CN103872298A - Negative electrode for nonaqueous electrolyte secondary batteries, method for manufacturing same, and lithium ion secondary battery - Google Patents

Negative electrode for nonaqueous electrolyte secondary batteries, method for manufacturing same, and lithium ion secondary battery Download PDF

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Publication number
CN103872298A
CN103872298A CN201310699399.2A CN201310699399A CN103872298A CN 103872298 A CN103872298 A CN 103872298A CN 201310699399 A CN201310699399 A CN 201310699399A CN 103872298 A CN103872298 A CN 103872298A
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secondary battery
nonaqueous electrolyte
anode
electrolyte secondary
particle
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CN103872298B (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
    • H01M4/36—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
    • 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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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M4/00—Electrodes
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    • 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
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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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
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    • H01M4/362—Composites
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    • 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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    • H01M4/621—Binders
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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 invention provides a negative electrode for nonaqueous electrolyte secondary batteries, a method for manufacturing the same, and a lithium ion secondary battery, wherein the negative electrode can maintain a high battery capacity and a low ratio of volume expansion even if the negative electrode is dried under low temperature (lower than 250 DEG C), is high in efficiency of initial charging and discharging, is excellent in cycling performance, and takes scattered Si particles in SiO2 as an active material. The negative electrode comprises: (A), the scattered Si particles in SiO2; (B), polyamide-imide resin; (C), an auxiliary conductive material comprising carbon fibers and carbon black; and (D), a material improving the permeability of an electrolyte.

Description

Anode for nonaqueous electrolyte secondary battery and manufacture method thereof and lithium rechargeable battery
Technical field
The present invention relates to anode for nonaqueous electrolyte secondary battery and manufacture method thereof and lithium rechargeable battery.
Background technology
In recent years, along with the significant development of electronic equipment, the communication equipment etc. of pocket, from the miniaturization of economy and equipment, the viewpoint of lighting, strongly wish the rechargeable nonaqueous electrolytic battery of high-energy-density.In the past, as the high capacity strategy of this rechargeable nonaqueous electrolytic battery, knownly for example in negative material, use the oxide of B, Ti, V, Mn, Co, Fe, Ni, Cr, Nb, Mo etc. and the method (No. 3008228 communique of patent, No. 3242751 communique of patent: patent documentation 1,2) of their composite oxides, by the M of liquation chilling 100-xsi x(x>=50 atom %, M=Ni, Fe, Co, Mn) as the method (No. 3846661 communique of patent: patent documentation 3) of negative material, in negative material, use the oxide of silicon method (No. 2997741 communique of patent: patent documentation 4), in negative material, use Si 2n 2o, Ge 2n 2o and Sn 2n 2the method (No. 3918311 communiques of the patent mat woven of fine bamboo strips: patent documentation 5) of O etc.
Wherein, silica can be expressed as SiO x(wherein, x is due to oxide film thereon, therefore 1 bigger than theoretical value), adopting in the analysis of X-ray diffraction, forms nano-silicon microdispersed structure in silica of number nm～tens of nm left and right.In addition, by silicon oxide powder is heat-treated at the temperature in inactive non-oxidizing atmosphere, more than 400 ℃, carry out disproportionation, thus can form that the size of the crystallite of silicon is controlled at SiO 2the particle that middle Si disperses.Should be at SiO 2although the battery capacity of the particle that middle Si disperses is less than silicon, compared with carbon, Unit Weight is up to 5～6 times, and volumetric expansion is also little, thinks and easily uses as negative electrode active material.
At SiO 2in the particle that middle Si disperses, add binding agent and in the situation of modulator electrode, the Kynoar (PVdF) using for study plot in electrochemistry, discharges and recharges if repeated multiple times, reversible capacity diminishes, cycle characteristics variation.On the other hand, if use polyimide binder (comprising the polyamic acid that is heated as polyimides), although cycle characteristics improves, but first efficiency becomes very low, it is 70% left and right, in the situation of actual modulated battery, need positive pole superfluously, can not expect only to increase with the capacity of 5～6 times of units activity materials the increase of partial balanced battery capacity.Propose to use carbon, alloy in negative material, in its binding agent, used the negative pole of polyamide-imide resin, but be not applied to the example that silicon is negative material (patent documentation 6～11).In addition, also proposed to use polyamide-imide resin in silicon oxide series negative material, but there is no the record (JP 2009-152037 communique: patent documentation 12) of concrete example.Like this, at SiO 2problem in the practicality of the particle that middle Si disperses is remarkable, is that first efficiency is low, as solve its means, can enumerate supplement irreversible capacity part method, suppress the method for irreversible capacity.
For example, thus reported that the method for supplementing irreversible capacity part by Li doped metal is in advance effective.But, the method (Unexamined Patent 11-086847 communique: patent documentation 13) that for Li doped metal, Li paper tinsel is pasted to negative electrode active material surface and the method (JP 2007-122992 communique: patent documentation 14) of carrying out Li evaporation on negative electrode active material surface etc. are disclosed, for the stickup of Li paper tinsel, and use at SiO 2the acquisition difficulty of the Li paper tinsel that the first efficiency of the negative pole of the particle that middle Si disperses conforms to, cost is high, adopts the evaporation of Li steam to exist manufacturing process to become the problem such as complicated, impracticable.
On the other hand, disclose the mass ratio that improves Si by not relying on Li doping, increased the method for first efficiency.One is that Si powder is added at SiO 2the method (No. 3982230 communique of patent: patent documentation 15) that makes the mass ratio of oxygen reduce in the powder that middle Si disperses, on the other hand, be by make silicon vapor that the method (JP 2007-290919 communique: patent documentation 16) of the hybrid solid that obtains silicon and silica occurs, separates out in the fabrication stage of silica simultaneously.
As these resolution policy, in patent documentation 17, disclose adjustment acid amides/acid imide ratio and suppressed the first Efficiency Decreasing from polyimides, meet the method (JP 2011-60676 communique: patent documentation 17) that cycle characteristics maintains simultaneously, but there is electrode dryly need high temperature, maintain the still problem such as insufficient for long-term cycle characteristics.
Prior art document
Patent documentation
Patent documentation 1: No. 3008228 communique of patent
Patent documentation 2: No. 3242751 communique of patent
Patent documentation 3: No. 3846661 communiques of the patent mat woven of fine bamboo strips
Patent documentation 4: No. 2997741 communique of patent
Patent documentation 5: No. 3918311 communique of patent
Patent documentation 6: Unexamined Patent 11-102708 communique
Patent documentation 7: Unexamined Patent 11-126612 communique
Patent documentation 8: No. 3422390 communique of patent
Patent documentation 9: No. 3422391 communiques of the patent mat woven of fine bamboo strips
Patent documentation 10: No. 3422392 communique of patent
Patent documentation 11: No. 3422389 communique of patent
Patent documentation 12: JP 2009-152037 communique
Patent documentation 13: Unexamined Patent 11-086847 communique
Patent documentation 14: JP 2007-122992 communique
Patent documentation 15: No. 3982230 communique of patent
Patent documentation 16: JP 2007-290919 communique
Patent documentation 17: JP 2011-60676 communique
Summary of the invention
The problem that invention will solve
Even the object of the present invention is to provide by negative pole low temperature drying (being less than 250 ℃) also maintain high battery capacity and low cubical expansivity, first efficiency for charge-discharge is high, cycle characteristics is excellent, with at SiO 2the particle that middle Si disperses is as anode for nonaqueous electrolyte secondary battery and the manufacture method thereof of active material and used the lithium rechargeable battery of this negative pole.
