CN103872298B - Anode for nonaqueous electrolyte secondary battery and its manufacturing method and lithium rechargeable battery - Google Patents

Anode for nonaqueous electrolyte secondary battery and its manufacturing method and lithium rechargeable battery Download PDF

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Publication number
CN103872298B
CN103872298B CN201310699399.2A CN201310699399A CN103872298B CN 103872298 B CN103872298 B CN 103872298B CN 201310699399 A CN201310699399 A CN 201310699399A CN 103872298 B CN103872298 B CN 103872298B
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anode
secondary battery
electrolyte secondary
nonaqueous electrolyte
particle
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CN103872298A (en
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宫胁悟
古屋昌浩
池田达彦
须之内和宏
池田正雄
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Shin Etsu Chemical Co Ltd
Dainichiseika Color and Chemicals Mfg Co Ltd
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Shin Etsu Chemical Co Ltd
Dainichiseika Color and Chemicals Mfg Co Ltd
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Priority claimed from JP2013213380A external-priority patent/JP6237094B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention maintains that high battery capacity and low volume expansion rate, first efficiency for charge-discharge are high, cycle characteristics is excellent, in SiO offer even if by cathode low temperature drying (be less than 250 DEG C)2The particle of middle Si dispersion as active material anode for nonaqueous electrolyte secondary battery and its manufacturing method and used the lithium rechargeable battery of the cathode.Anode for nonaqueous electrolyte secondary battery contains：(A) in SiO2Particle, (B) polyamide-imide resin, the additional conductive material of (C) comprising carbon fiber and carbon black of middle Si dispersions improve the substance of electrolyte impregnability with (D).

Description

Anode for nonaqueous electrolyte secondary battery and its manufacturing method and lithium ion secondary Battery
Technical field
The present invention relates to anode for nonaqueous electrolyte secondary battery and its manufacturing method and lithium rechargeable batteries.
Background technology
In recent years, with the significant development of the electronic equipment of pocket, communication equipment etc., from the small of economy and equipment From the perspective of type, lighting, it is strongly desired the non-aqueous electrolyte secondary battery of high-energy density.In the past, as this non- The high capacity strategy of Water-Electrolyte secondary cell, it is known that for example in negative material using B, Ti, V, Mn, Co, Fe, Ni, Cr, The method of the oxide of Nb, Mo etc. and their composite oxides (No. 3242751 No. 3008228 bulletin of patent, patent public affairs Report：Patent document 1,2), by the M of melt chilling100-xSix(x >=50 atom %, M=Ni, Fe, Co, Mn) is as negative material Method (No. 3846661 bulletin of patent：Patent document 3), the method (patent the of the oxide of silicon is used in negative material No. 2997741 bulletins：Patent document 4), in negative material use Si2N2O、Ge2N2O and Sn2N2Method (the patent mat woven of fine bamboo strips of O No. 3918311 bulletins：Patent document 5) etc..
Wherein, silica can be expressed as SiOx(wherein, for x due to oxide film thereon, 1 than theoretical value is bigger), Using in the analysis of X-ray diffraction, the nano-silicon of number nm~tens of nm or so the microdispersed structure in silica is formed.This Outside, it by being heat-treated in inactive non-oxidizing atmosphere, at 400 DEG C or more of temperature to silicon oxide powder, carries out Disproportionation, the size so as to form the crystallite of silicon be controlled in SiO2The particle of middle Si dispersions.It should be in SiO2Middle Si Although the battery capacity of the particle of dispersion is smaller than silicon, with carbon phase ratio, Unit Weight is up to 5~6 times, and volume expansion It is small, it is believed that easily to be used as negative electrode active material.
In SiO2Addition binding agent in the particle of middle Si dispersion and in the case of modulator electrode, for study plot in electrochemistry The Kynoar (PVdF) used, if repeated multiple times charge and discharge, reversible capacity become smaller, cycle characteristics is deteriorated.The opposing party Face, if using polyimide binder (including the polyamic acid for being heated as polyimides), although cycle characteristics improves, First efficiency becomes very low, is 70% or so, in the case of actual modulated battery, needs anode superfluously, it is impossible to expect only Increase the increase of the battery capacity of partial equilibrium with 5~6 times of capacity of units activity substance.It proposes in negative material and uses Carbon, alloy, use the cathode of polyamide-imide resin in its binding agent, but are not applied to the example of silicon systems negative material (patent document 6~11).In addition, also proposed using polyamide-imide resin in silicon oxide series negative material, but do not have Record (the special open 2009-152037 bulletins of specific use example：Patent document 12).In this way, in SiO2The grain of middle Si dispersions The problem in practical use of son is notable, is that first efficiency is low, as its means are solved, can enumerate supplement irreversible capacity part Method, inhibit irreversible capacity method.
Such as, it was recently reported that by adulterating Li metals in advance so as to supplement the method for irreversible capacity part it is effective.But It is to disclose the method (Unexamined Patent 11-086847 that Li foils are pasted to negative electrode active material surface in order to adulterate Li metals Bulletin：Patent document 13) and negative electrode active material surface carry out Li vapor depositions method (special open 2007-122992 bulletins：Specially Sharp document 14) etc., the stickup for Li foils, with having used in SiO2What the first efficiency of the cathode of the particle of middle Si dispersions was consistent The acquisitions of Li foils is difficult, of high cost, and using the vapor depositions of Li steams, there are manufacturing processes to become the problems such as complicated, impracticable.
On the other hand, it discloses and improves the mass ratio of Si by being adulterated independent of Li, increase the side of first efficiency Method.One is that Si powder is added in SiO2Make the method (patent of the mass ratio reduction of oxygen in the powder of middle Si dispersions No. 3982230 bulletin：Patent document 15), it is by silicon vapor being made to send out simultaneously in the fabrication stage of silica on the other hand Method (special open 2007-290919 bulletins raw, that the hybrid solid for obtaining silicon and silica is precipitated：Patent document 16).
As these resolution policy, adjustment amide/acid imide ratio is disclosed in patent document 17 to inhibit to carry out autohemagglutination Imido first efficiency reduces, while meets method (the special open 2011-60676 bulletins of cycle characteristics maintenance：Patent document 17), but there are the dryings of electrode to need high temperature, maintain the problems such as still insufficient for long-term cycle characteristics.
Existing technical literature
Patent document
Patent document 1：No. 3008228 bulletin of patent
Patent document 2：No. 3242751 bulletin of patent
Patent document 3：No. 3846661 bulletins of the patent mat woven of fine bamboo strips
Patent document 4：No. 2997741 bulletin of patent
Patent document 5：No. 3918311 bulletin of patent
Patent document 6：Unexamined Patent 11-102708 bulletins
Patent document 7：Unexamined Patent 11-126612 bulletins
Patent document 8：No. 3422390 bulletin of patent
Patent document 9：No. 3422391 bulletins of the patent mat woven of fine bamboo strips
Patent document 10：No. 3422392 bulletin of patent
Patent document 11：No. 3422389 bulletin of patent
Patent document 12：Special open 2009-152037 bulletins
Patent document 13：Unexamined Patent 11-086847 bulletins
Patent document 14：Special open 2007-122992 bulletins
Patent document 15：No. 3982230 bulletin of patent
Patent document 16：Special open 2007-290919 bulletins
Patent document 17：Special open 2011-60676 bulletins
Invention content
The subject that the invention solves
High battery capacity and low is maintained the purpose of the present invention is to provide even if by cathode low temperature drying (be less than 250 DEG C) Cubical expansivity, first efficiency for charge-discharge are high, cycle characteristics is excellent, in SiO2The particle of middle Si dispersions is as active material Anode for nonaqueous electrolyte secondary battery and its manufacturing method and the lithium rechargeable battery for having used the cathode.
