. Finally, by roll squeezer etc., coating is pressed, heats the most simultaneously, thus form positive electrode active material Matter layer 21B.In such a case, it is possible to repeat compressing repeatedly.

[manufacture of negative pole]

Then, negative pole 22 is manufactured.Such as, carry out mixing to be formed by negative material and binding agent and optional conductive agent Negative electrode mix, is then dispersed in organic solvent forming the negative electrode mix slurry of pasty state.Subsequently, by scraper or Scraping strip coating machines etc., are uniformly coated on this negative electrode mix slurry on two surfaces of negative electrode collector 22A, then make it It is dried.Finally, by roll squeezer etc., coating is pressed, heats the most simultaneously, thus form negative pole Active material layer 22B.

[assembling of nonaqueous electrolyte battery]

Then, by welding etc., positive wire 25 is arranged in positive electrode collector 21A, and will bear also by welding etc. Pole lead-in wire 26 is arranged in negative electrode collector 22A.Afterwards, positive pole 21 and negative pole 22 are wound via barrier film 23；By positive pole The front end of lead-in wire 25 is soldered to relief valve mechanism 15；And also the front end of negative wire 26 is soldered to battery case 11.Then, will Positive pole 21 and the negative pole 22 of winding are placed between a pair insulation board 12 and 13 and are contained in the inside of battery case 11.By positive pole 21 After being contained in battery case 11 with negative pole 22, nonaqueous electrolytic solution according to the first embodiment of the invention is injected into battery Shell 11 is interior and is immersed in barrier film 23.Afterwards, after via packing ring 17 caulked by battery cover 14, relief valve mechanism 15 and just temperature Degree coefficient unit 16 is fixed to the opening of battery case 11.This completes the nonaqueous electrolyte battery shown in Fig. 2 and Fig. 3.

In such nonaqueous electrolyte battery, when initial charge, comprise in nonaqueous electrolytic solution by formula (I) and (II) at least one in the heteropolyacid salt compound represented is electrolysed and is deposited, thus forms coating in negative terminal surface.By The fact that at least one in nonaqueous electrolytic solution comprises the heteropolyacid salt compound represented by formula (I) and (II), this can be embedding Enter the compound with deintercalate lithium ions and on negative pole, form stable SEI coating when the initial stage of use by charge/discharge, thus Inhibit solvent and the decomposition of electrolytic salt in nonaqueous electrolytic solution.The SEI formed by heteropoly acid and/or heteropoly compound is coated with Layer is inorganic and firm, and is embedding and resistance when deintercalate lithium ions is the least simultaneously, and therefore can recognize For causing the deterioration of capacity etc. hardly.Accordingly, it may be concluded that single fluorophosphoric acid of the lithium salts being bordering in electrolyte as tap Salt and/or difluorophosphoric acid salt add fashionable together with heteropoly acid and/or heteropoly compound, greatly suppress main electrolytic salt Decomposition, thus can be formed and there is low-resistance SEI coating.

Due to the electrolyte quilt of at least one being wherein dissolved with in the heteropolyacid salt compound represented by formula (I) and (II) The fact that be impregnated in negative electrode active material layer 22B, in the heteropolyacid salt compound that therefore source free style (I) and (II) represent The compound of at least one can be deposited in negative electrode active material layer 22B by charging or precharge.Accordingly, source free style (I) compound of at least one and in (II) heteropolyacid salt compound of representing may reside in anode active material particles In.

Further, owing to being wherein dissolved with the electricity of at least one in the heteropolyacid salt compound represented by formula (I) and (II) Solve the fact that liquid is impregnated in positive electrode active material layer 21B, the heteropolyacid salt chemical combination that therefore source free style (I) and (II) represent The compound of at least one in thing can be deposited in positive electrode active material layer 21B by charging or precharge.Accordingly, it is derived from The compound of at least one in the heteropolyacid salt compound represented by formula (I) and (II) may reside in positive active material In Li.

The compound of at least one in the heteropolyacid salt compound that source free style (I) and (II) represent in negative pole coating Presence or absence can such as by x-ray photoelectron power spectrum (XPS) analyze or time-of-flight type secondary ion mass spectrometry (ToF- SIMS) confirm.In this case, take battery apart, then rinse by dimethyl carbonate.This is done to removing and be present in table The solvent composition with low volatility on face and electrolytic salt.Expect, if entirely possible, take in an inert atmosphere Sample.

In second embodiment of the invention, comprise in nonaqueous electrolytic solution by formula (I) and (II) represent miscellaneous At least one in multi-acid salt compound.Accordingly, it is possible not only to suppress the deterioration of battery behavior when initial charge, and permissible Suppression electrode active material and side reaction of nonaqueous electrolytic solution in hot environment so that battery behavior can be improved.According to this The interpolation of the heteropolyacid salt compound inventing the second embodiment goes for one-shot battery and secondary cell, this is because During initial charge and also can obtain described effect when High temperature storage.

3. the 3rd embodiment

Nonaqueous electrolyte battery according to third embodiment of the present invention is described.Implement according to the present invention the 3rd The nonaqueous electrolyte battery of mode is the laminated membrane type nonaqueous electrolyte battery packed by laminated film.

(3-1) structure of nonaqueous electrolyte battery

Nonaqueous electrolyte battery according to third embodiment of the present invention is described.Fig. 6 is according to the present invention The exploded perspective structure example of the nonaqueous electrolyte battery of three embodiments；And Fig. 7 shows enlargedly along the volume shown in Fig. 6 Cross section around the I-I line of electrode body 30.