For solving the means of problem
The inventor is studied for the binding agent of the reduction that can suppress first efficiency for charge-discharge, the reduction of this first efficiency for charge-discharge is the active material that improves the battery capacity of material with carbon element, is the SiO that the distinctive volumetric expansion of negative electrode active material changes can suppress silicon 2the particle that middle Si disperses is as active material, at this SiO 2the shortcoming of the particle that middle Si disperses.Polyimide binder (comprising the polyamic acid that is heated as polyimides), although cycle characteristics excellence find polyimides self to confirm and the reacting of lithium, become the essential factor that makes first Efficiency Decreasing.In addition, polyimide binder (comprising the polyamic acid that is heated as polyimides), need to the high dry temperature more than 250 ℃ under the operation of imidizate, there is the restriction in battery manufacture operation.On the other hand, only remove by solvent the polyimide binder (new Japanese physics and chemistry リ カ コ mono-ト etc.) that just obtains acid imide film, can reduce baking temperature.Even for imidizate finishes also to become solvent-soluble type, (1) beyond imide, import heat-staple functional group, fragrant family atomic group as " interval group ", the concentration of imide is reduced, (2) pass through between position in conjunction with the importing of base etc., give strand bendability, (3) import and produce sterically hindered bulky substituting group at side chain, Inhibitory molecules associates.By carrying out any one in these, only just can obtain acid imide film by low temperature drying, but exist, resin glue design is freely upper produces restriction, and infringement polyimides is the problems such as the high elastic modulus of resin.
The inventor will separate to confirm as the necessary function of binding agent of applicable battery material that can low temperature drying, found that by selecting modulus of elasticity be 2, polyamide-imide resin more than 500MPa, even reduction baking temperature, also obtain high circulation and maintain characteristic, completed the present invention.In addition, prepare in the situation of battery, the superfluous positive pole needing is reduced becomes possibility, by the increase of battery capacity and the anodal minimizing of high price, can obtain the rechargeable nonaqueous electrolytic battery of industrial low price.
Therefore, the invention provides following anode for nonaqueous electrolyte secondary battery and lithium rechargeable battery.
[1]. anode for nonaqueous electrolyte secondary battery, it contains: (A) at SiO 2particle, (B) polyamide-imide resin, (C) that middle Si disperses is selected from the secondary, conductive material of carbon fiber and carbon black and (D) improves the material of electrolyte impregnability.
[2] .[1] described anode for nonaqueous electrolyte secondary battery, wherein, (B) composition is that modulus of elasticity is polyamide-imide resin more than 2,500MPa.
[3] .[1] or [2] described anode for nonaqueous electrolyte secondary battery, wherein, (B) polyamide-imide resin is synthetic by the composition that comprises the monomer component with ortho-tolidine skeleton, and it is more than 10 % by mole that above-mentioned monomer component is whole monomer components.
[4] .[1] anode for nonaqueous electrolyte secondary battery described in～[3] any one, wherein, (A) particle is the coated particle of further using carbon coating.
[5] .[1] anode for nonaqueous electrolyte secondary battery described in～[4] any one, wherein, (C) carbon fiber of composition is the carbon fiber with the aspect ratio 4～50 of conductivity.
[6] .[1] anode for nonaqueous electrolyte secondary battery described in～[5] any one, wherein, (C) carbon fiber of composition is the vapor grown carbon by carbon monoxide and hydrogen modulation.
[7] .[1] anode for nonaqueous electrolyte secondary battery described in～[6] any one, wherein, (D) composition is selected from ionic liquid, glycol ethers and crown ether.
[8] .[1] anode for nonaqueous electrolyte secondary battery described in～[7] any one, it is characterized in that, also contain graphite.
[9]. lithium rechargeable battery, it comprises the anode for nonaqueous electrolyte secondary battery described in any one of [1]～[8].
[10] .[1] manufacture method of described anode for nonaqueous electrolyte secondary battery, it is characterized in that, containing (A) at SiO 2in the raw material of the secondary, conductive material that particle, (B) polyamide-imide resin, (C) that middle Si disperses comprises carbon fiber and carbon black and (D) material of raising electrolyte impregnability, by mixing solvent and make slurry, coated the collector body of sheet, carried out vacuumize.
The effect of invention
According to the present invention, though can provide by negative pole low temperature drying (being less than 250 ℃) also maintain high battery capacity and low cubical expansivity, first efficiency for charge-discharge is high, cycle characteristics is excellent, with at SiO 2the particle that middle Si disperses is as the anode for nonaqueous electrolyte secondary battery of active material and used the lithium rechargeable battery of this negative pole.
Embodiment
Below to the detailed description of the invention.
Anode for nonaqueous electrolyte secondary battery of the present invention contains: (A) at SiO 2particle, (B) polyamide-imide resin, (C) that middle Si disperses is selected from the secondary, conductive material of carbon fiber and carbon black and (D) improves the material of electrolyte impregnability.
(A) at SiO 2the particle that middle Si disperses
This particle is can occlusion, emit the particle of lithium ion.The particle of Si is at SiO 2state, its particle diameter of middle dispersion can be by the confirmations such as laser diffraction and scattering formula particle size distribution method, preferably 0.1～50 μ m of the particle diameter of Si particle, more preferably 1～20 μ m.
At SiO 2the particle that middle Si disperses is as the active material of anode for nonaqueous electrolyte secondary battery of the present invention.The method that the product that this particle for example can adopt (1) that the particulate of silicon is mixed with silicon based compound burns till, (2) for the silicon monoxide gas cooled that the mixture that adds thermal silicon dioxide and metallic silicon is generated, separate out and Si oxide, the silicon monoxide gas cooled that heating organo-silicon compound are generated of the amorphous that obtains, separate out and the Si oxide of the amorphous that obtains, heat treated at temperature more than 400 ℃, method of carrying out disproportionation etc. obtains.Owing to obtaining making the homodisperse particle of crystallite of silicon, the therefore method of preferred (2).
Xenogenesis element can also adulterate in (A) particle.As the method for doping, can enumerate silicon monoxide gas cooled that the mixture that adds thermal silicon dioxide and metallic silicon is generated, separate out and while modulating Si oxide, in the mixture of silicon dioxide and metallic silicon, mix Ni, Mn, Co, B, P, Fe, Sn, In, Cu, S, Al, C etc., the compound of use and xenogenesis element in metallic silicon uses the method for the compound of the xenogenesis element that adulterated etc. in silicon dioxide.
In addition, (A) of the present invention is at SiO 2the mol ratio of the oxygen/silicon in the particle that middle Si disperses, conventionally 1 bigger than theoretical value, generate with 1.0< oxygen/silicon (mol ratio) <1.1, by by (A) particle etching under acid atmosphere generating, can be optionally only by SiO 2remove.By optionally only by SiO 2remove, 0.2< oxygen/silicon (mol ratio) <1.1 becomes possibility.Wherein, under so-called acid atmosphere, can be the aqueous solution, also can be to contain sour gas, there is no particular restriction for its composition, can enumerate such as hydrofluoric acid, hydrochloric acid, nitric acid, hydrogen peroxide, sulfuric acid, acetic acid, phosphoric acid, chromic acid, pyrophosphoric acid etc., can a kind separately or two or more is suitably used in combination.For treatment temperature, be not particularly limited.According to said method, can use the Si of 0.2< oxygen/silicon (mol ratio) <1.1 at SiO 2the particle of middle dispersion.