Means for solving the problems
The present inventor is for that can inhibit the binding agent of the reduction of first efficiency for charge-discharge to be studied, the first charge and discharge The reduction of electrical efficiency is the active material for the battery capacity for improving carbon material, i.e., silicon systems negative electrode active material can be inhibited peculiar Volume expansion variation SiO2The particle of middle Si dispersion as active material, in the SiO2The shortcomings that particle of middle Si dispersions.It is poly- Acid imide binding agent (includes the polyamic acid for being heated as polyimides), although cycle characteristics is excellent, finds to polyamides Asia Amine itself confirms to react with lithium, become make first efficiency reduction will be because.In addition, polyimide binder (is included and is heated into Polyamic acid for polyimides), the process of the imidizate under 250 DEG C or more of high dry temperature is needed, there are battery systems Make the restriction in process.On the other hand, the polyimide binder (Xin Benli of acid imide film is only just obtained by solvent removing Change one ト of リ カ Us etc.), drying temperature can be reduced.In order to become solvent soluble type imidizate terminates, (1) is in acyl Asia Amido imports heat-staple functional group in addition, aromatic system atomic group is used as " spacer group ", makes the concentration of imide reduce, (2) by the importing of meta position combination base etc., strand bendability is given, the volume that (3) import generation steric hindrance in side chain is big Substituent group, inhibit molecular association.By carrying out any one of these, only by low temperature drying with regard to acid imide film can be obtained, But there are generate restriction, and high elastic modulus for damaging polyimides system resins etc. is asked in the design of free binder resin Topic.
The present inventor will come true as function separation necessary to the binding agent for the suitable battery material for being capable of low temperature drying Recognize, as a result, it has been found that be 2 by selecting elasticity modulus, the polyamide-imide resin of more than 500MPa, even if reducing drying temperature, Also it obtains high circulation and maintains characteristic, complete the present invention.In addition, in the case of preparing battery, reduce the anode of superfluous needs It is possibly realized, by the reduction of the anode of the increase and high price of battery capacity, the nonaqueous electrolyte of industrial low price can be obtained Secondary cell.
Therefore, the present invention provides following anode for nonaqueous electrolyte secondary battery and lithium rechargeable battery.
[1] anode for nonaqueous electrolyte secondary battery contains：(A) in SiO2Particle, (B) polyamide of middle Si dispersions The substance of imide resin, the additional conductive material of (C) selected from carbon fiber and carbon black and (D) raising electrolyte impregnability.
[2] anode for nonaqueous electrolyte secondary battery described in [1], wherein, (B) ingredient is that elasticity modulus is 2, The polyamide-imide resin of more than 500MPa.
[3] [1] or the anode for nonaqueous electrolyte secondary battery described in [2], wherein, (B) polyamide-imide resin by Ingredient synthesis comprising the monomer component with ortho-tolidine skeleton, above-mentioned monomer component rub for the 10 of whole monomer components You are more than %.
[4] [1]~[3] any one of them anode for nonaqueous electrolyte secondary battery, wherein, (A) particle is into one The coated particle that step is coated with carbon.
[5] [1]~[4] any one of them anode for nonaqueous electrolyte secondary battery, wherein, the carbon fiber of (C) ingredient It is the carbon fiber of conductive aspect ratio 4~50.
[6] [1]~[5] any one of them anode for nonaqueous electrolyte secondary battery, wherein, the carbon fiber of (C) ingredient It is the vapor grown carbon by carbon monoxide and hydrogen modulation.
[7] [1]~[6] any one of them anode for nonaqueous electrolyte secondary battery, wherein, (D) ingredient is selected from ion Property liquid, glycol ethers and crown ether.
[8] [1]~[7] any one of them anode for nonaqueous electrolyte secondary battery, which is characterized in that also contain stone Ink.
[9] lithium rechargeable batteries are used negative it includes [1]~[8] any one of them non-aqueous electrolyte secondary battery Pole.
[10] manufacturing method of the anode for nonaqueous electrolyte secondary battery described in [1], which is characterized in that containing (A) In SiO2The particle of middle Si dispersion, (B) polyamide-imide resin, the additional conductive material of (C) comprising carbon fiber and carbon black and (D) in the raw material of substance for improving electrolyte impregnability, solvent is kneaded and slurry is made, is coated on the current collection of sheet Body is dried in vacuo.
The effect of invention
In accordance with the invention it is possible to high battery capacity and low is maintained offer even if by cathode low temperature drying (be less than 250 DEG C) Cubical expansivity, first efficiency for charge-discharge are high, cycle characteristics is excellent, in SiO2The particle of middle Si dispersions is as active material Anode for nonaqueous electrolyte secondary battery and the lithium rechargeable battery for having used the cathode.
Specific embodiment
Below to the detailed description of the invention.
The anode for nonaqueous electrolyte secondary battery of the present invention contains：(A) in SiO2Particle, (B) polyamides of middle Si dispersions The substance of amine imide resin, the additional conductive material of (C) selected from carbon fiber and carbon black and (D) raising electrolyte impregnability.
(A) in SiO2The particle of middle Si dispersions
The particle is the particle that can absorb, release lithium ion.The particle of Si is in SiO2The state of middle dispersion, its grain size energy Enough by confirmations such as Measurement of particle size distribution by laser diffraction, preferably 0.1~50 μm of the grain size of Si particles, more preferable 1~ 20μm。
In SiO2The particle of middle Si dispersions is used as the active material of the anode for nonaqueous electrolyte secondary battery of the present invention.It should The method that the product that particle can use such as (1) to mix the particle of silicon with silicon systems compound is burnt into, (2) will be for that will heat two The mixture of silica and metallic silicon generation silicon monoxide gas cooling, be precipitated obtained from amorphous Si oxide, will plus The silicon monoxide gas of hot organo-silicon compound generation cools down, the Si oxide of amorphous obtained from precipitation, at 400 DEG C or more At a temperature of heat, method for carrying out disproportionation etc. obtains.Due to obtaining the particle for uniformly dispersing the crystallite of silicon, It is preferred that the method for (2).
It also is able to adulterate xenogenesis element in (A) particle.As the method for doping, can enumerate heating silica and gold Belong to the silicon monoxide gas cooling of the mixture generation of silicon, be precipitated and when modulating Si oxide, in silica and metallic silicon In mixture, mixing Ni, Mn, Co, B, P, Fe, Sn, In, Cu, S, Al, C etc. use the chemical combination with xenogenesis element in metallic silicon Object, in silica using method for the compound for being doped with xenogenesis element etc..