This nonaqueous electrolyte battery has configuration which, is mainly provided with positive wire 31 and negative wire 32 Rolled electrode bodies 30 is contained in the inside of membranaceous package 40.The battery structure using this membranaceous package 40 is referred to as laminated film Type.

Such as, positive wire 31 and each in negative wire 32 from the inside of package 40 towards outside with identical Direction is drawn.Positive wire 31 is made up of such as metal material such as aluminum, and negative wire 32 by such as metal material such as copper, Nickel and stainless steel are constituted.Such metal material is for example formed as lamellar or network-like.

Package 40 is by such as by the aluminium lamination press mold obtained with this order bonding nylon membrane, aluminium foil and polyethylene film Constitute.Such as, this package 40 has a structure in which, in the structure shown here, makes the respective outer rim of two rectangular aluminum laminated films Portion is by fusion or utilizes binding agent to be adhering to each other by this way so that polyethylene film is relative with rolled electrode bodies 30 and sets Put.

For the generation preventing extraneous air from invading, contact membranes 41 is inserted into package 40 and positive wire 31 and negative pole Between each in lead-in wire 32.This contact membranes 41 is had cohesiveness by each in positive wire 31 and negative wire 32 Material constitute.The example of such material includes vistanex such as polyethylene, polypropylene, modified poly ethylene and modification Polypropylene.

Package 40 can also be made up of the laminated film with other laminar structures or by polymeric film such as polypropylene screen Or metal film replaces above-mentioned aluminium lamination press mold to constitute.

Fig. 7 shows the cross-sectional configuration of the I-I line along the rolled electrode bodies 30 shown in Fig. 6.This rolled electrode bodies 30 is logical Cross the rolled electrode that positive pole 33 and negative pole 34 being carried out is laminated and winds this layered product via barrier film 35 and electrolyte 36 and prepares Body, and its outermost perimembranous is by protecting band 37 protection.

Positive pole 33 is the most such positive pole, and wherein positive electrode active material layer 33B is arranged on two of positive electrode collector 33A On surface.

Negative pole 34 is the most such negative pole, and wherein negative electrode active material layer 34B is arranged on two of negative electrode collector 34A On surface, and in negative terminal surface, form at least one in the heteropolyacid salt compound that source free style (I) and (II) represents Coating.In the coating formed, the deposit deposited by the electrolysis of heteropolyacid salt compound takes three dimensional structure, and And when in this structure in nonaqueous electrolytic solution is included in battery system, define the gel coating comprising amorphous polyacid.Just Pole 33 and negative pole 34 are arranged in such a way so that negative electrode active material layer 34B and positive electrode active material layer 33B phase each other Right.Positive electrode collector 33A, positive electrode active material layer 33B, negative electrode collector 34A, negative electrode active material layer 34B and barrier film 35 Structure respectively with second embodiment of the invention in positive electrode collector 21A, positive electrode active material layer 21B, negative pole Those structures of collector body 22A, negative electrode active material layer 22B and barrier film 23 are identical.

Electrolyte 36 comprises electrolyte according to the first embodiment of the invention and can be maintained at by this electrolyte Macromolecular compound therein, and be so-called gelatinous electrolyte.Gel-like electrolyte is preferably as not only may be used To obtain high ion-conductivity (such as, be at room temperature more than 1mS/cm), and it is possible to prevent the generation that liquid leaks.

(3-2) manufacture method of nonaqueous electrolyte battery

Such as manufacture this nonaqueous electrolyte battery by following three manufacture method (the first to the 3rd manufacture method).

(3-2-1) the first manufacture method

In the first manufacture method, first, such as, respectively according to the positive pole 21 according to second embodiment of the invention and negative The identical manufacturing step of pole 22, forms positive electrode active material layer 33B on two surfaces of positive electrode collector 33A thus just manufactures Pole 33, and on two surfaces of negative electrode collector 34A formed negative electrode active material layer 34B thus manufacture negative pole 34.

Subsequently, before preparation comprises electrolyte, macromolecular compound and the solvent according to first embodiment of the invention Liquid solution, and be coated onto in each in positive pole 33 and negative pole 34, then make solvent volatilization to form gel electricity Solve matter 36.Subsequently, positive wire 31 is arranged in positive electrode collector 33A, and also negative wire 32 is arranged on negative pole collection In electricity body 34A.

Subsequently, the positive pole 33 and the negative pole 34 that are respectively formed on nonaqueous electrolyte 36 are laminated via barrier film 35, by this layer Laminate winds in their longitudinal direction, and makes protection band 37 adhere to its outermost perimembranous afterwards, thus manufactures rolled electrode bodies 30.Finally, such as, rolled electrode bodies 30 is placed between membranaceous two package 40, and makes packaging by heat fused etc. The outer edge of part 40 is adhering to each other, thus is enclosed wherein by rolled electrode bodies 30.Now, contact membranes 41 is inserted into positive wire 31 and negative wire 32 in each and package 40 between.This completes nonaqueous electrolyte battery.

(3-2-2) the second manufacture method

In the second manufacture method, first, positive wire 31 is arranged in positive pole 33, and also negative wire 32 is pacified It is contained in negative pole 34.Subsequently, positive pole 33 and negative pole 34 are laminated via barrier film 35, layered product is entered in their longitudinal direction Row winding, and afterwards, make protection band 37 adhere to its outermost perimembranous, thus be manufactured as the volume of the precursor of rolled electrode bodies 30 Around body.

