CN102318108A - Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry - Google Patents

Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry Download PDF

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Publication number
CN102318108A
CN102318108A CN2010800073074A CN201080007307A CN102318108A CN 102318108 A CN102318108 A CN 102318108A CN 2010800073074 A CN2010800073074 A CN 2010800073074A CN 201080007307 A CN201080007307 A CN 201080007307A CN 102318108 A CN102318108 A CN 102318108A
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formula
slurry
cement
electrode
lithium secondary
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高明天
有马博之
坂田英郎
中泽瞳
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Daikin Industries Ltd
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Daikin Industries Ltd
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Disclosed is an electrode mixture slurry that is stable with no gelation, and additionally disclosed are an electrode with good adhesion between the binder and collector and with ample flexibility, and a lithium secondary battery with excellent battery characteristics. The electrode mixture slurry for lithium secondary batteries comprises an electrode active material, a binder, and an organic solvent. The binder is a fluorine-containing polymer represented by the composition formula: (VDF)m(TFE)n(HFP)l (In the formula, VDF represents structural unit derived from vinylidene fluoride; TFE represents a structural unit derived from tetrafluoroethylene; HFP represents a structural unit derived from hexafluoropropylene; 0.45 <= m <= 1; 0.05 <= n <= 0.5; 0 <= l <= 0.1; where m + n + l = 1.), and includes a solvent-soluble thermoplastic resin that is not a fluorine-containing polymer.

Description

The electrode composition of lithium secondary battery is with slurry, the electrode that has used this slurry and lithium secondary battery
Technical field
The electrode composition of lithium secondary battery that the present invention relates to excellent in stability is with slurry, the electrode that is imbued with flexibility that has used this slurry and the improved lithium secondary battery of battery behavior.
Background technology
Lithium secondary battery as the power supply of various pocket electric/electronic devices, or be widely used as the battery of electric automobile etc.
Lithium secondary battery possesses positive pole, negative pole and nonaqueous electrolytic solution, also possesses barrier film usually, and the exploitation improvement of each parts is carried out just energetically.
Wherein, anodal following usually the making: for example positive active material is scattered in the organic solvent with cement (being knotted drug), as required conductive material, preparation anode mixture slurry, coat positive electrode collector after, drying is except that desolvating and rolling.
Cement as the positive pole usefulness of lithium secondary battery often used polyvinylidene fluoride (PVdF) in the past.Following technology is for example disclosed in the patent documentation 1: will be as the LiCoO of positive active material 2Mix with PVdF Deng the otide containing lighium thing with as the graphite of conductive agent, produce anode mixture, anode mixture is scattered in processes pulp-like in the N-methyl pyrrolidone, this slurry is coated on the aluminium foil positive electrode collector; In addition, will be as the carbonaceous material and the mixed cathode agent of making of PVdF of negative electrode active material, cathode agent is scattered in the N-methyl pyrrolidone processes pulp-like, this slurry is coated on the Copper Foil as negative electrode collector.After both are distinguished drying, use the roll squeezer extrusion molding, be processed into electrode slice.But, the organic solvent swelling of the nonaqueous electrolytic solutions such as propylene carbonate, ethylene carbonate, diethyl carbonate or its mixture that PVdF is easy to be used in the lithium rechargeable battery.Therefore, produced following problem: when repeating to discharge and recharge, and as the cementability variation between the metal forming of collector body, its result causes that inside battery resistance rises, and battery performance reduces.In addition; Use PVdF to lack flexibility as the electrode slice of cement; In making the process of rectangular cell, electrode slice is folded in the operation of 180 degree and in the process of making cylindrical battery, electrode slice is rolled in the operation of rouleau; Be easy to generate the problem that electrode composition strips down from electrode slice, the rate of finished products variation of production.
In addition; In the patent documentation 2; Having put down in writing a kind of is that the material with caoutchouc elasticity of main component is as cement with fluorine-containing bipolymers such as vinylidene fluoride (VdF)-hexafluoropropylene (HFP) copolymer, VdF-CTFE (CTFE) copolymers; The purpose of this material is, gives the positive active material zygosity, with expansion, the contraction of the positive active material of antagonism nonaqueous electrolytic solution secondary battery when discharging and recharging.Therefore but the crystallinity of such copolymer is poorer than PVdF, compares with PVdF more easily by the organic solvent swelling of nonaqueous electrolytic solution, and cement can stripping in the kind of some electrolyte, thereby can't accomplish its task.
As same cement, to put down in writing a kind of fluoro containing polymers copolymer in the patent documentation 3 and be used for cement, this fluoro containing polymers copolymer does not use PVdF by VdF, tetrafluoroethene (TFE) and HFP as the main component formation.The compositing range of the copolymer of putting down in writing in its claims, in molar fraction, VdF is 0.3～0.9, and HFP is 0.03～0.5, and TFE is 0～0.5, and the molar fraction of these three kinds of monomers adds up to 0.80～1.