In addition, (A) of the present invention is in SiO2The molar ratio of oxygen/silicon in the particle of middle Si dispersions, usually 1 than theoretical value It is bigger, with 1.0<Oxygen/silicon (molar ratio)<1.1 generations, by the way that (A) particle generated is etched under acid atmosphere, can select Property only by SiO2It removes.By selectively only by SiO2It removes, 0.2<Oxygen/silicon (molar ratio)<1.1 it is possibly realized.Wherein, Under so-called acidity atmosphere, it can be aqueous solution or contain sour gas, there is no particular restriction for composition, can enumerate example Such as hydrofluoric acid, hydrochloric acid, nitric acid, hydrogen peroxide, sulfuric acid, acetic acid, phosphoric acid, chromic acid, pyrophosphoric acid, can be with a kind individually or by 2 kinds It is appropriately combined use above.For treatment temperature, it is not particularly limited.According to the above method, 0.2 can be used<Oxygen/silicon (molar ratio)<1.1 Si is in SiO2The particle of middle dispersion.
(A) particle from assigning electric conductivity aspect, preferably becomes the coated particle that its surface is also coated with carbon.Make It is method that the particle that can enumerate makes (A) particle and carbon etc. conductive mixes, right in organic gas for the method for coating (A) particle surface carries out method, the method for combining the two of chemical vapor deposition (CVD) etc., preferably carries out chemical vapor deposition (CVD) Method.
For chemical vapor deposition (CVD), the heat treatment with above-mentioned silicon systems compound simultaneously or in addition exists to (A) particle The method that chemical vapor deposition (CVD) is carried out in organic gas is preferred, by importing organic gas instead in heat treatment It answers in device, so as to expeditiously carry out.It specifically, can be by silicon systems compound or (A) particle, in organic gas In, under the decompression of 50Pa~30,000Pa, carry out chemical vapor deposition at 700~1,200 DEG C and obtain.The above-mentioned preferred 50Pa of pressure~ 10,000Pa, more preferable 50Pa~2,000Pa.If degree of decompression is bigger than 30,000Pa, there is the graphite material of graphite-structure Ratio excessively becomes larger, as negative electrode material for nonaqueous electrode secondary battery in the case of, in addition to the reduction of battery capacity, cycle Property is likely to decrease.Chemical vapor deposition temperature preferably 800~1,200 DEG C, more preferable 900~1,100 DEG C.If treatment temperature ratio 700 DEG C low, it is possible to which prolonged processing becomes necessary.If on the contrary, than 1,200 DEG C of height are handled by chemical vapor deposition, and having can Melting adhesion, cohesion can be caused between particle, conductive cell envelope is not formed in cohesion face, as non-aqueous electrolyte secondary battery In the case of negative material, it is possible to which cycle performance reduces.Further more, processing time is according to the carbon amount of coating of target, processing temperature Degree, the concentration (flow velocity) of organic gas, import volume etc. suitably select, usually 1~10 hour, particularly 2~7 hours or so Economically and efficiency.
As the organic matter for being used as generating the raw material of organic gas in the present invention, selection is particularly in nonacid atmosphere Under can thermally decompose and generate the organic matter of carbon (graphite) under above-mentioned heat treatment temperature, it can be mentioned, for example methane, ethane, second The independent or mixture of the hydrocarbon such as alkene, acetylene, propane, butane, butylene, pentane, iso-butane, hexane, benzene,toluene,xylene, benzene second The ring of 1 ring such as alkene, ethylbenzene, diphenyl methane, naphthalene, phenol, cresols, nitrobenzene, chlorobenzene, indenes, coumarone, pyridine, anthracene, phenanthrene~3 Aromatic hydrocarbon or their mixture.In addition, the gas oil obtained in tar distillation process, creasote, carbolineum, naphtha are split Solution tar can also be used alone or mixture could be used that.
Amount of coating is not particularly limited, relative to coated particle, preferably 0.3~40 mass %, more preferable 0.5~30 matter Measure %.If carbon amount of coating is less than 0.3 mass %, it is possible to sufficient electric conductivity cannot be maintained, as a result as nonaqueous electrolyte Cyclicity declines sometimes during secondary battery cathode material.On the contrary, even if carbon amount of coating is more than 40 mass %, coating also can't see Amount increases the raising of the effect generated.
The physical property of (A) particle and coated particle to the present invention is not particularly limited, preferably 0.1~30 μm of average grain diameter, More preferable 0.2~20 μm.In addition, BET specific surface area preferably 0.5~30m2/ g, more preferable 1~20m2/g.Further more, average grain diameter It can be represented with the weight average particle diameter in the particle size distribution carried out using laser diffractometry.BET specific surface area is with passing through N2 Value when the BET1 points method of gas adsorbance evaluation measures.
(B) polyamide-imide resin
To the present invention polyamide-imide resin be not particularly limited, can a kind be used alone or by two or more It is appropriately combined use.It is preferred that the stretch modulus of dry coationg is the polyamide-imide resin of more than 2,500MPa.Pass through into For the range, the charge/discharge cycle characteristics as non-aqueous electrolyte secondary battery further improve.Stretch modulus preferably 2,500~ 7,000MPa.And then from further improving charge/discharge cycle characteristics aspect, tensile elongation preferably 25% is hereinafter, more It is preferred that 3~25%.
When improving the elasticity modulus of polyamide-imide resin, by being led in resin matrix, particularly in backbone portion Enter upright and outspoken structure, can realize.For example, by selection 1,1 '-biphenyl -4,4 '-dicarboxylic acids, ortho-tolidine diisocyanate The monomer material of contained biphenyl backbone etc. in ester, for polymerisation, so as to be possibly realized.In particular it is preferred to using having The monomer component of ortho-tolidine skeleton.It is synthesized by the monomer component comprising the monomer component with ortho-tolidine skeleton In the case of polyamide-imide resin, it is preferable that the monomer component with ortho-tolidine skeleton is whole monomer components 10 moles of more than %, the range of preferably 15~50 moles %.And then make tensile elongation be less than 25% when, in addition to above-mentioned Other than condition, for example, the total functional group's molal quantity for passing through the sour component by (I) in polybasic acid anhydride and/or polybasic carboxylic acid (X) ratio of total functional group's molal quantity (Y) of the ingredient with (II) in multicomponent isocyanate and/or polynary amine is adjusted to (X)/(Y)<1, molecular weight is controlled, can be realized.
<The assay method of elasticity modulus, tensile elongation>
In the present invention, the elasticity modulus of polyamide-imide resin is measured using following methods.
The solution of polyamide-imide resin is acquired, is applied on polyester film with glass bar.By it dry 15 at 120 DEG C After minute, envelope is removed, it is 2 hours dry at 240 DEG C, obtain dry coationg.It is obtained with the speed tensile of 20mm/ minutes Envelope obtains load-deformation curve, calculates elasticity modulus and tensile elongation.In addition, using same method, can measure Polyimide resin etc..
Next, the manufacturing method to polyamide-imide resin shows details.
Polyamide-imide resin in the present invention can be by making (I) in polybasic acid anhydride and/or polybasic carboxylic acid Sour component react and obtain with the ingredient of (II) in multicomponent isocyanate and/or polynary amine.