Subsequently, this coiling body is placed between two membranaceous packages 40, and make except in addition to outer edge It is adhering to each other by heat fused etc., thus coiling body is contained in bag-shaped package 40.Subsequently, preparation comprises according to this The electrolyte of bright first embodiment, the monomer as macromolecular materials, polymerization initiator and optional other material Expect the electrolyte composition of such as polymerization inhibitor, and be injected in bag-like package 40, and afterwards, by package 40 Opening carry out hermetic seal by heat fused etc..Subsequently, make monomer thermal polymerization to prepare macromolecular compound, thus formed solidifying Gelated electrolyte 36.This completes nonaqueous electrolyte battery.

(3-2-3) the 3rd manufacture method

In the 3rd manufacture method, first, except use, there is the macromolecular compound being coated on two surface Outside barrier film 35, in the way of identical with above-mentioned the second manufacture method, form coiling body and be contained in bag-shaped package In 40.

The example being coated in the macromolecular compound on this barrier film 35 included by vinylidene fluoride as gathering that component is constituted Compound, i.e. homopolymer, copolymer or multiple copolymer etc..Its instantiation includes Kynoar；By vinylidene fluoride and six The bipolymer that fluoropropene is constituted as component；And by vinylidene fluoride, hexafluoropropene and CTFE as group Divide the terpolymer constituted.

Macromolecular compound can comprise one or both or other macromolecular compound more kinds of and by inclined difluoro second The above-mentioned polymer that alkene is constituted as component.Subsequently, prepare electrolyte according to the first embodiment of the invention and noted Enter the inside to package 40, and afterwards, by the opening of the hermetic seal packages 40 such as heat fused.Finally, in heating After, weight is being applied while package 40, is making barrier film 35 via in macromolecular compound and positive pole 33 and negative pole 34 Each is in close contact.Accordingly, make electrolyte be impregnated in macromolecular compound, and make macromolecular compound gelatine with shape Become electrolyte 36.This completes nonaqueous electrolyte battery.

When the nonaqueous electrolyte battery manufactured by any one in above-mentioned first to the 3rd manufacture method is carried out preliminary filling When electricity or charging, negative terminal surface defines source free style (I) and in heteropolyacid salt compound that (II) represents at least one The coating planted.

According in third embodiment of the present invention, create and that in second embodiment of the invention The most identical effect.

4. the 4th embodiment

The nonaqueous electrolyte battery of the 4th embodiment according to the present invention is described.According to the present invention the 4th is real Execute the nonaqueous electrolyte battery of mode be the laminated membrane type nonaqueous electrolyte battery packed by laminated film and with according to this The nonaqueous electrolyte battery of the 3rd bright embodiment is identical, and difference is, in statu quo (directly) uses according to the present invention The electrolyte of the first embodiment.As a result, hereinafter, concentrate on according to those in third embodiment of the present invention Different points describes its structure.

(4-1) structure of nonaqueous electrolyte battery

In the nonaqueous electrolyte battery of the 4th embodiment according to the present invention, electrolyte is used to replace gel electrolysis Matter 36.As a result, rolled electrode bodies 30 has configuration which, wherein eliminates electrolyte 36, and electrolyte is immersed in barrier film In 35.

(4-2) manufacture method of nonaqueous electrolyte battery

Manufacture this nonaqueous electrolyte battery the most in the following manner.

First, such as, positive active material, binding agent and conductive agent carry out mixing to prepare cathode mix, and And be dispersed in the solvent of such as METHYLPYRROLIDONE to prepare cathode mix slurry by this cathode mix.Subsequently, This cathode mix slurry it is coated on two surfaces of positive electrode collector 33A and is dried, then gains being carried out Compressing to form positive electrode active material layer 33B.Thus manufacture positive pole 33.Subsequently, such as, by such as ultra-sonic welded, Means of spot welds etc., are engaged in positive electrode collector 33A by positive wire 31.

Further, such as, carry out mixing to prepare negative electrode mix by negative material and binding agent, be then dispersed in all As in the solvent of METHYLPYRROLIDONE to prepare negative electrode mix slurry.Subsequently, this negative electrode mix slurry is coated in On two surfaces of negative electrode collector 34A and be dried, then it is pressed to form negative electrode active material to gains Matter layer 34B.Thus manufacture negative pole 34.Subsequently, such as, by such as ultra-sonic welded, means of spot welds etc., negative wire 32 is engaged In negative electrode collector 34A.

Subsequently, positive pole 33 and negative pole 34 are wound via barrier film 35；Gains are placed in package 40；And it After, inject electrolyte according to the first embodiment of the invention, then package 40 is carried out hermetic seal.Thereby is achieved Nonaqueous electrolyte battery shown in Fig. 6 and Fig. 7.

In the 4th embodiment according to the present invention, create and that in second embodiment of the invention The most identical effect.

5. the 5th embodiment

The structure example of the nonaqueous electrolyte battery 20 according to fifth embodiment of the invention is described.Such as Fig. 8 Shown in, according to the nonaqueous electrolyte battery 20 of the 5th embodiment of the present invention, there is rectangular shape.

This nonaqueous electrolyte battery 20 manufactures in the following manner.As shown in Figure 8, first, rolled electrode bodies 53 is held It is contained in the pack case 51 as the Rectangular shell being made up of the metal of such as aluminum (Al), ferrum (Fe) etc..