In addition, put down in writing a kind of cement in the patent documentation 4, it is difficult in general solvent, had deliquescent electrolyte organic solvent swelling especially.Disclosed cement is the binary fluorinated copolymer of VdF50～80 mole % and TFE20～50 mole % and the ternary fluorinated copolymer that VdF50～80 mole %, TFE17～50 mole % and other comonomers are lower than 3 moles of % in the patent documentation 4; As the VdF/TFE based copolymer that uses among the embodiment, VdF/TFE copolymer and VdF/TFE/HFP copolymer have been put down in writing.Put down in writing in addition; In order to improve the cementability with collector body, also can contain resins such as polymethacrylates below the about 20 volume % of content, polymethyl methacrylate, polyacrylonitrile, polyimides, polyamide, polyamidoimide, Merlon in the cement.
In addition, propose in the patent documentation 5, in order to improve the cycle characteristics under the high temperature, as cement, except PVdF share polyimides, share aromatic polyamide in negative side with external side of the positive electrode.
In addition; A kind of method has been proposed in the patent documentation 6; It is handled the surface of collector body with acrylic acid series polymeric compounds, and has put down in writing in order to improve the cementability of collector body and cement; As its cement, also can use the mixture of the copolymer of PVdF 50～95 weight % and VdF and other polymer (for example TFE, HFP, CTFE etc.).
On the other hand,, also carrying out various exploitations, occurring the positive active material that contains Ni, Mn and reduced rare metal Co recently from aspects such as battery behavior, fail safe, resource (rare metal) exhaustions about positive active material.But these contain the positive electrode of Ni, Mn because alkalescence is high, thereby the easy gelation of slurry.In addition, about negative electrode active material, except the carbon-based material that in the past used, the active material that is made up of basic matterial has appearred also.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 04-249859 communique
Patent documentation 2: japanese kokai publication hei 04-095363 communique
Patent documentation 3: the special fair 08-004007 communique of Japan
Patent documentation 4: japanese kokai publication hei 10-233217 communique
Patent documentation 5: japanese kokai publication hei 11-031513 communique
Patent documentation 6: japanese kokai publication hei 09-199133 communique
Summary of the invention
The problem that invention will solve
Yet, comprise LiCoO 2, LiNiO 2, LiMn 2O 4Interior, lithium-contained composite oxide is essentially alkalescence, though its reason confirm as yet, causing gelation in slurry, have the impaired problem of stability of slurry with the anode mixture of PVdF perhaps many VdF based copolymer coexistence.Use under the situation of basic matterial as negative electrode active material at negative pole, also can have same problem.In addition, under the situation for alkaline negative pole, swelling is violent, thereby existing P VdF causes coming off of negative electrode active material easily.People are for also studying polyimides as cement, but resulting electrode is stone, have the problem that is easy to generate crackle.
In addition, poor slightly though the VdF/TFE based copolymer is imbued with flexibility with the cementability of collector body, also require to improve in this respect.
The object of the present invention is to provide a kind of stable electrode composition that does not produce gelation with slurry and manufacturing approach thereof, and then the cementability raising between a kind of mixture and the collector body is provided and is imbued with the electrode of flexibility and the lithium secondary battery of battery behavior excellence.
Be used to solve the scheme of problem
About said purpose; The inventor has carried out further research, and the result finds, among the VdF based copolymer; VdF/TFE based copolymer so that specified quantitative obtains VdF and TFE copolymerization is all of a sudden stable to the electrode active material of alkalescence; The electrode composition that mixes and prepare can know in addition that with slurry also homogeneous and stable the electrode that uses this electrode composition to form with slurry has excellent flexibility; Do not produce peeling off between electrode composition and the collector body yet, can also improve the battery behavior of lithium secondary battery.
The alkali resistance of this excellence is a special observed characteristic in the VdF/TFE based copolymer, and in other VdF based copolymers such as VdF/HFP based copolymer or VdF/CTFE based copolymer, fails to find.
Promptly; The electrode composition that the present invention relates to a kind of lithium secondary battery is used slurry; It is characterized in that; It uses slurry for the electrode composition of lithium secondary battery that contains electrode active material (A), cement (B) and organic solvent (C), and cement (B) contains fluoropolymer that (B1) composition formula (B1) representes and (B2) the solvable type thermoplastic resin of the solvent except that fluoropolymer (B1)
Composition formula (B1):
(VDF) m(TFE) n(HFP) l
(in the formula, VDF is the construction unit from vinylidene fluoride; TFE is the construction unit from tetrafluoroethene; HFP is the construction unit from hexafluoropropylene; 0.45≤m≤1; 0.05≤n≤0.5; 0≤l≤0.1, wherein, m+n+l=1.)
Electrode active material (A) is particularly suitable for containing the situation of positive active material (A1) of the lithium-contained composite metal oxide of formula (A1) expression; In addition, electrode active material (A) is particularly suitable for comprising the situation of the negative electrode active material (A2) of the basic matterial that contains Si and/or Sn.
Formula (A1):
Li xM 1 yM 2 1-yO 2
(in the formula, 0.4≤x≤1; 0.3≤y≤1; M 1For being selected from least a element in the group of forming by Ni and Mn; M 2For being selected from least a element in the group of forming by Co, Al and Fe.)