As polybasic acid anhydride, there are the compound with acid anhydride and carboxyl, the compound with multiple acid anhydrides, It can be mentioned, for example trimellitic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, oxygen The aromatic systems polybasic acid anhydrides such as union II O-phthalic acid dianhydride, 1,3,4- cyclohexanetricarboxylic acid -3,4- acid anhydride, 1,2,3,4- butane Alicyclic ring families polybasic acid anhydride such as tetracarboxylic dianhydride etc., can a kind be used alone or two or more is appropriately combined use. Use also is able to by these derivative derivatives, for example, trimellitic anhydride alkyl esters etc., the inclined benzene of intramolecular acid anhydride can be formed Three acid, inclined three formyl chloride of benzene etc..Consider cost, the preferably easiness obtained, trimellitic anhydride.Had using trimellitic anhydride etc. In the case of the compound of both acid anhydrides and carboxyl as functional group, even if without using polybasic carboxylic acid, polyamide can be also obtained Imide resin.
As polybasic carboxylic acid, it can be mentioned, for example terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, hexichol Methylmethane dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenyl sulfone dicarboxylic acids, 1,1 '-biphenyl -4,4 '-dicarboxylic acids, trimellitic acid, The aromatic systems polybasic carboxylic acid such as benzene tetracarboxylic acid, succinic acid, adipic acid, decanedioic acid, dodecanedioic acid, 1,2,3,4- butane tetracarboxylic acid Wait the fat such as aliphatic polycarboxylic acids, the unsaturated aliphatics polybasic carboxylic acids such as maleic acid, fumaric acid, 4- cyclohexene -1,2- dicarboxylic acids Ring type polybasic carboxylic acid etc., can a kind be used alone or two or more is appropriately combined use.Use also is able to by these to be spread out Raw derivative, such as the acid anhydrides such as the esters such as dimethyl terephthalate (DMT), phthalic anhydride.
As multicomponent isocyanate, it can be mentioned, for example methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), ditolyls Amine diisocyanate, benzene dimethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, hexa-methylene two Isocyanates, dicyclohexyl methyl hydride diisocyanate etc., polymer, the toluene di-isocyanate(TDI) of methyl diphenylene diisocyanate The polyisocyanates such as polymer.Wherein, preferably ortho-tolidine diisocyanate, naphthalene diisocyanate, it is more preferably o- Tolidine diisocyanate etc. has the monomer component of ortho-tolidine skeleton.These can a kind be used alone or will Two or more is appropriately combined use, additionally it is possible to which use is by these derivative derivatives, such as phenol, dimethlbenzene or ketone etc. Blocked isocyanate class.
As blocked isocyanate compound, for example, by 4,4 '-methyl diphenylene diisocyanate and dimethlbenzene acids Obtained compound (the mono- ト MS-50 of ミ リ オ ネ of Nippon Polyurethane Industry (Ltd.)), by 4,4 '-diphenylmethane diisocyanate Compound (mono- ト of U ロ ネ of Nippon Polyurethane Industry (Ltd.) that ester and aliphatic polyol, phenol or cresols class obtain 2503), the compound (DesmodurCT- of バ イ エ Le society obtained by the tripolymer of toluene di-isocyanate(TDI) and phenols Stable it is) etc. useful.These may be present in the reaction system of polyamide-imide resin, can also put into after completion of the reaction, is molten Solution.Particularly, about the latter, for the viscosity of control polyamideimide resin solution, the purpose of raising bin stability, have Effect.
As polynary amine, it can be mentioned, for example phenylenediamine, diaminodiphenyl-methane, methylene diamine, benzene dimethylamine, naphthalenes Diamines, toluenediamine, ortho-tolidine, hexamethylene diamine etc..These can a kind be used alone or two or more is appropriate Ground is applied in combination.
Polyamide-imide resin in the present invention can use common isocyanic acid ester process, use method of acyl chlorides etc. Manufacture.From reactivity, cost aspect, preferred isocyanate method.
Solvent can be used in the polymerization of polyamide-imide resin.For example, n-methyl-2-pyrrolidone can be enumerated (NMP), N- ethyl-2-pyrrolidones (NEP), N, N '-dimethyl acetamide (DMAc), N, N '-dimethyl formamide (DMF) etc. The esters system such as ester series solvent, dimethyl adipate, dimethyl succinate in amide system polar solvent, gamma-butyrolacton, δ-valerolactone etc. The sulfur-bearings systems such as ether series solvents, the dimethyl sulfoxide (DMSO) such as solvent, cresols, phenol solvent, diethylene glycol monomethyl ether as dimethlbenzene are molten Aromatic hydrocarbon series solvents such as agent, dimethylbenzene, naphtha etc..Wherein, preferably dissolving power, excellent NMP, the NEP of reactivity, from into Originally, the easiness obtained is set out, most preferably NMP.These solvents can a kind be used alone or be appropriately combined two or more It uses.
In addition, catalyst can be used in polymerization.Catalyst has amine, tricresyl phosphate such as triethylenediamine, pyridine Metals series catalysts such as the phosphorus such as phenyl ester, triphenyl phosphite series catalysts, octenoic acid zinc, octenoic acid tin etc..The addition of catalyst Amount, as long as not hindering to react, is then not particularly limited, relative to resin point, preferably 0.1~1 mass %.
Temperature is not particularly limited during polymerization, preferably 50~200 DEG C of range, more preferable 80~190 DEG C.If reaction Temperature is less than 50 DEG C, and reaction can not be successfully progress, need the prolonged reaction time.If reaction temperature is more than 200 DEG C, generation The probability of by-product improves, and the possibility raising of the three dimensional stress of polyamide-imide resin occurs, it is possible to be sent out in reaction system Raw gelation.
In the case of having used polynary amine, after first generating amic acid, imide ring is generated by closed loop process, this is closed Ring process can carry out in the polymerisation system of polyamide-imide resin, also can be temporarily molten by resin in the state of amic acid Liquid takes out, and closed loop is carried out in molding procedure behind.Above-mentioned polyamide-imide resin is used as to drying during binding agent Temperature, the temperature that can in time select from 120 degree to 200 degree.
(C) the additional conductive material selected from carbon fiber and carbon black
(C) additional conductive material is selected from carbon fiber and carbon black, can a kind be used alone or by two or more suitably group It closes and uses.It as carbon fiber, is not particularly limited, gas-phase growth of carbon fibre, pitch-based carbon fiber, PAN based carbon fibers can be enumerated Deng.Wherein, the preferred carbon fiber of dispersibility and excellent electric conductivity, in cathode, the carbon of preferably conductive aspect ratio 4~50 Fiber.Particularly, from manufacturing aspect, it is preferable to use easily fiber warpage shortens in modulation, is dispersed excellent And the conductive carbon fiber even if warpage shortens, modulates cathode.More specifically, by by 6~20nm of outer diameter, in length and breadth Lip pencil structural unit assembly-use than 2~30 becomes the carbon fibre of conductive aspect ratio 4~50 in the manufacture of cathode Dimension, coordinates in cathode, and cycle characteristics improves.Above-mentioned lip pencil structural unit aggregate is connected each other by graphite-based bottom surface Hollow carbon fiber, can enumerate in the fibre interior packet at least one for being applied to the shear stress of the hollow carbon fiber, adjacent The connection structure slided can be generated between the graphite-based bottom surface of structural unit aggregate.As such hollow carbon fiber, can enumerate Such as the vapor grown carbon modulated by carbon monoxide, the gas phase modulated in the presence of a catalyst by carbon monoxide and hydrogen can be enumerated and given birth to Long carbon.As such carbon fiber, specifically, AMC361 (registered trademark) of Ube Industries, Ltd etc. can be enumerated.