Then, the electrode pin 54 being arranged on battery cover 52 and the electrode terminal 55 drawn from rolled electrode bodies 53 are made It is connected to each other, then passes through battery cover 52 and carry out airtight.Afterwards, comprise by formula (I) and (II) from electrolyte inlet 56 injection The electrolyte of at least one in the heteropolyacid salt compound represented, then passes through sealing member 57 and seals.By to made The battery made is charged or is pre-charged, and completes the nonaqueous electrolyte battery 20 of the 5th embodiment according to the present invention, The chemical combination of at least one in this nonaqueous electrolyte battery 20, in the heteropolyacid salt compound that source free style (I) and (II) represent Thing is deposited on the surface of negative pole.

Rolled electrode bodies 53 by carry out being laminated via barrier film by positive pole and negative pole and winding layer laminate and obtain.Due to just Pole, negative pole, barrier film and electrolyte are identical with those according to the first embodiment of the invention, therefore eliminate theirs Describe in detail.

According to the nonaqueous electrolyte battery 20 of the 5th embodiment according to the present invention, the gas of electrolyte can be suppressed to produce Raw, and it is possible to prevent the generation ruptured that the rising of the interior pressure caused owing to gas produces causes.

6. the 6th embodiment

The nonaqueous electrolyte battery of the 6th embodiment according to the present invention is described.According to the present invention the 6th is real The nonaqueous electrolyte battery executing mode is laminated membrane type nonaqueous electrolyte battery, and wherein electrode body is by lamination positive pole and negative pole Formed and packed by laminated film, and in addition to the structure of electrode body, according to the non-water power of the 6th embodiment of the present invention Solve electrolyte cell identical with according in third embodiment of the present invention.For this reason, the most only describe according to the present invention The electrode body of the 6th embodiment.

[positive pole and negative pole]

As it is shown in figure 9, positive pole 61 is by formation positive electrode active material layer on two surfaces of rectangle positive electrode collector Obtain.The preferably positive electrode collector of positive pole 61 is integrally formed with positive terminal.Further, by being formed on rectangle negative electrode collector Negative electrode active material layer is similarly produced negative pole 62.

Positive pole 61 and negative pole 62 are laminated with the order of positive pole 61, barrier film 63, negative pole 62 and barrier film 63, thus cambium layer Piezoelectricity polar body 60.In this laminated electrode body 60, the laminated state of holding electrode can be carried out by bonding insulating tape etc..Lamination electricity Polar body 60 is packed by laminated film etc., and is hermetically sealed in together with nonaqueous electrolytic solution in battery, and it is possible to make Nonaqueous electrolytic solution is replaced with gel electrolyte.

Embodiment

It is specifically described the present invention referring to the following example, but should not be construed as and present invention is limited only to these in fact Execute example.In the following description, the quality of heteropoly acid is defined through deducting the quality of the combination water that heteropoly acid is had and obtaining The value obtained；And the quality of heteropolyacid salt compound is defined through deducting the combination water that heteropolyacid salt compound had Quality and the value that obtains.

Heteropoly acid or heteropoly compound in the following example 1 and 2 are as follows.

Compound A: there is the phosphotungstic acid lithium of structure with Keggin

Compound B: there is the silicotungstate lithium of structure with Keggin

Compound C: there is the silico-tungstic acid TBuA of structure with Keggin

Compound D: there is the silico-tungstic acid tetrabutyl of structure with Keggin

Compound E: there is the phosphotungstic acid heptahydrate of structure with Keggin

Compound F: there is the silico-tungstic acid heptahydrate of structure with Keggin

Compound G: there is phosphotungstic acid three decahydrate of structure with Keggin

Compound H: there is silico-tungstic acid three decahydrate of structure with Keggin

[embodiment 1]

In embodiment 1, the kind by changing heteropolyacid salt compound to be added evaluates laminated membrane type battery Characteristic.

[manufacture of positive pole]

Using the cobalt acid lithium (LiCoO as positive active material of 94 mass parts₂), the stone as conductive agent of 3 mass parts The Kynoar as binding agent (PVdF) of ink and 3 mass parts mixes, and is then added thereto to N-methylpyrrole Alkanone is to obtain cathode mix slurry.Subsequently, this cathode mix slurry is uniformly coated on as positive electrode collector On two surfaces of aluminum (Al) paper tinsel of 10 μ m-thick, and after drying, by roll squeezer gains are pressed with Form positive plate, this positive plate is formed the positive electrode active material layer of the bulk density with 3.40g/cc.Finally, by this just Pole piece is cut into 50mm width and the shape of 300mm length, and by welding, the positive wire being made up of aluminum (Al) is arranged on positive pole The end of collector body, thus manufactured positive pole.

[manufacture of negative pole]

Using the mesophase-carbon micro-beads as negative electrode active material (MCMB) of 97 mass parts and 3 mass parts as bonding The Kynoar (PVdF) of agent mixes, and is then added thereto to N-Methyl pyrrolidone to obtain negative electrode mix slurry Material.Subsequently, this negative electrode mix slurry is uniformly coated on two surfaces of the Copper Foil of 10 μ m-thick as negative electrode collector On, and after drying, be pressed to form negative plate to gains by roll squeezer, formed in this negative plate There is the negative electrode active material layer of the bulk density of 1.80g/cc.Finally, this negative plate is cut into 50mm width and the shape of 300mm length Shape, and by welding, the negative wire being made up of nickel (Ni) is arranged on the end of negative electrode collector, thus manufactured negative pole.

[preparation of nonaqueous electrolytic solution]

Using the lithium hexafluoro phosphate as electrolytic salt (LiPF6) of 0.8mol/kg and by weight 1.0% as miscellaneous many The compound A of phosphate compounds is dissolved in ethylene carbonate (EC) and the mixing of diethyl carbonate (DEC) of the mass ratio with 5/5 In solution.