In addition, the present invention relates to a kind of electrode of lithium secondary battery, it obtains through electrode composition of the present invention is coated collector body and carried out drying with slurry.
In addition, the present invention relates to a kind of lithium secondary battery, it as positive pole and/or negative pole, and possesses nonaqueous electrolytic solution with electrode of the present invention.
The effect of invention
According to the present invention; Can provide homogeneous and stable electrode composition to use slurry, can provide in addition use that this electrode composition forms with slurry with the excellent in adhesion of collector body and be imbued with the electrode of flexibility and then can provide the battery behavior that uses this electrode composition excellent lithium secondary battery.
Embodiment
The electrode composition of lithium secondary battery of the present invention contains electrode active material (A), cement (B) and organic solvent (C) with slurry.Below, each composition is described.
(A) electrode active material
Among the present invention, electrode active material can be positive active material (A1), also can be negative electrode active material (A2).
(A1) positive active material
As positive active material (A1), be the lithium-contained composite metal oxide of formula (A1) expression.
Formula (A1):
Li xM 1 yM 2 1-yO 2
(in the formula, 0.4≤x≤1; 0.3≤y≤1; M 1For being selected from least a element in the group of forming by Ni and Mn; M 2For being selected from least a element in the group of forming by Co, Al and Fe.)
Specifically, be preferably
Formula (A1-1):
LiNi xCo yAl zO 2
(in the formula, 0.7≤x≤1; 0≤y≤0.3; 0≤z≤0.03; 0.9≤x+y+z≤1.1),
Formula (A1-2):
LiNi xCo yMn zO 2
(in the formula, 0.3≤x≤0.6; 0≤y≤0.4; 0.3≤z≤0.6; 0.9≤x+y+z≤1.1),
Formula (A1-3):
Li xMn zO 2
(in the formula, 0.4≤x≤0.6; 0.9≤z≤1) or
Formula (A1-4):
LiFe xCo yMn zO 2
(in the formula, 0.3≤x≤0.6; 0.1≤y≤0.4; 0.3≤z≤0.6; 0.9≤x+y+z≤1.1) the lithium-contained composite metal oxide of expression.
As the object lesson of the lithium-contained composite metal oxide of formula (A1-1) expression, can enumerate for example LiNi 0.8Co 0.2O 2, LiNi 0.7Co 0.3O 2, LiNi 0.82Co 0.15Al 0.03O 2, LiNi 0.7Co 0.2Al 0.1O 2, LiNi 0.85Co 0.1Al 0.5O 2Deng, wherein be preferably LiNi 0.82Co 0.15Al 0.03O 2(NCA).
As the object lesson of the lithium-contained composite metal oxide of formula (A1-2) expression, can enumerate for example LiNi 0.5Mn 0.5O 2, LiNi 0.75Mn 0.25O 2, LiNi 0.25Mn 0.75O 2, LiNi 1/3Co 1/3Mn 1/3O 2, LiNi 0.4Co 0.2Mn 0.4O 2, LiNi 0.3Co 0.5Mn 0.2O 2Deng, wherein be preferably LiNi 1/3Co 1/3Mn 1/3O 2(NCM).
As the object lesson of the lithium-contained composite metal oxide of formula (A1-3) expression, can enumerate for example Li 0.5MnO 2(spinel manganese), LiMnO 2Deng.
As the object lesson of the lithium-contained composite metal oxide of formula (A1-4) expression, can enumerate for example LiFe 1/3Co 1/3Mn 1/3O 2, Li 0.5Fe 1/3Co 1/3Mn 1/3O 2, LiFe 0.4Co 0.3Mn 0.3O 2, Li 0.5Fe 0.4Co 0.3Mn 0.3O 2Deng.
In addition, can also use LiCoO 2, LiNiO 2, LiMn 2O 4Deng.
(A2) negative electrode active material
As negative electrode active material (A2), but illustration goes out known basic matterial, for example contains the material that is alkalescence of Si and/or Sn.Specifically, also can use the metallic compound that can insert lithium ion, for example metal oxide or metal nitride, Si, SiCuAl, SiNiAg, CoSn 2Deng.As metal oxide, can enumerate the metal oxide that contains Si, Sn, as metal nitride, can enumerate Li 2.6Co 0.4N etc.
(B) cement
Among the present invention, as cement, using the VdF/TFE of composition formula (B1) expression is fluoropolymer (B1) and these two kinds of polymer of the solvable type thermoplastic resin of solvent (B2) (wherein, except the B1).
(B1) VdF/TFE is a fluoropolymer
Cement (B1) contains the fluoropolymer of composition formula (B1) expression.Need to prove that construction unit VDF, TFE and HFP can link in any order, also can randomly exist.
Composition formula (B1):
(VDF) m(TFE) n(HFP) l
(in the formula, VDF is the construction unit from vinylidene fluoride; TFE is the construction unit from tetrafluoroethene; HFP is the construction unit from hexafluoropropylene; 0.45≤m≤1; 0.05≤n≤0.5; 0≤l≤0.1, wherein, m+n+l=1.)