As carbon black, acetylene black, Ketjen black (Ketjen black), furnace black etc. can be enumerated.
(D) substance of electrolyte impregnability is improved, as long as improving the substance of electrolyte impregnability, then has no special limit It is fixed, as long as it is remained in after dry in binder resin and is easily dissolved in electrolyte, does not generate too big shadow to cell reaction Loud substance, can a kind be used alone or two or more is appropriately combined use.It can be mentioned, for example as vapour pressure and Resin components such as ionic liquid, glycol ethers, crown ether and the PVdF resins of the high liquid of boiling point etc., can add on a small quantity makes With.These never significantly hinder to set out in terms of the discharge and recharge reaction of lithium ion, by adding ionic liquid, glycol ethers Class, crown ether-like, so as to improve electrolyte impregnability.In addition, although the resins such as PVdF resins are reduced with weight, also confirm pair In the improvement of electrolyte impregnability.For the additive amount of the substance of these raising electrolyte impregnabilities, relative to (B) ingredient Wait the solid sub-prime amount of binding agents, preferably 0.1~20.0 mass %, more preferable 1.0~10.0 mass %.It is such by becoming Range does not interfere the curing of resin used in the binding agent of (B) ingredient etc., shortens ageing time, and battery behavior becomes good.
<The confirmation method of electrolyte impregnability>
The confirmation of electrolyte impregnability carries out by the following method.The electrode of making is punched into 2cm2, electrolysis will be used as The ethylene carbonate of liquid solvent composition and the solution mixed with 1 to 1 volume fraction of diethyl carbonate, in the drying chamber for punching The electrode of sanction instills 1cc, as terminal at the time of electrode electrolyte solvent composition is uniformed, with the second with Mini liquid suction pipe Table measures.Using after instillation until the time of terminal be less than 30 seconds substance as the present invention " raising electrolyte impregnability Substance ".Further more, in above-mentioned confirmation method, the difference of result that the electrode that same formula makes generates is used as within 3%, survey Determine no problem.Above-mentioned confirmation method, be packed into since in actual battery after electrolyte until actually using time (0.5~ 48 hours) from the point of view of, it is the judgement with very short time.The basis of the numerical value, (1) visually judge the state of moistened surface and are impregnated into Internal state is extremely difficult, (2) for after instillation until the time of terminal be less than 30 seconds battery it is multiple and after instilling it is straight Time to terminal is that the battery of 60 seconds or more is multiple, is loaded into after electrolyte until the time actually begun to use shortens (0.5 Hour) in the case of, it is thus identified that up to the battery that the time of terminal is less than 30 seconds has fifty-fifty reached predetermined volumes after instillation Data, but for after instillation until the time of terminal is the battery of 60 seconds or more, it is thus identified that it is multiple not reach predetermined volumes Battery.As a result, in the present invention, by the Material Definitions that the time up to terminal after instillation is less than 30 seconds " to improve electrolyte The substance of impregnability ".
(D) ionic liquid of ingredient is the general name that liquid ionic substance is also shown under room temperature, have cation into Point and anion component.As the cation constituent of ionic liquid, ammonium cation, pyrrolidines can be enumeratedCation, piperidines Cationic (the following general formula (1)), imidazolesCationic (the following general formula (2)), pyridineCationic (the following general formula (3)), Cationic (the following general formula (4)), sulfonium cation (the following general formula (5) etc.).
(R1~R4Alkyl or alkoxyalkyl for the carbon number 1~18 being same or different to each other.In addition, R1~R4In 2 A cyclic structure with shared same functional group.By R1And R2The situation connected with the saturated hydrocarbyl of carbon number 4 is particularly referred to as PyrrolidinesCation, by R1And R2The situation connected with the saturated hydrocarbyl of carbon number 5 is particularly referred to as piperidinesCation.)
(R5、R6Alkyl or alkoxyalkyl for the carbon number 1~18 being same or different to each other.)
(R7、R8Alkyl or alkoxyalkyl for the carbon number 1~18 being same or different to each other.Moreover, taking on aromatic rings It can be 2 or more for base.)
(R9~R12Alkyl or alkoxyalkyl for the carbon number 1~18 being same or different to each other.In addition, R9~R12In 2 A cyclic structure with shared same functional group.)
(R13~R15Alkyl or alkoxyalkyl for the carbon number 1~18 being same or different to each other.In addition, R13~R15In 2 cyclic structures that can have shared same functional group.)
In addition, as anion component, following anion component is enumerated as an example.Bis- (fluoroform sulphurs can be illustrated Acyl group) imines anion, bis- (pentafluoroethane sulfonyl) imines anion, bis- (fluorosulfonyl) imines anion, trifluoro methylsulphur It is acid radical anion, methyl sulfate anions, ethyl sulphate anion, methane sulfonate anion, ethanesulfonic acid root anion, right Toluenesulfonate anion, anion hydrogen sulphate, tetrafluoroborate anion, bis- [oxalate (2-)] borate anions, Trifluoro (trifluoromethyl) borate anion, hexafluoro-phosphate radical anion, dimethyl phosphate radical anion, diethylphosphate root Anion, three (pentafluoroethyl group) trifluoro phosphate radical anions, chloride ion, bromide ion, iodide ion, cdicynanmide are cloudy Ion etc..
By the combination of above-mentioned cation and anion, various ionic liquids can be selected.It but can in the present invention The ionic liquid used is not only defined in the combination of above-mentioned anionic-cationic.In addition, the property as the ionic liquid used Matter without decomposition reaction or is difficult to due to being used in negative side, under the current potential being preferably precipitated in lithium in cathode The ionic liquid of decomposition reaction.
In the case ofs the width for considering electrochemical window, the easiness etc. obtained, preferred piperidinesSalt, imidazolesSalt, it is especially excellent Selection of land can illustrate N- Methyl-N-propyl piperidinesBis- (trifluoromethane sulfonyl group) inferior amine salts (hereinafter, PP13-TFSI), N- first Base-N- propyl pyrrole alkaneBis- (trifluoromethane sulfonyl group) inferior amine salts (hereinafter, P13-TFSI), N- methyl-N- butyl pyrrolidinesBis- (trifluoromethane sulfonyl group) inferior amine salts (hereinafter, P14-TFSI), N, N, bis- (the fluoroform sulphurs of N- trimethyl-N- propyl ammoniums Acyl group) inferior amine salt (hereinafter, TMPA-TFSI), 1- ethyl -3- methyl-imidazolesBis- (fluoromethane sulfonyl) inferior amine salts (hereinafter, EMIm-FSI), 1- ethyls -3- methyl-imidazolesThree (pentafluoroethyl group) three fluorophosphate (hereinafter, EMIm-FAP), 1- (2- methoxies Base ethyl) -1- crassitudesThree (pentafluoroethyl group) three fluorophosphate (hereinafter, MOEMPL-FAP) etc..