(A) particle, also uses its surperficial coated particle of carbon coating from giving the aspect of conductivity, preferably becoming.As the method for coating, can enumerate make (A) particle and carbon etc. there is the method for the mix particles of conductivity, in organic gas to (A) particle surface carry out the method for chemical vapor deposition (CVD), by the method etc. of both combinations, preferably carry out the method for chemical vapor deposition (CVD).
For chemical vapor deposition (CVD), the method of simultaneously or in addition (A) particle being carried out to chemical vapor deposition (CVD) in organic gas with the heat treated of above-mentioned silicon based compound is preferred, by organic gas being imported in reactor when the heat treatment, thereby can carry out expeditiously.Particularly, can be by silicon based compound or (A) particle, in organic gas, 50Pa～30, under the decompression of 000Pa, at 700～1,200 ℃, carry out chemical vapor deposition and obtain.Preferred 50Pa～10 of above-mentioned pressure, 000Pa, more preferably 50Pa～2,000Pa.If degree of decompression is larger than 30,000Pa, the ratio with the graphite material of graphite-structure excessively becomes large, and as in the situation of negative electrode material for nonaqueous electrode secondary battery, except the reduction of battery capacity, cyclicity likely reduces.Preferably 800～1,200 ℃ of chemical vapor deposition temperature, more preferably 900～1,100 ℃.If treatment temperature is lower than 700 ℃, likely processes for a long time and become necessary.On the contrary, if higher than 1,200 ℃, by chemical vapor deposition processing, likely between particle, cause melting adhesion, cohesion, do not form conductive cell envelope at cohesion face, as in the situation of negative electrode material for nonaqueous electrode secondary battery, likely cycle performance reduces.Have, the processing time is suitably selected according to concentration (flow velocity), the import volume etc. of the carbon amount of coating of target, treatment temperature, organic gas, is generally 1～10 hour, is also efficiency especially about 2～7 hours economically again.
As the organic substance of the raw material as generation organic gas in the present invention, selecting particularly can thermal decomposition under above-mentioned heat treatment temperature and the organic substance of Formed (graphite) under nonacid atmosphere, can enumerate for example methane, ethane, ethene, acetylene, propane, butane, butylene, pentane, iso-butane, independent or the mixture of the hydrocarbon such as hexane, benzene, toluene, dimethylbenzene, styrene, ethylbenzene, diphenyl methane, naphthalene, phenol, cresols, nitrobenzene, chlorobenzene, indenes, coumarone, pyridine, anthracene, the luxuriant and rich with fragrance aromatic hydrocarbon of 1 ring～3 rings or their mixture of waiting.In addition the gas oil, creasote, the carbolineum that in tar distillation operation, obtain,, naphtha-cracked tar also can use separately or mixture also can use.
Amount of coating is not particularly limited, with respect to coated particle, preferably 0.3～40 quality %, more preferably 0.5～30 quality %.If carbon amount of coating is less than 0.3 quality %, likely can not maintain sufficient conductivity, result during as negative electrode material for nonaqueous electrode secondary battery sometimes cyclicity decline.On the contrary, even if carbon amount of coating exceedes 40 quality %, also can't see amount of coating increases the raising of the effect producing.
Physical property to (A) particle of the present invention and coated particle is not particularly limited, and average grain diameter is 0.1～30 μ m preferably, more preferably 0.2～20 μ m.In addition preferably 0.5～30m of BET specific area, 2/ g, more preferably 1～20m 2/ g.Have, the weight average particle diameter in the particle size distribution that average grain diameter can be carried out with employing laser diffractometry represents again.BET specific area is with passing through N 2value when the BET1 point method that gas adsorbance is evaluated is measured.
(B) polyamide-imide resin
Polyamide-imide resin of the present invention is not particularly limited, can a kind uses individually or two or more is suitably used in combination.Preferably the stretch modulus of dry coationg is polyamide-imide resin more than 2,500MPa.By becoming this scope, further improve as the charge/discharge cycle characteristics of rechargeable nonaqueous electrolytic battery.Stretch modulus preferably 2,500～7,000MPa.And then from the aspect of further raising charge/discharge cycle characteristics, tensile elongation is preferably below 25%, more preferably 3～25%.
While improving the modulus of elasticity of polyamide-imide resin, by resin matrix, particularly import upright and outspoken structure in main chain part, can realize.For example, by selecting 1,1 '-biphenyl-4, in 4 '-dicarboxylic acids, ortho-tolidine vulcabond, the monomer material of contained biphenyl backbone etc., for polymerization reaction, thereby becomes possibility.Especially, preferably use the monomer component with ortho-tolidine skeleton.Under situation by the synthetic polyamide-imide resin of the monomer component that comprises the monomer component with ortho-tolidine skeleton, preferably, it is more than 10 % by mole that the monomer component with ortho-tolidine skeleton is whole monomer components, is preferably the scope of 15～50 % by mole.And then, making tensile elongation is below 25% time, except above-mentioned condition, for example, be (X)/(Y) <1 by (I) being selected to total functional group molal quantity (X) of the sour composition in polybasic acid anhydride and/or polybasic carboxylic acid with the rate regulation of the total functional group molal quantity (Y) that (II) is selected from the composition in multicomponent isocyanate and/or polynary amine, control molecular weight, can realize.
The assay method > of < modulus of elasticity, tensile elongation
In the present invention, the modulus of elasticity of polyamide-imide resin adopts following method to measure.
Gather the solution of polyamide-imide resin, be applied on polyester film with glass bar.It after dry 15 minutes, is peeled off tunicle at 120 ℃, at 240 ℃, be dried 2 hours, obtain dry coationg.With the speed of the 20mm/ minute tunicle obtaining that stretches, obtain load-deformation curve, calculate modulus of elasticity and tensile elongation.In addition, adopt and use the same method, can measure polyimide resin etc.
Next, the manufacture method of polyamide-imide resin is illustrated to details.
Polyamide-imide resin in the present invention can be selected from composition in multicomponent isocyanate and/or polynary amine and reacts and obtain by making (I) be selected from sour composition in polybasic acid anhydride and/or polybasic carboxylic acid and (II).
As polybasic acid anhydride, have have acid anhydride and carboxyl compound, there is multiple acid anhydrides' compound, can enumerate the fragrant family polybasic acid anhydrides such as such as trimellitic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, oxygen di-O-phthalic acid dianhydride, 1,3,4-cyclohexane tricarboxylic acids-3,4-acid anhydride, 1,2,3, the alicyclic ring family polybasic acid anhydrides such as 4-butane tetracarboxylic acid dianhydride etc., can a kind use separately or two or more are suitably used in combination.Can also use by these derivative derivatives, for example, trimellitic anhydride alkyl esters etc., can form the trimellitic acid of intramolecular acid anhydride, benzene three formyl chlorides etc. partially.Consider the easiness of cost, acquisition, preferably trimellitic anhydride.Use trimellitic anhydride etc. has in acid anhydrides and the situation of carboxyl as the compound of functional group, even if do not use polybasic carboxylic acid, also can obtain polyamide-imide resin.