If the moisture (water content) in the nonaqueous electrolytic solution measured by karl fischer method is 18ppm.Further, as It is 80ppm by the acid content in the nonaqueous electrolytic solution that acid-base titrations is measured.

[assembling of battery]

Barrier film and negative pole that microporous polypropylene membrane by positive pole, by the thickness with 7 μm is made carry out layer with this order Pressure, winds repeatedly in their longitudinal direction by layered product, then by the end of adhesive tape fixing wound body to form platypelloid type Rolled electrode bodies.This rolled electrode bodies is contained in the bag-like package being made up of aluminium lamination press mold, and injects 2g wherein Electrolyte.Finally, by heat fused, the opening of aluminium lamination press mold is sealed in vacuum atmosphere.Thus manufacture embodiment The cylindrical battery of 1-1.

As take apart after precharging this battery as a result, it is possible to confirm, negative terminal surface defines gel coating.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd B is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 18ppm and 82ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd C is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 15ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd D is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 16ppm and 63ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd E is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 168ppm and 721ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd F is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 223ppm and 582ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd G is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 531ppm and 2,120ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And mixing cpd H is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 622ppm and 2,064ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And the compound E of mixing by weight 2.0% is as the nonaqueous electrolytic solution of heteropolyacid salt compound.In comparative example 1-5, one Differentiation compound E becomes soluble so that can not measure the moisture after making the heteropolyacid salt compound dissolution of whole addition Content and acid content.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And the compound F of mixing by weight 2.0% is as the nonaqueous electrolytic solution of heteropolyacid salt compound.In comparative example 1-6, one Differentiation compound F becomes soluble so that can not measure the moisture after making the heteropolyacid salt compound dissolution of whole addition Content and acid content.Further, a part for the heteropoly acid structure of the compound F added ruptures (destroying, collapse).

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And the compound G of mixing by weight 2.0% is as the nonaqueous electrolytic solution of heteropolyacid salt compound.As with in embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution that identical mode is measured are respectively 2,156ppm and 3,590ppm.Further, A part for the heteropoly acid structure of the compound G added ruptures.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and wherein replaces compound A And the compound H of mixing by weight 2.0% is as the nonaqueous electrolytic solution of heteropolyacid salt compound.As with in embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution that identical mode is measured are respectively 2,261ppm and 3,356ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses without adding miscellaneous many The nonaqueous electrolytic solution of acid.As the moisture in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 and acid contain Amount is respectively 12ppm and 56ppm.As the result taking this battery after precharging apart, it is impossible to confirm sinking in negative terminal surface Long-pending thing.

The battery of embodiment 1-1 to 1-4 and comparative example 1-1 to 1-9 is carried out following initial capacity and loop test with And high speed discharge test.

[evaluation of battery]

Cell expansion amount after (a) initial charge

After the initial cells thickness of each battery in measuring above-described embodiment and comparative example, at the environment of 23 DEG C In carry out constant current charge with the constant current of 800mA until voltage reaches 4.2V, and it is straight to continue charging with the constant voltage of 4.2V 3 hours are reached to total charging time.Afterwards, the cell thickness after initial charge is measured.In order to show cell expansion amount, according under The rate of change of cell thickness after row expression formula calculating initial charge.

After initial charge, the rate of change [%] of cell thickness={ (cell thickness after initial charge)/(initial cells is thick Degree) } × 100

Cell expansion amount after (b) High temperature storage

About each battery in above-described embodiment and comparative example, in the environment of 23 DEG C, the constant current with 800mA enters Row constant current charge is until voltage reaches 4.2V, and it is little to reach 3 with the constant voltage continuation charging of 4.2V until total charging time Time.Afterwards, the cell thickness after initial charge is measured.

Subsequently, will be saved in the battery of charged state in the thermostat of 85 DEG C 12 hours, and afterwards, measure high temperature dwell Cell thickness after depositing.In order to show cell expansion amount, according to the change of cell thickness after following expression formula calculating High temperature storage Rate.

The rate of change [%] of cell thickness after High temperature storage=(cell thickness after High temperature storage)/(after initial charge Cell thickness) } × 100

Test result is shown in table 1 below.

Table 1

It is noted that using according to each of in the inclusion compound A to D of embodiment of the present invention from table 1 In battery as the electrolyte of heteropolyacid salt compound, when can suppress initial charge and the also battery after High temperature storage Expand.It is believed that the increase of cell thickness is relevant to the moisture in electrolyte and acid content；And it is miscellaneous in its structure Moisture that polyacid is comprised and proton when charging with electrode vigorous reaction thus cause decomposing so that cell thickness increases, and And cause the deterioration of battery behavior.

This is effective for improving battery behavior to remove for water of crystallization from the structure of heteropoly acid.But, when from When removing water of crystallization in the heteropoly acid containing proton, a part of structure is difficult to be kept, and dissolubility in the electrolytic solution becomes poor, And it is difficult to obtain intended effect.In heteropolyacid salt compound according to the embodiment of the present invention, owing to handing over proton The cationic stabilized the changed structure of heteropoly acid, therefore can improve High temperature storage characteristic, and do not moisturize content and acid Each of in content.