As glycol ethers, selected from the glycol ethers that boiling point is high, steam forces down, does not hinder lithium secondary battery reaction substantially It selects, can in time be selected from glycol ether system, propylene glycol system and dialkyl group glycol ethers.Dialkyl group glycol ethers are to use alkyl Replace ethylene glycol, diethylene glycol (DEG), triethylene glycol end hydrogen product.
Specifically, in glycol ether system, the butyldiglycol high with the solubility of water (230 degree, 25 degree of boiling point can be enumerated Vapour pressure 0.01hPa), methyl triethylene glycol (249 degree, 25 degree below vapour pressure 0.01hPa of boiling point), butyltriglycol (boiling point 271 Degree, 25 degree of below vapour pressure 0.01hPa), benzyl diethylene glycol (DEG) (302 degree, 25 degree below vapour pressure 0.01hPa of boiling point), with water The small hexyl diethylene glycol (DEG) of solubility (259 degree, 25 degree below vapour pressure 0.01hPa of boiling point), 2- ethylhexyl diglycol (boiling points 272 degree, 25 degree of below vapour pressure 0.1hPa) etc., in propylene glycol system, the methyl propanediol high with the solubility of water can be enumerated (242 degree, 25 degree vapour pressure 0.03hPa of boiling point), butyl propylene glycol (boiling point 274 degree, 25 degree steam small with the solubility of water Press below 0.01hPa), phenyl propylene glycol (242 degree, 25 degree below vapour pressure 0.1hPa of boiling point) etc., in dialkyl group glycol ethers system, Dibutyl diethylene glycol (DEG) (254 degree, 25 degree vapour pressure 0.01hPa of boiling point) etc. can be enumerated.
Crown ether-like is cricoid polyethers (products of several ether unit connections), can enumerate 12 hat, 4 ether, 15 5 ethers of hat, 18 hats 6 Ether, dibenzo-18 crown-6 etc..
[anode for nonaqueous electrolyte secondary battery]
The anode for nonaqueous electrolyte secondary battery of the present invention contains (A) in SiO2The particle of middle Si dispersions, (B) springform The polyamide-imide resin for more than 2,500MPa, the additional conductive material of (C) comprising carbon fiber and carbon black and (D) is measured to improve The substance of electrolyte impregnability.(A) content of ingredient, relative to cathode, preferably 70~99.9 mass %, more preferable 80~99 matter Measure %, further preferred 80~95 mass %, particularly preferred 80~88 mass %.(B) content of ingredient, it is excellent relative to cathode Select 0.1~30 mass %, more preferable 1~20 mass %.Further more, above-mentioned divide content for solid.(C) component content, relative to negative Pole, preferably 0.01~10.00 mass %, more preferable 0.1~2.0 mass %.(D) component content, relative to cathode, preferably 0.1 ~5.0 mass %, more preferable 0.2~1.0 mass %.
In cathode, graphite, other active materials (Sn, SnC other than (A) ingredient can be added2O4) etc. other active matters Matter.As other active materials, difficult graphitized carbon, easy graphitized carbon and these high temperature firing product, spheroidizing product, scale are included Shape product, surface treatment product etc..Wherein, preferably (A) ingredient is used in combination with graphite.By being used in combination, electrode capacity can be adjusted.Example Such as, cathode entirety dosage can freely be adjusted from 200mAh/g- electrodes to 2000mAh/g- electrodes, be selected.In addition, pass through by This active material of more than two kinds is used in mixed way, and is met as organizing the high-voltage side capacity of more than 3.8V of battery, below 3.0V Low potential side capacity is possibly realized.
The conductive agent other than (C) ingredient can be added in cathode.The type of conductive agent is not particularly limited, as long as Do not cause in the battery of composition decomposition, rotten electronic conductivity material, specifically, can use Al, Ti, Fe, Ni, It is the metal powders such as Cu, Zn, Ag, Sn, Si, metallic fiber, native graphite, Delanium, various coke powders, mesocarbon, each The graphite of kind resin sintered body etc..The content of conductive agent, relative to cathode, preferably 0.1~30 mass %, more preferable 1~10 matter Measure %.
In addition, other than above-mentioned polyamide-imide resin, as viscosity modifier, can add carboxymethyl cellulose, Sodium Polyacrylate, other acrylic acid series polymeric compounds or aliphatic ester etc., content, relative to cathode, from 0.01~10 matter The range of amount % is suitably set.
Cathode (molding can be for example formed as described below in the negative electrode material for nonaqueous electrode secondary battery of the present invention Body).Following methods can be enumerated：At (A) in SiO2Particle, (B) polyamide-imide resin, (C) of middle Si dispersions include carbon fibre Additional conductive material, (D) of peacekeeping carbon black are improved in the substance and other additives as needed of electrolyte impregnability, will The dissolvings of the suitable binding agents such as NMP (N-Methyl pyrrolidone), ethyl-methyl pyrrolidones, gamma-butyrolacton, water, dispersion it is molten Agent is kneaded, and slurry is made, is coated on the collector of sheet, is dried in vacuo.As collector, as long as copper foil, nickel The material that foil etc. is used usually as the collector of cathode can use thickness, surface treatment with no particular limitation.Further more, The forming method that pulpous state mixture is shaped to sheet is not particularly limited, well known method can be used.Further more, to above-mentioned true The dry method of sky, temperature are not particularly limited, according to the present invention, even less than 250 DEG C, 180~240 DEG C, it can also carry For maintaining, high battery capacity and low volume expansion rate, first efficiency for charge-discharge are high, cycle characteristics is excellent, is dispersed in SiO with Si2In Particle as active material anode for nonaqueous electrolyte secondary battery and used the lithium rechargeable battery of the cathode.It is right Drying time is not particularly limited, and properly selects, and is 0.5~5.0 hour or so.
[non-aqueous electrolyte secondary battery]
Using the anode for nonaqueous electrolyte secondary battery of the present invention, lithium rechargeable battery can be manufactured.Such case Under, obtained lithium rechargeable battery has a feature in terms of above-mentioned cathode is used, other anodes, electrolyte, non-aqueous The material of agent, partition board, collector etc. and cell shapes etc. can use well known material and shape etc., be not particularly limited.Example Such as, as a positive electrode active material, LiCoO can be used2、LiNiO2、LiMn2O4、Li(Mn1/3Ni1/3Co1/3)O2、V2O5、MnO2、 TiS2、MoS2Wait oxide and chalcogen compound of transition metal etc..As electrolyte, using for example comprising lithium hexafluoro phosphate, height The non-aqueous solution of the lithium salts such as lithium chlorate, as nonaqueous solvents, can by propylene carbonate, ethylene carbonate, dimethoxy-ethane, Gamma-butyrolacton, 2- methyltetrahydrofurans, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, vinylene carbonate, carbonic acid fluorine It is used alone for a kind of ethyl etc. or two or more is appropriately combined use.It is further possible to using each other than this The non-water system electrolyte of kind, solid electrolyte.