As polybasic carboxylic acid, can enumerate for example terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl methane dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenyl sulfone dicarboxylic acids, 1, 1 '-biphenyl-4, 4 '-dicarboxylic acids, trimellitic acid, the fragrant family polybasic carboxylic acid such as Pyromellitic Acid, butanedioic acid, adipic acid, decanedioic acid, dodecanedioic acid, 1, 2, 3, the aliphat polybasic carboxylic acids such as 4-BTCA, maleic acid, the unsaturated aliphatic polybasic carboxylic acids such as fumaric acid, 4-cyclohexene-1, the ester ring type polybasic carboxylic acids such as 2-dicarboxylic acids etc., can a kind use separately or two or more is suitably used in combination.Can also use by these derivative derivatives the acid anhydrides such as ester class, phthalic anhydride such as such as dimethyl terephthalate (DMT).
As multicomponent isocyanate, can enumerate such as methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), tolidine vulcabond, XDI, naphthalene diisocyanate, IPDI, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate etc., the polyisocyanates such as the polymer of methyl diphenylene diisocyanate, the polymer of toluene di-isocyanate(TDI).Wherein, preferably ortho-tolidine vulcabond, naphthalene diisocyanate, more preferably ortho-tolidine vulcabond etc. has the monomer component of ortho-tolidine skeleton.These can a kind use individually or two or more are suitably used in combination, and can also use by these derivative derivatives the such as blocked isocyanate class of phenol, xylenols or ketone etc.
As blocked isocyanate compound, for example, by 4, compound that 4 '-methyl diphenylene diisocyanate and xylenols acids obtain (the ミ リ オ ネ mono-ト MS-50 of Japanese polyurethane industry (strain) system), by 4, compound (コ ロ ネ mono-ト 2503 of Japanese polyurethane industry (strain) system), the compound (DesmodurCT-stable of バ イ エ Le society system) being obtained by tripolymer and the phenols of toluene di-isocyanate(TDI) etc. that 4 '-methyl diphenylene diisocyanate and aliphatic polyol, phenol or cresols class obtain are useful.These can be present in the reaction system of polyamide-imide resin, also can after reaction completes, drop into, dissolve.Especially, about the latter, for controlling the viscosity of polyamideimide resin solution, the object of raising bin stability, produce effect.
As polynary amine, can enumerate such as phenylenediamine, diaminodiphenyl-methane, methylene diamine, benzene dimethylamine, naphthylenediamine, toluenediamine, ortho-tolidine, hexamethylene diamine etc.These can a kind use individually or two or more are suitably used in combination.
Polyamide-imide resin in the present invention, can adopt common isocyanates method, use the manufacture such as method of acyl chlorides.From aspect reactive, cost, preferred isocyanate method.
In the polymerization of polyamide-imide resin, can use solvent.For example, can enumerate METHYLPYRROLIDONE (NMP), N-ethyl-2-pyrrolidone (NEP), N, N '-dimethylacetylamide (DMAc), N, the acid amides such as N '-dimethyl formamide (DMF) are such aromatic hydrocarbon series solvents such as sulfur-bearing series solvent, dimethylbenzene, naphtha such as the ether such as phenol solvent, diethylene glycol monomethyl ether series solvent, dimethyl sulfoxide (DMSO) of the ester series solvents such as lactone series solvent, dimethyl adipate, the dimethyl succinates such as polar solvent, gamma-butyrolacton, δ-valerolactone, cresols, xylenols etc.Wherein, preferred dissolution power, reactive excellent NMP, NEP, from cost, the easiness that obtains, most preferably NMP.These solvents can a kind use individually or two or more are suitably used in combination.
In addition, in polymerization, can use catalyst.Catalyst has the metal series catalysts such as the phosphorus series catalysts such as the such as amine such as triethylenediamine, pyridine, triphenyl phosphate, triphenyl phosphite, octenoic acid zinc, octenoic acid tin etc.The addition of catalyst, only otherwise hinder reaction, is not particularly limited, and divides, preferably 0.1～1 quality % with respect to resin.
When polymerization, temperature is not particularly limited the preferably scope of 50～200 ℃, more preferably 80～190 ℃.If reaction temperature is less than 50 ℃, reaction cannot be carried out smoothly, needs the long reaction time.If reaction temperature exceedes 200 ℃, the probability that generates accessory substance improves, and the possibility that the three dimensional stress of polyamide-imide resin occurs raises, and likely in reaction system, gelation occurs.
Use in the situation of polynary amine, first generate after amic acid, generate imide ring through closed loop operation, this closed loop operation can be carried out in the polymerization reaction system of polyamide-imide resin, also can temporarily under the state of amic acid, resin solution be taken out, in molding procedure thereafter, carry out closed loop.Baking temperature when above-mentioned polyamide-imide resin is used as to binding agent, can in time select the temperature from 120 degree to 200 degree.
(C) be selected from the secondary, conductive material of carbon fiber and carbon black
(C) secondary, conductive material is selected from carbon fiber and carbon black, can a kind uses individually or two or more is suitably used in combination.As carbon fiber, be not particularly limited, can enumerate gas-phase growth of carbon fibre, pitch-based carbon fiber, PAN based carbon fiber etc.Wherein, preferably the carbon fiber of dispersiveness and excellent electric conductivity, in negative pole, preferably has the carbon fiber of the aspect ratio 4～50 of conductivity.Especially, from the aspect of manufacturing, even preferably use in modulation easily fiber warpage is shortened, excellent dispersion and warpage shorten and also have the carbon fiber of conductivity, modulates negative pole.More specifically, by by the lip pencil construction unit assembly-use of external diameter 6～20nm, aspect ratio 2～30 in the manufacture of negative pole, become the carbon fiber of the aspect ratio 4～50 with conductivity, in negative pole, coordinate, cycle characteristics improve.Above-mentioned lip pencil construction unit aggregate is the hollow carbon fiber mutually connecting by graphite-based bottom surface, and in can being set forth in fiber, at least 1 of bag is for putting on the shear stress of this hollow carbon fiber, can produce the syndeton of slip between the graphite-based bottom surface of the construction unit aggregate of adjacency.As such hollow carbon fiber, can enumerate the vapor grown carbon of for example being modulated by carbon monoxide, can be set forth in the vapor grown carbon of being modulated by carbon monoxide and hydrogen under catalyst existence.As such carbon fiber, particularly, can enumerate the AMC361 (registered trade mark) of Ube Industries, Ltd etc.
As carbon black, can enumerate acetylene black, Ketjen black (Ketjen black), furnace black etc.
(D) material of raising electrolyte impregnability, as long as improving the material of electrolyte impregnability, be not particularly limited, remain in resin glue and the material that is easily dissolved in electrolyte, cell reaction is not had much impact as long as after dry, can a kind use or two or more is suitably used in combination separately.For example can enumerate resinous principles such as ionic liquid, glycol ethers, crown ether and PVdF resin as vapour pressure and the high liquid of boiling point etc., can add on a small quantity use.Setting out in these aspects that discharge and recharge reaction that never hinder significantly lithium ion, by adding ionic liquid, glycol ethers, crown ether-like, thereby improves electrolyte impregnability.In addition,, although the resins such as PVdF resin reduce with weight, also confirm the effect of improving for electrolyte impregnability.The addition that improves the material of electrolyte impregnability for these, divides quality, preferably 0.1～20.0 quality %, more preferably 1.0～10.0 quality % with respect to the solid of the binding agents such as (B) composition.By becoming such scope, do not hinder solidifying of the resin that uses in the binding agent of (B) composition etc., shorten ageing time, it is good that battery behavior becomes.