[embodiment 2]

In example 2, by changing as the addition each of in the compound A to D of heteropolyacid salt compound Evaluate the characteristic of laminated membrane type battery.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 0.01%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 0.05%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 0.1%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 15ppm and 65ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 0.5%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 16ppm and 73ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 1.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 18ppm and 80ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 2.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 21ppm and 84ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 3.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 31ppm and 91ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound A as heteropolyacid salt compound of meter 5.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 43ppm and 98ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 0.01%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 0.05%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 0.1%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 15ppm and 66ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 0.5%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 16ppm and 78ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 1.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 18ppm and 82ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 2.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 22ppm and 95ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 3.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 30ppm and 98ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound B as heteropolyacid salt compound of meter 5.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 43ppm and 103ppm.

Manufacturing battery in the way of identical with embodiment 1-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 0.01%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 56ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 0.05%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 56ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 0.1%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 12ppm and 56ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 0.5%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 14ppm and 57ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 1.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 15ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 2.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 16ppm and 61ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 3.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 20ppm and 61ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses and is wherein mixed with by weight The nonaqueous electrolytic solution of the compound C as heteropolyacid salt compound of meter 5.0%.As in the way of identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution measured are respectively 22ppm and 62ppm.

Manufacturing battery in the way of identical with embodiment 2-1, difference is, uses such non-aqueous solution electrolysis Liquid, this nonaqueous electrolytic solution by using by weight 1.0% fluoroethylene carbonate (FEC), 0.8mol/kg as electrolyte Lithium hexafluoro phosphate (the LiPF of salt₆) and the compound A as heteropolyacid salt compound of by weight 1.0% be dissolved in 5/ Prepared by the ethylene carbonate (EC) of the mass ratio of 5 and the mixed solution of diethyl carbonate (DEC).As with embodiment 1-1 In moisture in the nonaqueous electrolytic solution measured of identical mode and acid content be respectively 18ppm and 82ppm.

Manufacturing battery in the way of identical with embodiment 2-25, difference is, uses and wherein replaces compound A And mixing cpd B is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 18ppm and 83ppm.

Manufacturing battery in the way of identical with embodiment 2-25, difference is, uses and wherein replaces compound A And mixing cpd C is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 16ppm and 59ppm.

Manufacturing battery in the way of identical with embodiment 2-25, difference is, uses and wherein replaces compound A And mixing cpd D is as the nonaqueous electrolytic solution of heteropolyacid salt compound.Such as measure in the way of identical with embodiment 1-1 Moisture and acid content in nonaqueous electrolytic solution are respectively 18ppm and 71ppm.

Manufacturing battery in the way of identical with embodiment 2-25, difference is, replaces fluoroethylene carbonate (FEC), vinylene carbonate (VC) is added.Such as the water in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 Content and acid content is divided to be respectively 18ppm and 81ppm.

Manufacturing battery in the way of identical with embodiment 2-29, difference is, replaces compound A and hybridization Compound B is as heteropolyacid salt compound.As the moisture in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 contains Amount and acid content are respectively 18ppm and 82ppm.

Manufacturing battery in the way of identical with embodiment 2-29, difference is, replaces compound A and hybridization Compound C is as heteropolyacid salt compound.As the moisture in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 contains Amount and acid content are respectively 18ppm and 58ppm.

Manufacturing battery in the way of identical with embodiment 2-29, difference is, replaces compound A and hybridization Compound D is as heteropolyacid salt compound.As the moisture in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 contains Amount and acid content are respectively 17ppm and 66ppm.

[evaluation of battery]

Cell expansion amount after (a) initial charge

Cell expansion amount after (b) High temperature storage

Calculate cell thickness after each operation in initial charge and High temperature storage in the same manner as in example 1 Rate of change.

Test result is shown in table 2 below and table 3.

Table 2

Table 3

From table 2 it is noted that pass through to use heteropolyacid salt compound according to the embodiment of the present invention, wider The deterioration of electrolyte can be suppressed in the range of addition, thus suppress the cell expansion after initial charge to High temperature storage.Especially It is, after initial charge from the viewpoint of cell expansion, the addition of heteropolyacid salt compound is preferably by weight More than 0.01% and no more than by weight 3.0%.Further, after including High temperature storage in the comment of the viewpoint of cell expansion, The addition of heteropolyacid salt compound is preferably by weight more than 1.0% and is not more than by weight 3.0%.

Preferably the lithium salts of heteropoly acid is as heteropolyacid salt compound.In ammonium salt, although ammonium cation is for charge/discharge Stability be somewhat inferior to lithium ion, but even if each of be used for suppressing under high addition in moisture and acid content The effect increased is the highest.About the anionicsite of heteropoly acid, from the viewpoint of the characteristic when High temperature storage, silico-tungstic acid is Preferably.It is believed that this is due to the fact that and causes, i.e. the coating produced by siliceous heteropolyacid salt compound is electricity Chemically stable.

Further, from table 3 it is noted that work as carbonic acid fluoro Asia both of which being used in combination as reactive cyclic carbonate When ethyl ester and vinylene carbonate, can more effectively suppress cell expansion during initial charge.

[embodiment 3: the confirmation of the effect of the heteropoly acid each of having in structure with Keggin and Preyssler structure]

Heteropoly acid or heteropoly compound in the following example are as follows.

Compound I: there is the phosphotungstic acid lithium of Preyssler structure

Compound J: there is the phosphotungstic acid potassium of Preyssler structure

Compound K: there is phosphotungstic acid 40 tetrahydrate of Preyssler structure

Compound L: there is phosphotungstic acid three decahydrate of structure with Keggin

In the following description, the quality of heteropoly acid be defined through deducting the quality of the combination water that heteropoly acid is had and The value obtained；And the quality of heteropolyacid salt compound is defined through deducting the combination water that heteropolyacid salt compound is had Quality and the value that obtains.