Wherein,, consider that m, n and the l in the preferred formula (B1) is respectively 0.50≤m≤0.90,0.10≤n≤0.50 and 0≤l≤0.08, and (wherein, m+n+l=1) VdF/TFE is a fluorinated copolymer from the aspect that flexibility and alkali resistance are good as fluoropolymer.
Wherein, consider that m in the preferred formula (B1) and n are respectively 0.50≤m≤0.90 and 0.10≤n≤0.50 (wherein, m+n=1) VdF/TFE binary fluorinated copolymer from the aspect that flexibility and alkali resistance are good.Consider that from alkali resistance, the good aspect of flexibility preferred n (TFE) is 0.10～0.40, particularly 0.15～0.40 material in addition.
In addition, consider preferred 0.50≤m≤0.90,0.09≤n≤0.49 and 0.01≤l≤0.04 (wherein, m+n+l=1) VdF/TFE/HFP ternary fluorinated copolymer from the aspect that flexibility and alkali resistance are good.Consider the copolymer of the copolymer of preferred 0.60≤m≤0.90,0.09≤n≤0.45,0.01≤l≤0.04 and then 0.60≤m≤0.70,0.30≤n≤0.40,0.02≤l≤0.04 from alkali resistance, the good aspect of flexibility in addition.
No matter binary system or ternary system if the content of TFE is compared with above-mentioned scope were difficult to be dissolved in the organic solvent at most, and on the other hand, alkali resistance reduces, flexibility reduces if cross at least easily, possibly can't fully realize effect of the present invention.
About the molecular weight of VdF/TFE based copolymer, the number-average molecular weight during GPC (gel permeation chromatography) measures is preferably 10000～500000 in the polystyrene conversion value.If low excessively less than 10000 molecular weight, can't film forming, very big if surpass the thixotropy of 500000 electrode compositions in addition, have the tendency that is difficult to coat electrode collector.In addition, in order to improve cycle characteristics, the copolymer that preferred molecular weight is higher is considered from this respect, for example is preferably 150000～500000 under the situation of terpolymer.
The VdF/TFE based copolymer that uses as cement (B1) among the present invention can wherein, mainly be preferably free radical copolymerization method through known polymerization polymerization.That is, as polymerization, so long as the method for carrying out with the mode of free radical then its means have no restriction, for example through initiations such as organic or inorganic radical polymerization initiator, heat, light or ionizing rays.The form of polymerization also can be used polymerisation in solution, polymerisation in bulk, suspension polymerisation, emulsion polymerisation etc.
The alkali resistance of this VdF/TFE based copolymer is excellent; Nitrogenous for the N-methyl pyrrolidone that uses as the solvent of PVdF, dimethyl formamide, dimethylacetylamide etc. is that organic solvent is solvable certainly; Also solvable for normally used lower boiling general organic solvent; Also do not cause gelation even mix, and can give flexibility, and the swellability in nonaqueous electrolytic solution is also little electrode with electrode active material.
(B2) the solvable type thermoplastic resin of solvent
Among the present invention, cement (B2) is the solvable type thermoplastic resin of solvent, and the solvable type thermoplastic resin of this solvent has the effect of the cementability of raising and collector body.Among the present invention; " the solvable type thermoplastic resin of solvent " is meant; In organic solvent (C); At 25 ℃ of thermoplastic resins that dissolve more than the 5 quality % down and form uniform solution, be preferably at least a cement that is selected from the group of forming by polyvinylidene fluoride (PVdF), polyacrylic acid based polymer, polymethylacrylic acid based polymer, polyimides, polyamide and polyamidoimide.
As PVdF, the material that can directly use in the past the cement as secondary lithium batteries to use.When using PVdF as cement (B2), from keep flexibility, the good aspect of adaptation is considered, be preferably 10～90 quality % of cement (B1) and total amount (B2), further be preferably 50～90 quality %.That is, cement (B1) is being born the effect of giving flexibility, and cement (B2) is being born the effect of giving adaptation, thereby can be according to purpose combination (cooperation) evenly at random.
As the polyacrylic acid based polymer, but illustration goes out for example polyacrylic acid, its ammonium salt, sodium salt; Polyalkyl acrylate; Polyacrylic acid amide; Alkoxysilyl modified polyacrylate etc.
As the polymethylacrylic acid based polymer, but illustration goes out for example polymethylacrylic acid, its ammonium salt, sodium salt; Polyalkyl methacrylate; The polymethylacrylic acid acid amides; Alkoxysilyl modified polymethyl acid esters etc.
When use is selected from least a cement in the group of being made up of acrylic acid series polymeric compounds, polymethylacrylic acid based polymer, polyimides, polyamide and polyamidoimide as cement (B2); From keeping flexibility, the good aspect consideration of adaptation, be preferably 1～20 quality % of cement (B1) and total amount (B2).