In addition, in the case of obtaining electrochemical capacitor, electrochemical capacitor has spy in terms of above-mentioned cathode is used Sign, material and capacitor shape for other electrolyte, partition board etc. etc. are simultaneously not limited.For example, as electrolyte, use example The non-aqueous solution of lithium hexafluoro phosphate, lithium perchlorate, boron lithium fluoride, hexafluoroarsenate lithium lithium salts is such as included, as nonaqueous solvents, energy Enough by propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxy-ethane, gamma-butyrolacton, 2- methyl 1 kind of tetrahydrofuran etc. is used alone or two or more is appropriately combined use.It is further possible to using each other than this The non-water system electrolyte of kind, solid electrolyte.
[embodiment]
Embodiment described below and comparative example, specifically describe the present invention, but the present invention is not limited by following embodiments System.
[embodiment 1]
<The modulation of electroconductive particle>
It it is 5 μm by average grain diameter, BET specific surface area 3.5m2The Si oxide SiO of/gx(x=1.01) 100g is packed into interval In formula heating furnace.It will be depressurized in stove with oily rotary vacuum pump, while 1,000 DEG C will be warming up in stove, after reaching 1,000 DEG C, Made CH with 0.3NL/ minutes4Gas flows into, and carries out the carbon coating treatment of 5 hours.Further more, degree of decompression at this time is 800Pa.Processing After cool down, obtained the SiO of 97.5g2The particle of middle Si dispersions has carried out the black particles of carbon coating.Obtained black particles are Average grain diameter is 5.2 μm, BET specific surface area 6.5m2/ g, relative to black particles 5.1 mass % of carbon amount of coating conduction Property particle.
<The synthesis 1 of polyamideimide resin solution>
While nitrogen is made to flow into 4 mouthfuls of flasks of 2L, while being loaded as the trimellitic anhydride 192g of polybasic acid anhydride, (1.0 rub You), as multicomponent isocyanate ortho-tolidine diisocyanate 132g (0.5 mole), 4,4 '-diphenyl methane two is different Cyanate 120g (O.48 mole), NMP1105g, being warming up to 100 DEG C, (monomer component with ortho-tolidine skeleton rubs for 25 You are %).After 3 hours, 160 DEG C are raised the temperature to, after carrying out reaction in 6 hours in this state, is carried out with NMP416g dilute It releases, cools down.When becoming 90 DEG C, the バ イ エ Le society DesmodurCT-stable12g as blocked isocyanate are put into, Stirring 3 hours.For obtained polyamideimide resin solution, tested, obtained using the method for SIS C2351 The value of 22.5 mass % of non-volatile content (200 DEG C, 2 hours), 110dPas/30 DEG C of viscosity.In addition, the springform of dry coationg It is 2,956MPa to measure, tensile elongation 20.4%.
<The modulation of cathode>
In above-mentioned 88 mass parts of electroconductive particle, using 3 μm of 1.0 mass parts of Delanium powder and as fine carbon fibre 6~20nm of outer diameter of dimension, the lip pencil structural unit aggregate of aspect ratio 2~30 Ube Industries, Ltd AMC361 (note Volume trade mark) 0.25 mass parts and 0.75 mass parts of acetylene black (AB) and 10 mass parts of above-mentioned polyamideimide resin solution mix It closes, and then adds in NMP20 mass parts and slurry is made, the N- Methyl-N-propyl piperidines of ionic liquid is added in the slurryBis- (trifluoromethane sulfonyl group) inferior amine salts (PP13-TFSI) (0.2 mass parts of weight of binder), are made slurry.This is starched Expect on the copper foil of 12 μm of thickness, change gap during coating, be coated with several thickness, after 1 hour dry at 80 DEG C, led to Roll-in is crossed, electrode is press-formed, after which is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, cathode is made.This is negative The electrolyte impregnability of pole is confirmed as 11 seconds.
<The modulation of anode>
Use Japan Chemical Industry society LiCoO2(mono- De C-10 of trade name セ Le シ) 94 mass parts, will electrochemically work 3 mass parts of industry society acetylene black and Wu Yu chemistry society Kynoar (PVdF) (trade name KF- Port リ マ mono-) 3 mass parts are mixed It closes, and then adds in NMP30 mass parts, slurry is made, which is coated on to aluminium foil 15 μm thick, it is 1 hour dry at 80 DEG C Afterwards, by roll-in, electrode is press-formed, after which is dried in vacuo 10 hours at 150 DEG C, is punched into 2cm2, it is made just Pole.
<Cell evaluation>
Here, for the charge-discharge characteristic of cathode evaluated, to electrode using lithium metal, as nonaqueous electrolyte, Lithium hexafluoro phosphate is made with the concentration of 1 mole/L using in 1/1 (volume ratio) mixed liquor of ethylene carbonate and diethyl carbonate The non-aqueous electrolytic solution of dissolving, partition board have used polyethylene microporous film 30 μm thick, and evaluation is modulated in argon glove box Use lithium rechargeable battery.
The lithium rechargeable battery of modulation is taken out from argon glove box, 25 DEG C are maintained in cryostat, is used Charging/discharging of secondary cell experimental rig ((strain) Na ガ ノ systems), with 0.15mA/cm2Constant current carry out charging until experiment electricity The voltage in pond reaches 0.005V.Electric discharge is with 0.15mA/cm2Constant current carry out, terminate at the time of cell voltage reaches 1.3V Electric discharge, is obtained first charge-discharge capacities and first efficiency (%)：The charging capacity of first discharge capacity/first.
Using using LiCoO2With acetylene black and the PVdF anode modulated and with above-mentioned electroconductive particle and polyamidoimide The cathode of modulation adjusts the capacity of anode and cathode so that first efficiency and the first efficiency to electrode lithium are substantially equal, just Pole and cathode are used makes work in 1/1 (volume ratio) mixed liquor of ethylene carbonate and diethyl carbonate with the concentration of 1 mole/L The non-aqueous electrolytic solution that lithium hexafluoro phosphate for nonaqueous electrolyte dissolves, by thick 30 μm of polyethylene microporous film be used for every Plate modulates evaluation lithium rechargeable battery in argon glove box.
The lithium rechargeable battery of modulation is taken out from argon glove box, 25 DEG C are maintained in cryostat, is used Charging/discharging of secondary cell experimental rig ((strain) Na ガ ノ systems) carries out charging until experiment electricity with the comparable constant current of 0.5CmA The voltage in pond reaches 4.2V, reduces current value at the time of 4.2V is reached, and carries out constant-voltage charge until 0.1CmA is suitable.It puts Electricity is carried out with the comparable constant currents of 0.5CmA, terminates to discharge at the time of cell voltage reaches 2.5V, repeatedly above charge and discharge Experiment has carried out the charge and discharge test of 200 cycles of evaluation lithium rechargeable battery.By first charge/discharge capacity and 200 The conservation rate (%) after discharge capacity and 200 cycles after cycle：The discharge capacity of the discharge capacity/first of 200th cycle It is shown in table 1.