The confirmation method > of < electrolyte impregnability
The confirmation of electrolyte impregnability is carried out by the following method.The electrode stamping-out of making is become to 2cm 2using the solution mixing with 1 to 1 volume fraction as the ethylene carbonate of electrolyte solvent composition and diethyl carbonate, in hothouse, for the electrode of stamping-out, splash into 1cc with Mini liquid suction pipe, using electrode with the moment of electrolyte solvent composition homogenization as terminal, measure with stopwatch.To splash into afterwards until the time of terminal is that 30 seconds following materials are as " improving the material of electrolyte impregnability " of the present invention.Have, in above-mentioned confirmation method, adopting the difference of the result of the electrode generation of same formula making is in 3%, measures no problem again.Above-mentioned confirmation method until reality is used the time (0.5～48 hour) starting, is the judgement with the utmost point short time from pack electrolyte into actual battery after.The basis of this numerical value, (1) state of visual judgement moistened surface and to be impregnated into inner state extremely difficult, (2) for after splashing into until to be 30 seconds following batteries multiple the time of terminal and splash into after until the time of terminal be that 60 seconds above batteries are multiple, by after packing electrolyte into until under the situation of the actual time shorten of bringing into use (0.5 hour), after having confirmed to splash into, until being 30 seconds following batteries, the time of terminal reaches fifty-fifty the data of predetermined volumes, but for after splashing into until the time of terminal be 60 seconds above batteries, multiple batteries that do not reach predetermined volumes are confirmed.Thus, in the present invention, will after splashing into, until being 30 seconds following materials, the time of terminal be defined as " material that improves electrolyte impregnability ".
(D) ionic liquid of composition is the general name that also shows liquid ionic substance under normal temperature, has cation constituent and anion component.As the cation constituent of ionic liquid, can enumerate ammonium cation, pyrrolidines cation, piperidines
Figure BSA0000099181780000122
cation (following general formula (1)), imidazoles cation (following general formula (2)), pyridine cation (following general formula (3)),
Figure BSA0000099181780000138
cation (following general formula (4)), sulfonium cation (following general formula (5) etc.).
Figure BSA0000099181780000131
(R 1～R 4for alkyl or the alkoxyalkyl of the carbon number 1～18 that is same to each other or different to each other.In addition R, 1～R 4in 2 circuluses can with total same functional group.By R 1and R 2be called especially pyrrolidines by the situation that the saturated hydrocarbyl of carbon number 4 connects
Figure BSA0000099181780000139
cation, by R 1and R 2be called especially piperidines by the situation that the saturated hydrocarbyl of carbon number 5 connects
Figure BSA00000991817800001310
cation.)
Figure BSA0000099181780000132
(R 5, R 6for alkyl or the alkoxyalkyl of the carbon number 1～18 that is same to each other or different to each other.)
Figure BSA0000099181780000133
(R 7, R 8for alkyl or the alkoxyalkyl of the carbon number 1～18 that is same to each other or different to each other.And the substituting group on aromatic rings can be more than 2.)
Figure BSA0000099181780000134
(R 9～R 12for alkyl or the alkoxyalkyl of the carbon number 1～18 that is same to each other or different to each other.In addition R, 9～R 12in 2 circuluses can with total same functional group.)
Figure BSA0000099181780000135
(R 13～R 15for alkyl or the alkoxyalkyl of the carbon number 1～18 that is same to each other or different to each other.In addition R, 13～R 15in 2 circuluses can with total same functional group.)
In addition,, as anion component, enumerate following anion component as an example.Can illustrate two (trifluoromethane sulfonyl group) imines anion, two (pentafluoroethane sulfonyl) imines anion, two (fluorosulfonyl) imines anion, trifluoromethanesulfonic acid root anion, methylsulfate anion, ethyl sulphate anion, methanesulfonate anion, ethyl sulfonic acid root anion, p-methyl benzenesulfonic acid root anion, bisulfate ion anion, tetrafluoroborate anion, two [oxalate (2-)] borate anion, trifluoro (trifluoromethyl) borate anion, hexafluoro-phosphate radical anion, dimethyl phosphate radical anion, diethyl phosphate radical anion, three (pentafluoroethyl group) trifluoro phosphate radical anion, chloride ion, bromide ion, iodide ion, dicyanamide anion (dca) etc.
By the combination of above-mentioned cation and anion, can select various ionic liquids.But the ionic liquid that can use in the present invention has more than the combination that is defined in above-mentioned anionic-cationic.In addition, as the character of the ionic liquid using, owing to using in negative side, the ionic liquid that does not carry out decomposition reaction or be difficult to carry out decomposition reaction under the current potential of therefore preferably separating out at negative pole at lithium.
Consider under the situation of width, the easiness of acquisition etc. of electrochemical window preferably piperidines
Figure BSA0000099181780000141
salt, imidazoles
Figure BSA0000099181780000142
salt, particularly preferably, can illustrate N-methyl-N-propyl group piperidines two (trifluoromethane sulfonyl group) inferior amine salt (following, PP13-TFSI), N-methyl-N-propyl pyrrole alkane
Figure BSA0000099181780000144
two (trifluoromethane sulfonyl group) inferior amine salt (following, P13-TFSI), N-methyl-N-butyl pyrrolidine two (trifluoromethane sulfonyl group) inferior amine salt (following, P14-TFSI), N, N, two (trifluoromethane sulfonyl group) inferior amine salts of N-trimethyl-N-propyl ammonium (following, TMPA-TFSI), 1-ethyl-3-methyl-imidazoles
Figure BSA0000099181780000146
two (fluoromethane sulfonyl) inferior amine salt (following, EMIm-FSI), 1-ethyl-3-methyl-imidazoles
Figure BSA0000099181780000147
three (pentafluoroethyl group) three fluorophosphates (following, EMIm-FAP), 1-(2-methoxy ethyl)-1-crassitude
Figure BSA0000099181780000148
three (pentafluoroethyl group) three fluorophosphates (following, MOEMPL-FAP) etc.
As glycol ethers, high from boiling point, steam forces down, hinder not significantly the glycol ethers of lithium secondary battery reaction and select, can in time from glycol ether system, propylene glycol system and dialkyl group glycol ethers, select.Dialkyl group glycol ethers is the product that replaces the hydrogen of the end of ethylene glycol, diethylene glycol (DEG), triethylene glycol with alkyl.
Particularly, in glycol ether system, (boiling point 230 is spent can to enumerate the butyldiglycol high with the solubility of water, 25 degree vapour pressure 0.01hPa), methyl triethylene glycol (spend by boiling point 249, 25 degree vapour pressure 0.01hPa are following), butyl triethylene glycol (spend by boiling point 271, 25 degree vapour pressure 0.01hPa are following), benzyl diethylene glycol (DEG) (spend by boiling point 302, 25 degree vapour pressure 0.01hPa are following), (boiling point 259 is spent with hexyl diethylene glycol (DEG) that the solubility of water is little, 25 degree vapour pressure 0.01hPa are following), 2-ethylhexyl diethylene glycol (DEG) (spend by boiling point 272, 25 degree vapour pressure 0.1hPa are following) etc., in propylene glycol system, (boiling point 242 is spent can to enumerate the methyl propanediol high with the solubility of water, 25 degree vapour pressure 0.03hPa), (boiling point 274 is spent with butyl propylene glycol that the solubility of water is little, 25 degree vapour pressure 0.01hPa are following), phenyl propylene glycol (spend by boiling point 242, 25 degree vapour pressure 0.1hPa are following) etc., in dialkyl group glycol ethers system, (boiling point 254 is spent can to enumerate dibutyl diethylene glycol (DEG), 25 degree vapour pressure 0.01hPa) etc.