Under the situation about using as the binding agent of negative pole; Combinations thereof (cooperation) is preferred when using graphite as negative electrode active material; When using the high active material of swellabilities such as silicon dioxide, metal, alloy, preferably use polyimides, polyamide, polyamidoimide as cement (B2) and mix the cement (B1) of 1～40 quality % of (B1) and total amount (B2).In this case, cement (B2) is being born the effect that suppresses swellability, and cement (B1) is being born the effect of giving flexibility.
(C) organic solvent
Electrode composition of the present invention with slurry be through with electrode active material (A) and cement (B) and after the electrode material mixed and dispersed such as electric conducting material stated in organic solvent, obtain.
As the organic solvent (C) that uses in the preparation of electrode composition of the present invention with slurry; Except N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide etc. are nitrogenous is the organic solvent, can enumerate ketones solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK); Esters solvent such as ethyl acetate, butyl acetate; Ether solvent such as oxolane, dioxane; And their lower boiling general organic solvents such as mixed solvent.Wherein, particularly consider, be preferably the N-methyl pyrrolidone from stability of slurry, the excellent aspect of coating.
In addition, use slurry in order to make stable electrode composition, the moisture of organic solvent (C) is very important.That is, to make moisture be below the 100ppm and then be 30ppm when following, manifests fewly by the alkalescence of alkaline electrode active material generation, can suppress gelation.
(D) other electrode materials
Among the present invention, in the scope of not damaging effect of the present invention, can mix other electrode materials as required.
As other electrode materials, but illustration goes out for example electric conducting material etc.As electric conducting material, can enumerate for example material with carbon element such as carbon black such as acetylene black, Ketjen black class and graphite etc.
As the preparation method of electrode composition of the present invention, be generally following method: cement (B) is dissolved in the organic solvent (C), electrode active material (A), electric conducting material dispersions such as (D) are mixed in the resulting solution with slurry.In addition, after also can the powder of for example cement (B), electrode active material (A), electric conducting material (D) being pre-mixed each other, add organic solvent (C) and the preparation slurry.
Electrode composition of the present invention is with in the slurry; Negative or positive electrode no matter, the mixed proportion of cement (B) ((B1) and total (B2)) be in the solid constituent (electrode active material (A), cement (B), electric conducting material (D) etc.) 0.1～20 quality %, be preferably 1～10 quality %.The combined amount of electrode active material (A) be in the solid constituent 80～98 quality %, be preferably 90～97 quality %.The combined amount of the electric conducting material (D) during hybrid conductive material (D) be in the solid constituent 1～20 quality %, be preferably 2～10 quality %.As the solid component concentration of slurry, consider from operation property, coating, the good aspect of stability of slurry, be preferably 40～70 quality %.
Electrode composition of the present invention is the stream material of the stable and homogeneous of not gelation with slurry, through coating collector body and drying, rolling, cut into predetermined size, can make electrode.Manufacture method and condition anodal and negative pole can adopt usual way and condition.
, for example can enumerate aluminium foil, etching aluminium foil, be coated with the aluminium foil of conducting paste etc. with the collector body of slurry as the coating electrode composition.
Electrode of the present invention owing to use is imbued with VdF/TFE based copolymer that flexibility do not cause gelation yet as cement (B1), improved the cementability with collector body with cement (B2), so the bonding force of electrode composition and collector body is good; Even be processed into the electrode of coiling (spiral) shape or folding shape; Do not produce the crackle of electrode composition layer yet or peel off, in addition, owing to be difficult to by the nonaqueous electrolytic solution swelling; Even thereby repeated charge, battery behavior can significantly not reduce yet.
In addition, the invention still further relates to a kind of lithium secondary battery, it as positive pole and/or negative pole, and possesses nonaqueous electrolytic solution with electrode of the present invention.
When using electrode of the present invention as positive pole, negative pole can use the electrode of the present invention that contains the negative electrode active material that alloy etc. is made up of basic matterial, also can be for using the negative pole of known material with carbon element as negative electrode active material.Use cathode of carbon material to make as follows: through material known and method, the cement that utilizes negative electrode active material and negative pole to use prepares cathode agent, with its coating or be adhered on the negative electrode collector such as Copper Foil.As the cathode of carbon material active material; Use can mix/carbonaceous material of dedoping lithium etc.; For example electric conductive polymer such as polyacene, polypyrrole or coke, polymer carbon, carbon fiber etc.; In addition; Consider from the aspect that the energy density of per unit volume is big, preferred thermally decomposed carbon class, coke class (petroleum coke, pitch coke, coal coke etc.), carbon black (acetylene black etc.), glassy carbon, high-molecular organic material sintered body (with high-molecular organic material under the temperature more than 500 ℃, in inert gas flow or in a vacuum sintering form) etc.
As nonaqueous electrolytic solution, can use the material that known dissolving electrolyte salt is formed in organic solvent in known dissolving electrolyte salt.