[embodiment 2]
In 88 mass parts of electroconductive particle obtained in embodiment 1, by 3 μm of 1.0 mass parts of Delanium powder and work 0.25 mass parts of AMC361 (registered trademark) and 0.75 mass of acetylene black of Ube Industries, Ltd for fine carbon fiber 10 mass parts of polyamideimide resin solution of part and embodiment 1 mix, and then add in NMP20 mass parts and slurry is made, The dibutyl ethylene glycol solution (0.2 mass parts of weight of binder) as glycol ether is added in the slurry, slurry is made. By the slurry on the copper foil of 12 μm of thickness, change gap during coating, be coated with several thickness, dry 1 is small at 80 DEG C Shi Hou by roll-in, is press-formed electrode, after which is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, it is made negative Pole.The electrolyte impregnability of the cathode is confirmed as 13 seconds.Obtained cathode is tested similarly to Example 1.By result It is shown in table 1.
[embodiment 3]
In 88 mass parts of electroconductive particle obtained in embodiment 1, by 3 μm of 1.0 mass parts of Delanium powder and work 0.25 mass parts of AMC361 (registered trademark) and 0.75 mass of acetylene black of Ube Industries, Ltd for fine carbon fiber 10 mass parts of polyamideimide resin solution of part and embodiment 1 mix, and then add in NMP20 mass parts and slurry is made, The 12 4 ether powder of hat (0.2 mass parts of weight of binder) as crown ether are added in the slurry, slurry is made.By the slurry On the copper foil of 12 μm of thickness, change gap during coating, be coated with several thickness, after 1 hour dry at 80 DEG C, passed through Roll-in is press-formed electrode, after which is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, cathode is made.The cathode Electrolyte impregnability be confirmed as 15 seconds.Obtained cathode is tested similarly to Example 1.Show the result in table 1.
[embodiment 4]
In 88 mass parts of electroconductive particle obtained in embodiment 1, by 3 μm of 1.0 mass parts of Delanium powder and work 0.25 mass parts of AMC361 (registered trademark) and 0.75 mass of acetylene black of Ube Industries, Ltd for fine carbon fiber 10 mass parts of polyamideimide resin solution of part and embodiment 1 mix, and then add in NMP20 mass parts and slurry is made, PVdF resins (0.5 mass parts of weight of binder) are added in the slurry, slurry is made.By the slurry 12 μm of thickness copper On foil, change gap during coating, be coated with several thickness, after 1 hour dry at 80 DEG C, pass through roll-in, extrusion forming Electrode after the electrode is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, cathode is made.The electrolyte of the cathode is impregnated with Property is confirmed as 17 seconds.Obtained cathode is tested similarly to Example 1.Show the result in table 1.
[comparative example 1]
In 88 mass parts of electroconductive particle obtained in embodiment 1, by 3 μm of 1.0 mass parts of Delanium powder and work 0.25 mass parts of AMC361 (registered trademark) and 0.75 mass of acetylene black of Ube Industries, Ltd for fine carbon fiber 10 mass parts of polyamideimide resin solution of part and embodiment 1 mix, and then add in NMP20 mass parts and slurry is made. By the slurry on the copper foil of 12 μm of thickness, change gap during coating, be coated with several thickness, dry 1 is small at 80 DEG C Shi Hou by roll-in, is press-formed electrode, after which is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, it is made Cathode.The electrolyte impregnability of the cathode is confirmed as 85 seconds.
[comparative example 2]
In 90 mass parts of electroconductive particle obtained in embodiment 1, by new one ト EN-20 of Japan Chemical society リ カ Us 10 mass parts of the polyimide resin solution mixing of (registered trademark), and then add in NMP20 mass parts and slurry is made.This is starched Expect on the copper foil of 12 μm of thickness, change gap during coating, be coated with several thickness, after 1 hour dry at 80 DEG C, led to Roll-in is crossed, electrode is press-formed, after which is dried in vacuo 2 hours at 200 DEG C, is punched into 2cm2, cathode is made.This is negative The electrolyte impregnability of pole is confirmed as 75 seconds.
The polyamide-imide resin that is used in embodiment and comparative example, polyimide resin are measured using following methods Elasticity modulus.
On polyester film, the solution of polyamide-imide resin, polyimide resin is taken, with glass rod coating.By its After being dried 15 minutes at 120 DEG C, envelope is removed, it is 2 hours dry at 240 DEG C, obtain dry coationg.The quilt that will be obtained Film was obtained load-deformation curve, is calculated elasticity modulus with the speed tensile of 20mm/ minutes.
Further more, to electrode LiCoO2Result of the test is that the capacity of every 1 battery is described with mAh.In testing electrode Li, Li has found sufficiently large capacity, therefore be suitble to calculate the capacity of the cathode of target relative to the cathode of combination.
[table 1]
AB：Acetylene black
AMC：Ube Industries, Ltd's system：AMC361 (registered trademark)
PP13-TFSI：N- Methyl-N-propyl piperidinesBis- (trifluoromethane sulfonyl group) inferior amine salts
PVdF：Kynoar

Claims (8)

1. anode for nonaqueous electrolyte secondary battery contains：(A) in SiO2In be dispersed with the particle of Si, (B) by comprising with The ingredient synthesis of the monomer component of ortho-tolidine skeleton, above-mentioned monomer component are 10~50 moles of % of whole monomer components Polyamide-imide resin, the additional conductive material of (C) selected from carbon fiber and carbon black and (D) are selected from piperidinesSalt, glycol ethers, One kind or two or more substance in crown ether and Kynoar.
2. anode for nonaqueous electrolyte secondary battery described in claim 1, wherein, (B) ingredient is that elasticity modulus is 2, The polyamide-imide resin of more than 500MPa.
3. the anode for nonaqueous electrolyte secondary battery described in claims 1 or 2, wherein, (A) particle is further to be coated with carbon Coated particle.
4. the anode for nonaqueous electrolyte secondary battery described in claims 1 or 2, wherein, the carbon fiber of (C) ingredient is that have to lead The carbon fiber of electrical aspect ratio 4~50.
5. the anode for nonaqueous electrolyte secondary battery described in claims 1 or 2, wherein, the carbon fiber of (C) ingredient is by an oxygen Change carbon and the vapor grown carbon of hydrogen modulation.
6. the anode for nonaqueous electrolyte secondary battery described in claims 1 or 2, which is characterized in that also contain graphite.
7. lithium rechargeable battery, it includes claim 1~6 any one of them anode for nonaqueous electrolyte secondary battery.
8. the manufacturing method of anode for nonaqueous electrolyte secondary battery described in claim 1, which is characterized in that containing (A) In SiO2In be dispersed with the particle of Si, (B) is synthesized by the ingredient comprising the monomer component with ortho-tolidine skeleton, is above-mentioned Monomer component is the polyamide-imide resin of 10~50 moles of % of whole monomer components, and (C) is selected from carbon fiber and carbon black Additional conductive material and (D) are selected from piperidinesThe original of one kind or two or more substance in salt, glycol ethers, crown ether and Kynoar In material, solvent is kneaded and slurry is made, the collector of sheet is coated on, is dried in vacuo.
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