Crown ether-like is the polyethers (product that several ether units connect) of ring-type, can enumerate 12 hat 4 ethers, 15 hat 5 ethers, 18 hat 6 ethers, dibenzo-18-hat-6 etc.
[anode for nonaqueous electrolyte secondary battery]
Anode for nonaqueous electrolyte secondary battery of the present invention contains (A) at SiO 2particle, (B) modulus of elasticity that middle Si disperses is polyamide-imide resin, the secondary, conductive material that (C) comprises carbon fiber and carbon black and the material that (D) improves electrolyte impregnability more than 2,500MPa.(A) content of composition, with respect to negative pole, preferably 70～99.9 quality %, more preferably 80～99 quality %, further preferably 80～95 quality %, particularly preferably 80～88 quality %.(B) content of composition, with respect to negative pole, preferably 0.1～30 quality %, more preferably 1～20 quality %.Have again, above-mentionedly divide content for solid.(C) component content, with respect to negative pole, preferably 0.01～10.00 quality %, more preferably 0.1～2.0 quality %.(D) component content, with respect to negative pole, preferably 0.1～5.0 quality %, more preferably 0.2～1.0 quality %.
In negative pole, can add (A) composition graphite, other active materials (Sn, SnC in addition 2o 4) etc. other active materials.As other active materials, comprise difficult graphitized carbon, easily graphitized carbon and these high temperature and burn till product, spheroidizing product, flakey product, surface treatment product etc.Wherein, preferably by (A) composition and graphite use.By and use, can adjust electrode capacity.For example, all consumptions of negative pole can freely be adjusted, select to 2000mAh/g-electrode from 200mAh/g-electrode.In addition,, by this active material of more than two kinds is mixed and used, meet as high-voltage side the capacity more than 3.8V of Battery pack, low potential side capacity below 3.0V and become possibility.
Conductive agent beyond negative pole can add (C) composition.Kind to conductive agent is not particularly limited, as long as do not cause the material of decomposition, rotten electronic conductivity in the battery forming, particularly, can use the graphite of the metal dusts such as Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn, Si, metallic fiber, native graphite, Delanium, various coke powder, mesocarbon, various resin sintered bodies etc.The content of conductive agent, with respect to negative pole, preferably 0.1～30 quality %, more preferably 1～10 quality %.
In addition, except above-mentioned polyamide-imide resin, as viscosity modifier, can add carboxymethyl cellulose, Sodium Polyacrylate, other acrylic acid series polymeric compounds or fatty acid ester etc., its content, with respect to negative pole, suitably sets from the scope of 0.01～10 quality %.
Negative electrode material for nonaqueous electrode secondary battery of the present invention, for example formation negative pole as described below (formed body).Can enumerate following method: at (A) at SiO 2in the secondary, conductive material that particle, (B) polyamide-imide resin, (C) that middle Si disperses comprises carbon fiber and carbon black, the material and other additives as required that (D) improves electrolyte impregnability, by mixing the solvent of the dissolving of the applicable binding agents such as NMP (1-METHYLPYRROLIDONE), ethyl-methyl pyrrolidones, gamma-butyrolacton, water, dispersion, make slurry, coated the collector body of sheet, carried out vacuumize.As collector body, as long as the material that Copper Foil, nickel foil etc. use usually used as the collector body of negative pole, can use with no particular limitation thickness, surface treatment.Have again, the forming method that pulpous state mixture is shaped to sheet is not particularly limited, can adopt known method.Have again, above-mentioned vacuum drying method, temperature are not particularly limited, according to the present invention, even 250 ℃ following, 180～240 ℃, also can provide and maintain high battery capacity and low cubical expansivity, first efficiency for charge-discharge is high, cycle characteristics is excellent, be dispersed in SiO with Si 2in particle as the anode for nonaqueous electrolyte secondary battery of active material with used the lithium rechargeable battery of this negative pole.To being not particularly limited drying time, suitably select, be about 0.5～5.0 hour.
[rechargeable nonaqueous electrolytic battery]
Use anode for nonaqueous electrolyte secondary battery of the present invention, can manufacture lithium rechargeable battery.In this case, the aspect that the lithium rechargeable battery obtaining is stated negative pole in the use has feature, material and the cell shapes etc. of other positive pole, electrolyte, nonaqueous solvents, dividing plate, collector body etc. can be used known material and shape etc., are not particularly limited.For example, as positive active material, can use LiCoO 2, LiNiO 2, LiMn 2o 4, Li (Mn 1/3ni 1/3co 1/3) O 2, V 2o 5, MnO 2, TiS 2, MoS 2deng oxide and the chalcogen compound etc. of transition metal.As electrolyte, use the non-aqueous solution that for example comprises the lithium salts such as lithium hexafluoro phosphate, lithium perchlorate, as nonaqueous solvents, propylene carbonate, ethylene carbonate, dimethoxy-ethane, gamma-butyrolacton, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, vinylene carbonate, carbonic acid fluoro ethyl etc. a kind can be used separately or two or more is suitably used in combination.In addition, also can use this various non-water system electrolyte, solid electrolyte in addition.
In addition, obtain under the situation of electrochemical capacitor, the aspect that electrochemical capacitor is stated negative pole in the use has feature, for other material and the capacitor shape etc. of electrolyte, dividing plate etc. indefinite.For example, as electrolyte, use the non-aqueous solution that for example comprises the lithium salts such as lithium hexafluoro phosphate, lithium perchlorate, boron lithium fluoride, hexafluoroarsenate lithium, as nonaqueous solvents, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxy-ethane, gamma-butyrolacton, 2-methyltetrahydrofuran etc. a kind can be used separately or two or more is suitably used in combination.In addition, also can use this various non-water system electrolyte, solid electrolyte in addition.
[embodiment]
Embodiment and comparative example are below shown, the present invention is specifically described, but the present invention is not limited by following embodiment.
[embodiment 1]
The modulation > of < electroconductive particle
Be that 5 μ m, BET specific area are 3.5m by average grain diameter 2the Si oxide SiO of/g x(x=1.01) 100g packs in batch kiln.To in stove, reduce pressure with oily rotary vacuum pump, will in stove, be warmed up to 1,000 ℃ simultaneously, reach after 1,000 ℃, within 0.3NL/ minute, to make CH 4gas flows into, and carries out the carbon coating treatment of 5 hours.Have, degree of decompression is now 800Pa again.After processing, lower the temperature, obtained the SiO of 97.5g 2the black particles that the particle that middle Si disperses has carried out carbon coating.The black particles obtaining is that average grain diameter is that 5.2 μ m, BET specific area are 6.5m 2/ g, with respect to the electroconductive particle of the carbon amount of coating 5.1 quality % of black particles.