Use organic solvent as dissolving electrolyte salt; Not special the qualification; Can use propylene carbonate, ethylene carbonate, butylene carbonate, gamma-butyrolacton, 1,2-dimethoxy-ethane, 1, known varsols such as 2-diethoxyethane, dimethyl carbonate, diethyl carbonate; 1 kind in the fluorine kind solvents such as fluoroethylene carbonate, fluorine ether, fluorocarbons acid esters perhaps more than 2 kinds.
As electrolytic salt, can enumerate for example LiClO 4, LiAsF 6, LiBF 4, LiPF 6, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2Deng, consider preferred especially LiPF from the aspect that cycle characteristics is good 6, LiBF 4, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2Or their combination.
The concentration of electrolytic salt need be for more than 0.8 mol and then be more than 1.0 mol.The upper limit is different with organic solvent according to dissolving electrolyte salt, is generally 1.5 mol.
Lithium secondary battery of the present invention can be made through these each member storages are sealed in the battery case.Need to prove, can the clamping barrier film between positive pole and negative pole.
Embodiment
Next, the present invention is explained more specifically, but the present invention is not limited thereto based on embodiment.
Embodiment 1
(anode mixture is with the preparation of slurry)
Weighing is as each electrode material shown in the object table 1, and feasible positive active material (A1) by quality ratio: cement (B1)+(B2): conduction material (D) is 95: 5: 5.Cement (B1)+(B2) is dissolved in the N-methyl pyrrolidone (NMP), and making concentration is 10 quality %, in the nmp solution of this cement, adds the positive active material (A1) and the electric conducting material (D) of scheduled volume then, and fully mixes with mixer.Append NMP one by one while stirring, making solid component concentration is 50 quality %, and the preparation anode mixture is used slurry.
(anodal making)
Prepared above-mentioned anode mixture is filtered with the sieve of slurry through Ni sieve aperture (200 order), make the particle diameter homogenizing of solid constituent.Then, the anode mixture after filtering being implemented vacuum defoamation with slurry handles.After anode mixture is accomplished with the deaeration of slurry, utilize spreader at thickness be as collector plate on the Al paper tinsel of 22 μ m the coating anode mixture (the positive pole dry mass of filming is 18mg/cm with slurry 2Amount).After the coating, use blast drier or heating plate, NMP is volatilized fully, make strip-shaped positive electrode 100～120 ℃ of dryings.
It is following with each composition of slurry to be used to prepare anode mixture.
Anode mixture is with slurry (A1)
(A1-1): LiNi 0.82Co 0.15Al 0.03O 2(Toda Kogyo Corp.'s manufacturing)
(A1-2): LiNi 1/3Co 1/3Mn 1/3O 2(Nippon Chemical Ind's manufacturing)
Cement (B1)
(B1-1): VdF/TFE copolymer (VdF/TFE=80/20 mole % ratio)
(B1-2): VdF/TFE/HFP copolymer (VdF/TFE/HFP=65/32.5/2.5 mole % ratio)
Cement (B2)
(B2-1): PVdF (KF1120 that Wu Yu KCC makes)
Organic solvent (C)
(C-1): N-methyl pyrrolidone (moisture 30ppm)
Measure the density of the positive pole of made according to following main points.The result lists in table 1.
(mensuration of density)
Making anodal is the roll squeezer 2 times of 75 μ m at 70 ℃ through roll gap, and then roll gap is changed to behind the 35 μ m through 2 times, measures anodal area, thickness, weight then, calculates density (g/cm 3).
(having or not of crackle)
Behind the anodal cut growth 3cm of made, wide 6cm, carry out 180 ° and fold, launch then, through the Visual Confirmation positive pole flawless is arranged.The result lists in table 1.
[table 1]
Table 1
Figure BDA0000082362780000111
Result by table 1 can know, compares with PVdF, and copolymerization has the copolymer of TFE higher as the flexibility of cement, thereby density improves easily.Can know in addition, compare that alkali resistance is high, soft copolymerization has the copolymer of TFE to suppress anodal crackle with PVdF.
Embodiment 2
As cement (B2), use the resin shown in the table 2 with the ratio shown in the table 2, in addition likewise make positive pole with embodiment 1, investigate density and flawless is arranged.The result lists in table 2.
Cement (B2)
(B2-2): polymethyl methacrylate (PMMA) (manufacturing of Aldrich society)
(B2-3): methyl methacrylate (MMA)/methacrylic acid (MA) (MMA/MA=1: 0.016 mol ratio) (manufacturing of Aldrich society)
(B2-4): polyamidoimide (PAI) (HPC7200 that Hitachi Chemical Co., Ltd. makes)
(B2-5): polyimides (PI) (HCI-7000 that Hitachi Chemical Co., Ltd. makes)
[table 2]
Table 2
Figure BDA0000082362780000121
Result by table 2 can know, share cement (B1) and (B2) anodal flexibility is high, is difficult to break.
Embodiment 3
With the kind shown in the table 3 and ratio use cement (B1) with (B2), in addition likewise makes positive pole with embodiment 2, investigation has flawless.The result lists in table 3.
[table 3]
Table 3
Figure BDA0000082362780000131
Result by table 3 can know that even reduce the amount of cement (B2), flexibility is also high, is difficult to break.