[manufacture of positive pole]

[manufacture of negative pole]

[preparation of nonaqueous electrolytic solution]

Using the lithium hexafluoro phosphate (LiPF as electrolytic salt of 0.8mol/kg₆) and the conduct of by weight 1.0% miscellaneous many The compound I of phosphate compounds is dissolved in ethylene carbonate (EC) and the mixing of diethyl carbonate (DEC) of the mass ratio with 5/5 In solution.

[assembling of battery]

Employ by the Kynoar of 2 μ m thick being coated in each of the microporous polypropylene membrane with 7 μ m thick The barrier film prepared on surface.Positive pole and negative pole are laminated via barrier film, layered product are wound in their longitudinal direction many Secondary, and afterwards, by the end of adhesive tape fixing wound body to form the rolled electrode bodies of platypelloid type.Subsequently, by this winding Electrode body is contained in the bag-like package being made up of aluminium lamination press mold, and injects the electrolyte of 2g wherein.Subsequently, in vacuum The opening of aluminium lamination press mold is sealed by atmosphere by heat fused.Afterwards, gains are heated, apply from outside simultaneously Pressure, thus manufactured the laminated membrane type test secondary cell being formed with gel electrolyte layer.

As take apart after precharging this battery as a result, it is possible to confirm, negative terminal surface defines gel coating. Further, it is respectively such as the moisture in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 and acid content 15ppm and 65ppm.

Manufacturing battery in the way of identical with embodiment 3-1, difference is, uses and wherein replaces compound I And mixing cpd J is as the nonaqueous electrolytic solution of heteropoly compound.As non-in measure in the way of identical with embodiment 1-1 Moisture and acid content in water electrolysis liquid are respectively 15ppm and 62ppm.

Manufacturing test secondary cell in the way of identical with embodiment 3-1 to 3-2, difference is, heteropoly acid Compound is adjusted to by weight 2.0% relative to the addition of nonaqueous electrolytic solution.As with the side identical with embodiment 1-1 Moisture and acid content in the nonaqueous electrolytic solution that formula is measured are respectively 20ppm and 74ppm in embodiment 3-3, and in reality Execute and example 3-4 is respectively 18ppm and 70ppm.

Manufacturing test secondary cell in the way of identical with embodiment 3-1 to 3-2, difference is, uses respectively Compound K and L as heteropoly compound replace compound I and J as heteropoly compound.As with embodiment 1-1 In moisture in the nonaqueous electrolytic solution measured of identical mode and acid content in comparative example 3-1, be respectively 483ppm and 1, 955ppm, and in comparative example 3-2, it is respectively 531ppm and 2,120ppm.

Manufacturing test secondary cell in the way of identical with embodiment 3-1 to 3-2, difference is, uses respectively Compound K and L as heteropoly compound replace compound I and J as heteropoly compound；And heteropoly compound In each of addition be adjusted to by weight 2.0%.As non-aqueous in measure in the way of identical with embodiment 1-1 Moisture and acid content in electrolyte are respectively 1,918ppm and 3,213ppm in comparative example 3-3, and at comparative example 3-4 In be respectively 2,156ppm and 3,590ppm.

Manufacturing test secondary cell in the way of identical with embodiment 3-1, difference is, not to non-water power Solve and liquid adds heteropoly compound or heteropoly acid.As in the nonaqueous electrolytic solution measured in the way of identical with embodiment 1-1 Moisture and acid content be respectively 12ppm and 56ppm.

[evaluation of battery]

Cell expansion amount after (a) initial charge

Cell expansion amount after (b) High temperature storage

Test result is shown in table 4 below.

Table 4

As from table 4 it is clear that with without compared with adding the comparative example 3-5 of heteropoly acid or heteropoly compound, Use in the embodiment 3-1 to 3-4 as the compound I or compound J of the heteropoly compound with Preyssler structure, Cell expansion after each of can suppressing in initial charge and High temperature storage.

On the other hand, the change as the salt-free heteropoly acid with Preyssler structure or structure with Keggin is being used In the comparative example 3-1 to 3-4 of compound K or compound L, although cell expansion during High temperature storage can be suppressed, but initially fill Cell expansion during electricity increases.

From table 4 it is believed that the increase of cell thickness and phase each of in the moisture electrolyte and acid content Close；And heteropoly acid is comprised in its structure moisture and proton when charging with electrode vigorous reaction thus cause decomposing, Cell thickness is increased, and causes the deterioration of battery behavior.This is for improving battery behavior with from the structure of heteropoly acid It is effective for removing water of crystallization.But, when removing water of crystallization from the heteropoly acid containing proton, a part of structure is difficult to quilt Keeping, dissolubility in the electrolytic solution becomes poor, and is difficult to obtain intended effect.

Heteropoly compound can suppress when initial charge to cell expansion during High temperature storage.Especially since tool The heteropoly compound having Preyssler structure has the anion that the anion of wherein structure with Keggin is condensed further, And it is stable for changing for the pH in base exchange process, therefore, it is possible to improve High temperature storage characteristic, and does not increase Each of add in moisture and acid content.

Further, by the addition of heteropoly acid or heteropoly compound is regulated to by weight 2.0%, it is possible to obtain more High expansion suppression.

[embodiment 4: the confirmation of the effect of the heteropoly acid each of having in structure with Keggin and Preyssler structure]

Heteropoly acid or heteropoly compound in the following example are identical with those in embodiment 3.