The synthetic 1> of < polyamideimide resin solution
Limit flows in 4 mouthfuls of flasks of 2L nitrogen, limit packs trimellitic anhydride 192g (1.0 moles) as polybasic acid anhydride, ortho-tolidine vulcabond 132g (0.5 mole), 4 as multicomponent isocyanate into, 4 '-methyl diphenylene diisocyanate 120g (O.48 mole), NMP1105g, be warmed up to 100 ℃ (monomer component with ortho-tolidine skeleton is 25 % by mole).After 3 hours, raise the temperature to 160 ℃, carry out in this state, after reaction in 6 hours, diluting with NMP416g, cooling.While becoming 90 ℃, drop into the バ イ エ Le DesmodurCT-stable12g processed of society as blocked isocyanate, stir 3 hours.For the polyamideimide resin solution obtaining, adopt the method for SIS C2351 to test, obtain the value of non-volatile content 22.5 quality % (200 ℃, 2 hours), viscosity 110dPas/30 ℃.In addition, the modulus of elasticity of dry coationg is 2,956MPa, and tensile elongation is 20.4%.
The modulation > of < negative pole
In above-mentioned electroconductive particle 88 mass parts, mix using 3 μ m Delanium powder 1.0 mass parts with as AMC361 (registered trade mark) 0.25 mass parts of the Ube Industries, Ltd of the lip pencil construction unit aggregate of the external diameter 6～20nm of fine carbon fiber, aspect ratio 2～30 and acetylene black (AB) 0.75 mass parts and above-mentioned polyamideimide resin solution 10 mass parts, and then add NMP20 mass parts and make slurry, in this slurry, add N-methyl-N-propyl group piperidines of ionic liquid
Figure BSA0000099181780000181
two (trifluoromethane sulfonyl group) inferior amine salt (PP13-TFSI) (0.2 mass parts of weight of binder), makes slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 11 seconds.
The modulation > of < positive pole
Use the LiCoO processed of Japan Chemical Industry society 2(trade name セ Le シ mono-De C-10) 94 mass parts, electrochemical industry society's acetylene black 3 mass parts processed and Wu Yu chemistry society's Kynoar processed (PVdF) (trade name KF-Port リ マ mono-) 3 mass parts are mixed, and then add NMP30 mass parts, make slurry, this slurry is coated to the aluminium foil of thick 15 μ m, dry after 1 hour at 80 ℃, by roll-in, extrusion forming electrode, by this electrode, at 150 ℃, vacuumize is after 10 hours, and stamping-out becomes 2cm 2, make positive pole.
< cell evaluation >
At this, in order to evaluate the charge-discharge characteristic of the negative pole obtaining, electrode is used to lithium metal, as nonaqueous electrolyte, use the non-aqueous electrolytic solution that with the concentration of 1 mole/L, lithium hexafluoro phosphate is dissolved in 1/1 (volume ratio) mixed liquor of ethylene carbonate and diethyl carbonate, dividing plate has used the polyethylene microporous film of thick 30 μ m, modulation evaluation lithium rechargeable battery in argon glove box.
From argon glove box, the lithium rechargeable battery of modulation is taken out, in cryostat, remain on 25 ℃, use charging/discharging of secondary cell experimental rig ((strain) Na ガ ノ system), with 0.15mA/cm 2determine that electric current charges until the voltage of test cell reaches 0.005V.Electric discharge is with 0.15mA/cm 2the electric current of determining carry out, the moment that reaches 1.3V at cell voltage finishes electric discharge, obtains first charging-discharge capacity and first efficiency (%): first discharge capacity/first charging capacity.
Use LiCoO 2negative pole anodal and that modulate with above-mentioned electroconductive particle and polyamidoimide with acetylene black and PVdF modulation, the capacity of anodal and negative pole of adjusting is so that first efficiency and roughly equal to the first efficiency of electrode lithium, in using 1/1 (volume ratio) mixed liquor at ethylene carbonate and diethyl carbonate, anodal and negative pole make using the concentration of 1 mole/L the non-aqueous electrolytic solution dissolving as the lithium hexafluoro phosphate of nonaqueous electrolyte, the polyethylene microporous film of thick 30 μ m, for dividing plate, is modulated to evaluation lithium rechargeable battery in argon glove box.
From argon glove box, the lithium rechargeable battery of modulation is taken out, in cryostat, remain on 25 ℃, use charging/discharging of secondary cell experimental rig ((strain) Na ガ ノ system), with suitable the determining of 0.5CmA, electric current charges until the voltage of test cell reaches 4.2V, in the moment that reaches 4.2V, current value is reduced, carry out constant-voltage charge until 0.1CmA is suitable.Electric discharge is carried out with the suitable electric current of determining of 0.5CmA, and the moment that reaches 2.5V at cell voltage finishes electric discharge, discharges and recharges test repeatedly above, has carried out evaluating the test that discharges and recharges circulating with 200 of lithium rechargeable battery.Conservation rate (%) by after the discharge capacity after first charge/discharge capacity and 200 circulations and 200 circulations: the discharge capacity/first discharge capacity of the 200th circulation is shown in table 1.
[embodiment 2]
In electroconductive particle 88 mass parts that obtain in embodiment 1, mix using 3 μ m Delanium powder 1.0 mass parts with as AMC361 (registered trade mark) 0.25 mass parts of Ube Industries, Ltd and the polyamideimide resin solution of acetylene black 0.75 mass parts and embodiment 1 10 mass parts of fine carbon fiber, and then add NMP20 mass parts and make slurry, in this slurry, add the dibutyl ethylene glycol solution (0.2 mass parts of weight of binder) as glycol ether, make slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 13 seconds.The negative pole obtaining is tested similarly to Example 1.Show the result in table 1.
[embodiment 3]
In electroconductive particle 88 mass parts that obtain in embodiment 1, mix using 3 μ m Delanium powder 1.0 mass parts with as AMC361 (registered trade mark) 0.25 mass parts of Ube Industries, Ltd and the polyamideimide resin solution of acetylene black 0.75 mass parts and embodiment 1 10 mass parts of fine carbon fiber, and then add NMP20 mass parts and make slurry, in this slurry, add the 12 hat 4 ether powder (0.2 mass parts of weight of binder) as crown ether, make slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 15 seconds.The negative pole obtaining is tested similarly to Example 1.Show the result in table 1.
[embodiment 4]
In electroconductive particle 88 mass parts that obtain in embodiment 1, mix using 3 μ m Delanium powder 1.0 mass parts with as AMC361 (registered trade mark) 0.25 mass parts of Ube Industries, Ltd and the polyamideimide resin solution of acetylene black 0.75 mass parts and embodiment 1 10 mass parts of fine carbon fiber, and then add NMP20 mass parts and make slurry, in this slurry, add PVdF resin (0.5 mass parts of weight of binder), make slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 17 seconds.The negative pole obtaining is tested similarly to Example 1.Show the result in table 1.
[comparative example 1]
In electroconductive particle 88 mass parts that obtain in embodiment 1, mix using 3 μ m Delanium powder 1.0 mass parts with as AMC361 (registered trade mark) 0.25 mass parts of Ube Industries, Ltd of fine carbon fiber and the polyamideimide resin solution of acetylene black 0.75 mass parts and embodiment 1 10 mass parts, and then add NMP20 mass parts and make slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 85 seconds.
[comparative example 2]
In electroconductive particle 90 mass parts that obtain in embodiment 1, the polyimide resin solution of the リ カ processed コ mono-ト EN-20 (registered trade mark) of new Japanese physics and chemistry society 10 mass parts are mixed, and then add NMP20 mass parts and make slurry.By this slurry, on the Copper Foil of thickness 12 μ m, the gap while changing coating with several thickness coating, is dried after 1 hour at 80 ℃, by roll-in, and extrusion forming electrode, by this electrode, at 200 ℃, vacuumize is after 2 hours, and stamping-out becomes 2cm 2, make negative pole.The electrolyte impregnability of this negative pole is confirmed as 75 seconds.