Embodiment 4
Use cement (B1) and (B2) with the kind shown in the table 4 and ratio; In addition likewise make anodal with embodiment 2; Behind Continuous pressing device for stereo-pattern on the positive pole of made (PR51 that ACE GLOBAL LTD makes), it is peeled off, through the state of visualization anode mixture layer.The result lists in table 4.
[table 4]
Table 4
Figure BDA0000082362780000141
Result by table 4 can know, and is if share cement (B1) and (B2), then good with the adaptation of collector body.
Embodiment 5
Use the positive pole shown in the table 5, make lithium secondary battery (layer-built battery) through following method.For these lithium secondary batteries, according to following main points research multiplying power property (レ one ト characteristic) and cycle characteristics.The result lists in table 5.
(making of lithium secondary battery (layer-built battery))
(Hitachi changes into Co., Ltd. and makes to the Delanium powder.Trade name MAG-D) adds the butadiene-styrene rubber that disperses with distilled water in, make and count 6 quality %, and process pulp-like with the disperser mixing with solid constituent; This pulp-like material is coated negative electrode collector (thickness is the Copper Foil of 10 μ m) equably to be gone up also dry; Form anode mixture layer,, cut off the back drying thereafter through the roll squeezer extrusion molding; The welding lead body is made banded negative pole.
Strip-shaped positive electrode is cut into 40mm * 72mm (positive terminal that has 10mm * 10mm), and the negative pole with band shape cuts into 42mm * 74mm (negative terminal that has 10mm * 10mm), welding lead body on each terminal in addition.In addition, be that the microporous polyethylene film of 20 μ m cuts into the size of 78mm * 46mm and as barrier film, with the mode of clamping barrier film positive pole and negative pole is set with thickness, and put it in the long-pending packaging material of aluminium lamination.Then, (in the volume ratio of ethylene carbonate (EC) and methyl ethyl carbonate (EMC) is with the concentration dissolving LiPF of 1 mol in 3/7 the solvent in packaging material, to add 2ml electrolyte respectively 6The material that forms) also sealing, the making capacity is the layer-built battery of 72mAh.
(multiplying power property)
About charging, charging to charging current with 1.0C, 4.2V is 1/10C, to 3.0V, obtains discharge capacity with the current discharge that is equivalent to 0.2C.Then, charging to charging current with 1.0C, 4.2V is 1/10C, to 3.0V, obtains discharge capacity with the current discharge that is equivalent to 2C.By the ratio of discharge capacity with the discharge capacity of 0.2C of this 2C, the following calculating formula of substitution is obtained multiplying power property.
Multiplying power property (%)=2C discharge capacity (mAh)/0.2C discharge capacity (mAh) * 100
(cycle characteristics)
About cycle characteristics; To discharge and recharge condition (charging to charging current with 1.0C, 4.2V will be 1/10C above-mentioned; With the current discharge that is equivalent to 1C to 3.0V) under the charge and discharge cycles of carrying out as 1 circulation, the discharge capacity after measuring discharge capacity and 100 after the initial circulation and circulating.The value that cycle characteristics will be obtained according to following calculating formula is as the value of presented higher holdup.
Presented higher holdup (%)=100 cyclic discharge capacity (mAh)/1 cyclic discharge capacity (mAh) * 100
[table 5]
Table 5
Figure BDA0000082362780000151
Result by table 5 can know, uses and has share cement (B1) and positive pole (B2), has also kept battery behavior.
Embodiment 6
Use Si (negative electrode active material with 45: 45: 10 ratio of mass ratio.Fuji Silysia Chemical Ltd. makes), the cement (B) shown in acetylene black (the DENKA BLACK that Deuki Kagaku Kogyo Co., Ltd makes) and the table 6 ((B1) and (B2)); Use NMP as solvent, the preparation cathode agent is used slurry with the disperser mixing.This slurry is coated negative electrode collector (thickness is the Copper Foil of 10 μ m) equably go up also drying, form anode mixture layer, thereafter through the roll squeezer extrusion molding, drying after cutting off, the welding lead body is made banded negative pole.
Use A1-2 (LiNi 1/3Co 1/3Mn 1/3O 2) as positive active material, share cement B1-1 and cement B2-1 with 50/50 (mass ratio), in addition likewise make anodal with embodiment 1.
Use this negative pole and positive pole, likewise make lithium secondary battery (layer-built battery), likewise measure cycle characteristics with embodiment 5 with embodiment 5.The result lists in table 6.
[table 6]
Table 6
Figure BDA0000082362780000161
Result by table 6 can know, using under the situation of basic matterial as negative electrode active material, also can keep cycle characteristics.
Embodiment 7
Among the embodiment 6, negative electrode active material is changed to SiO 2(manufacturing of Aldrich society) or Sn particle (manufacturing of Aldrich society); Cement with kind shown in the table 7 and mixed negative pole; In addition likewise make lithium secondary battery with embodiment 6, and these lithium secondary batteries are carried out the cycle characteristics test of embodiment 5 and the folding test of embodiment 3.The result lists in table 7.