Manufacturing test secondary cell in the way of identical with embodiment 3-1, difference is, as shown in table 5 Change the addition of the compound I as heteropoly acid.

Manufacturing test secondary cell in the way of identical with embodiment 3-1, difference is, uses compound J As heteropoly acid；And change the addition of compound J as shown in table 5.

Manufacturing test secondary cell in the way of identical with embodiment 3-1 to 3-2, difference is, will be by weight The fluoroethylene carbonate (FEC) of gauge 1% joins in nonaqueous electrolytic solution.

Manufacturing test secondary cell in the way of identical with embodiment 3-1 to 3-2, difference is, will be by weight The vinylene carbonate (VC) of gauge 1% joins in nonaqueous electrolytic solution.

Manufacturing test secondary cell in the way of identical with comparative example 3-1 to 3-2, difference is, will be by weight The fluoroethylene carbonate (FEC) of gauge 1% joins in nonaqueous electrolytic solution.

Manufacturing test secondary cell in the way of identical with comparative example 3-1 to 3-2, difference is, will be by weight The vinylene carbonate (VC) of gauge 1% joins in nonaqueous electrolytic solution.

[evaluation of battery]

Cell expansion amount after (a) initial charge

Cell expansion amount after (b) High temperature storage

Test result is shown in table 5 below.

Table 5

As from table 5 it is clear that in the heteropoly compound according to compound I and compound J, can be in wide interpolation Cell expansion inhibition is obtained in weight range.Further, the potassium salt of heteropoly acid is preferably as heteropoly compound.At this potassium salt In, due to the content relative reduction of polyanion, in terms of cell expansion inhibition, therefore somewhat it is inferior to lithium salts；But, its There is the effect of the high increase for each of suppressing in moisture and acid content.

Further, in the case of using the heteropoly compound according to compound I and compound J, by non-aqueous solution electrolysis Reactive cyclic carbonate is used in combination in liquid, cell expansion inhibition during initial charge can be greatly improved.

On the other hand, in each comparative example using heteropoly acid, even if by reactive cyclic carbonate being used in combination, also The most fully obtain cell expansion inhibition.

7. other embodiment

It is not construed as the present invention and is limited to the above-mentioned embodiment according to the present invention, and can carry out various wherein Change and application, as long as no the main points of the deviation present invention.

Such as, in above-mentioned embodiment and working Examples, it has been described that there is laminated membrane type or cylindrical battery The battery of structure and there is the battery of rectangular battery structure, but should not be construed as the present invention and be limited to this.Such as, the present invention Can apply to have the battery of other battery structure such as Coin shape and coin shape and had and be wherein laminated electrode The battery of laminar structure, and identical effect can be obtained.Further, about the structure of electrode body, it is possible not only to application volume Geometric pattern and the various structures of such as laminated-type and meander configuration can be applied.

The application comprises excellent with the Japan submitted to Japan Office respectively on March 2nd, 2010 and on June 17th, 2010 The first relevant theme disclosed in power patent application JP 2010-044810 and JP 2010-138776, by entire contents also Enter herein as reference.

It will be understood by those of skill in the art that can according to design require and other factors carry out various change, combination, Sub-portfolio and change, as long as they are in the range of claims or its equivalent.

Claims

1. a nonaqueous electrolyte, including:

Solvent；

Electrolytic salt；And

Heteropolyacid salt compound, described heteropolyacid salt compound is phosphotungstic acid compound or silico-tungstic acid compound,

Wherein, in nonaqueous electrolytic solution, the amount of acid composition is not more than 100ppm, and described acid composition refers to Bronsted acid,

Described nonaqueous electrolyte comprises at least one member in the cyclic carbonate that choosing freely descends formula (III) or (IV) to represent,

Wherein,

Each in R1 to R4 represents hydrogen group, halogen group, alkyl or haloalkyl, and condition is at least in R1 to R4 Individual expression halogen group or haloalkyl, and

Wherein,

Each in R5 and R6 represents hydrogen group or alkyl.

Nonaqueous electrolyte the most according to claim 1, comprises by weight more than 0.01% and is not more than by weight 3% Described heteropolyacid salt compound.

Nonaqueous electrolyte the most according to claim 1, wherein,

Described electrolytic salt comprises the free lithium hexafluoro phosphate (LiPF of choosing₆), LiBF4 (LiBF₄), lithium perchlorate (LiClO₄) With hexafluoroarsenate lithium (LiAsF₆) at least one member in the group that forms.

4. a nonaqueous electrolyte battery, including:

Positive pole；

Negative pole；And

Nonaqueous electrolyte, wherein,

The gel coating comprising the amorphous polyacid containing one or more multielements and/or polyacid compound is arranged on described negative On at least one of surface of pole,

Wherein,

Each in R5 and R6 represents hydrogen group or alkyl.

Nonaqueous electrolyte battery the most according to claim 4, wherein, described coating is derived from heteropolyacid salt compound, described Heteropolyacid salt compound is phosphotungstic acid compound or silico-tungstic acid compound.

Nonaqueous electrolyte battery the most according to claim 4, by the pack package being made up of laminated film.

Nonaqueous electrolyte battery the most according to claim 6, wherein,

In the case of the initial charge with the fully charged voltage of 4.2V, after initial charge, the rate of change of cell thickness is not more than 15%.

Nonaqueous electrolyte battery the most according to claim 6, wherein,

After preserving 12 hours in the environment of 85 DEG C under fully charged state, the rate of change of cell thickness is not more than 15%.