Adopt following method to measure the polyamide-imide resin using in embodiment and comparative example, the modulus of elasticity of polyimide resin.
On polyester film, take the solution of polyamide-imide resin, polyimide resin, be coated with glass bar.It after dry 15 minutes, is peeled off tunicle at 120 ℃, at 240 ℃, be dried 2 hours, obtained dry coationg.The tunicle obtaining is stretched with the speed of 20mm/ minute, obtain load-deformation curve, calculate modulus of elasticity.
Have again, to electrode LiCoO 2result of the test is to have recorded the capacity of every 1 battery with mAh.In electrode Li test, Li, with respect to the negative pole of combination, finds enough large capacity, is therefore applicable to the capacity of the negative pole that calculates target.
[table 1]
Figure BSA0000099181780000221
AB: acetylene black
AMC: Ube Industries, Ltd's system: AMC361 (registered trade mark)
PP13-TFSI:N-methyl-N-propyl group piperidines
Figure BSA0000099181780000222
two (trifluoromethane sulfonyl group) inferior amine salt
PVdF: Kynoar

Claims (10)

1. anode for nonaqueous electrolyte secondary battery, it contains: (A) at SiO 2particle, (B) polyamide-imide resin, (C) that middle Si disperses is selected from the secondary, conductive material of carbon fiber and carbon black and (D) improves the material of electrolyte impregnability.
2. anode for nonaqueous electrolyte secondary battery claimed in claim 1, wherein, (B) composition is that modulus of elasticity is polyamide-imide resin more than 2,500MPa.
3. the anode for nonaqueous electrolyte secondary battery described in claim 1 or 2, wherein, (B) polyamide-imide resin is synthetic by the composition that comprises the monomer component with ortho-tolidine skeleton, and it is more than 10 % by mole that above-mentioned monomer component is whole monomer components.
4. the anode for nonaqueous electrolyte secondary battery described in claim 1～3 any one, wherein, (A) particle is the coated particle of further using carbon coating.
5. the anode for nonaqueous electrolyte secondary battery described in claim 1～4 any one, wherein, (C) carbon fiber of composition is the carbon fiber with the aspect ratio 4～50 of conductivity.
6. the anode for nonaqueous electrolyte secondary battery described in claim 1～5 any one, wherein, (C) carbon fiber of composition is the vapor grown carbon by carbon monoxide and hydrogen modulation.
7. the anode for nonaqueous electrolyte secondary battery described in claim 1～6 any one, wherein, the material that (D) improves electrolyte impregnability is selected from ionic liquid, glycol ethers and crown ether.
8. the anode for nonaqueous electrolyte secondary battery described in claim 1～7 any one, is characterized in that, also contains graphite.
9. lithium rechargeable battery, it comprises the anode for nonaqueous electrolyte secondary battery described in claim 1～8 any one.
10. the manufacture method of anode for nonaqueous electrolyte secondary battery claimed in claim 1, is characterized in that, is containing (A) at SiO 2in the raw material of the secondary, conductive material that particle, (B) polyamide-imide resin, (C) that middle Si disperses comprises carbon fiber and carbon black and (D) material of raising electrolyte impregnability, by mixing solvent and make slurry, coated the collector body of sheet, carried out vacuumize.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106785026A (en) * 2016-11-29 2017-05-31 德阳九鼎智远知识产权运营有限公司 A kind of lithium battery electrolytes and preparation method thereof and its lithium ion battery
CN107851776A (en) * 2015-08-04 2018-03-27 三井化学株式会社 Lithium ion secondary battery cathode and lithium rechargeable battery and the manufacture method of lithium ion secondary battery cathode comprising it
CN110402511A (en) * 2017-03-15 2019-11-01 日本电气株式会社 Secondary cell adhesive composition
CN110959208A (en) * 2017-07-24 2020-04-03 株式会社村田制作所 Negative electrode for secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
CN111180692A (en) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 Negative electrode active material for battery and preparation method thereof
CN114204104A (en) * 2020-09-17 2022-03-18 马自达汽车株式会社 Lithium ion secondary battery and method for manufacturing same
US12148925B2 (en) 2019-12-31 2024-11-19 Berzelius (Nanjing) Co., Ltd. Anode active material for batteries, and method for preparing same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3621135B1 (en) * 2017-05-01 2022-06-01 Murata Manufacturing Co., Ltd. Negative electrode for lithium-ion rechargeable battery, and lithium-ion rechargeable battery
KR102343706B1 (en) * 2018-02-09 2021-12-24 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
KR20230033489A (en) * 2021-09-01 2023-03-08 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery and rechargeable lithium battery including same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS579069A (en) * 1980-06-20 1982-01-18 Toshiba Battery Co Ltd Alkaline battery
US20050244711A1 (en) * 2002-06-26 2005-11-03 Atsushi Fukui Negative electrode for lithium secondary cell and lithium secondary cell
CN101404330A (en) * 2007-10-02 2009-04-08 三星Sdi株式会社 Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
CN102024937A (en) * 2009-09-14 2011-04-20 信越化学工业株式会社 Negative electrode for nonaqueous electrolyte secondary batteries and lithium ion secondary battery
CN102227837A (en) * 2008-11-28 2011-10-26 住友化学株式会社 Electrode film, electrode, method for manufacturing electrode, and electrical storage device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS579069A (en) * 1980-06-20 1982-01-18 Toshiba Battery Co Ltd Alkaline battery
US20050244711A1 (en) * 2002-06-26 2005-11-03 Atsushi Fukui Negative electrode for lithium secondary cell and lithium secondary cell
CN101404330A (en) * 2007-10-02 2009-04-08 三星Sdi株式会社 Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
CN102227837A (en) * 2008-11-28 2011-10-26 住友化学株式会社 Electrode film, electrode, method for manufacturing electrode, and electrical storage device
CN102024937A (en) * 2009-09-14 2011-04-20 信越化学工业株式会社 Negative electrode for nonaqueous electrolyte secondary batteries and lithium ion secondary battery

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107851776A (en) * 2015-08-04 2018-03-27 三井化学株式会社 Lithium ion secondary battery cathode and lithium rechargeable battery and the manufacture method of lithium ion secondary battery cathode comprising it
CN106785026A (en) * 2016-11-29 2017-05-31 德阳九鼎智远知识产权运营有限公司 A kind of lithium battery electrolytes and preparation method thereof and its lithium ion battery
CN110402511A (en) * 2017-03-15 2019-11-01 日本电气株式会社 Secondary cell adhesive composition
CN110402511B (en) * 2017-03-15 2024-06-18 日本电气株式会社 Binder composition for secondary battery
CN110959208A (en) * 2017-07-24 2020-04-03 株式会社村田制作所 Negative electrode for secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
CN110959208B (en) * 2017-07-24 2023-12-08 株式会社村田制作所 Negative electrode for secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
CN111180692A (en) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 Negative electrode active material for battery and preparation method thereof
CN111180692B (en) * 2019-12-31 2021-10-08 安普瑞斯（南京）有限公司 Negative electrode active material for battery and preparation method thereof
US12148925B2 (en) 2019-12-31 2024-11-19 Berzelius (Nanjing) Co., Ltd. Anode active material for batteries, and method for preparing same
CN114204104A (en) * 2020-09-17 2022-03-18 马自达汽车株式会社 Lithium ion secondary battery and method for manufacturing same

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