[table 7]
Table 7
Figure BDA0000082362780000171
Result by table 7 can know, even using SiO 2Or under the situation of Sn particle as negative electrode active material,,, can keep capacity and give flexibility through share VdF/TFE/HFP copolymer (B1-2) though do not have flexibility when using polyamidoimide (B2-4) or polyimides (B2-5) separately.

Claims (15)

1. the electrode composition of a lithium secondary battery is used slurry, and it is that the electrode composition that contains the lithium secondary battery of electrode active material (A), cement (B) and organic solvent (C) is used slurry, and this electrode composition is characterised in that with slurry cement (B) contains:
(B1) fluoropolymer of composition formula (B1) expression and
(B2) the solvable type thermoplastic resin of the solvent except that fluoropolymer (B1),
Composition formula (B1):
(VDF) m(TFE) n(HFP) l
In the formula, VDF is the construction unit from vinylidene fluoride; TFE is the construction unit from tetrafluoroethene; HFP is the construction unit from hexafluoropropylene; 0.45≤m≤1; 0.05≤n≤0.5; 0≤l≤0.1, wherein, m+n+l=1.
2. electrode composition as claimed in claim 1 is used slurry, and wherein, electrode active material (A) is positive active material (A1), and contains the lithium-contained composite metal oxide of formula (A1) expression,
Formula (A1):
Li xM 1 yM 2 1-yO 2
In the formula, 0.4≤x≤1; 0.3≤y≤1; M 1For being selected from least a element in the group of forming by Ni and Mn; M 2For being selected from least a element in the group of forming by Co, Al and Fe.
3. electrode composition as claimed in claim 2 is used slurry, and positive active material (A1) is formula (A1-1), formula (A1-2), formula (A1-3) or formula (A1-4),
Formula (A1-1):
LiNi xCo yAl zO 2
In the formula, 0.7≤x≤1; 0≤y≤0.3; 0≤z≤0.03; 0.9≤x+y+z≤1.1,
Formula (A1-2):
LiNi xCo yMn zO 2
In the formula, 0.3≤x≤0.6; 0≤y≤0.4; 0.3≤z≤0.6; 0.9≤x+y+z≤1.1,
Formula (A1-3):
Li xMn zO 2
In the formula, 0.4≤x≤0.6; 0.9≤z≤1,
Formula (A1-4):
LiFe xCo yMn zO 2
In the formula, 0.3≤x≤0.6; 0.1≤y≤0.4; 0.3≤z≤0.6; 0.9≤x+y+z≤1.1.
4. electrode composition as claimed in claim 1 is used slurry, and wherein, electrode active material (A) is for comprising the negative electrode active material (A2) of basic matterial, and said basic matterial contains Si and/or Sn.
5. use slurry like each described electrode composition of claim 1～4; Wherein, cement (B2) is for being selected from least a cement in the group of being made up of polyvinylidene fluoride, polyacrylic acid based polymer, polymethylacrylic acid based polymer, polyimides, polyamide and polyamidoimide.
6. use slurry like each described electrode composition of claim 1～5, wherein, cement (B1) contains the fluorinated copolymer that m, n and l in the formula (B1) is respectively 0.50≤m≤0.90,0.10≤n≤0.50 and 0≤l≤0.08, wherein, and m+n+l=1.
7. use slurry like each described electrode composition of claim 1～6, wherein, cement (B1) contains the binary fluorinated copolymer that m and n in the formula (B1) are respectively 0.50≤m≤0.90 and 0.10≤n≤0.50, wherein, and m+n=1.
8. use slurry like each described electrode composition of claim 1～6, wherein, cement (B1) contains the fluorinated copolymer that m, n and l in the formula (B1) is respectively 0.50≤m≤0.90,0.09≤n≤0.49 and 0.01≤l≤0.04, wherein, and m+n+l=1.
9. use slurry like each described electrode composition of claim 1～8, wherein, the moisture of organic solvent (C) is below the 30ppm.
10. the electrode of a lithium secondary battery, it obtains through each described electrode composition of claim 1～9 is coated on the collector body with slurry and carried out drying.
11. a lithium secondary battery, it as positive pole and/or negative pole, and possesses nonaqueous electrolytic solution with the described electrode of claim 10.
12. the electrode composition of a lithium secondary battery is with the manufacturing approach of slurry; This method makes electrode active material (A) and cement (B) be scattered in the electrode composition of making lithium secondary battery in the organic solvent (C) and uses slurry; This manufacturing approach is characterised in that cement (B) contains:
(B1) fluoropolymer of composition formula (B1) expression and
(B2) the solvable type thermoplastic resin of the solvent except that fluoropolymer (B1),
And the moisture of organic solvent (C) is below the 100ppm,
Composition formula (B1):
(VDF) m(TFE) n(HFP) l
In the formula, VDF is the construction unit from vinylidene fluoride; TFE is the construction unit from tetrafluoroethene; HFP is the construction unit from hexafluoropropylene; 0.45≤m≤1; 0.05≤n≤0.5; 0≤l≤0.1, wherein, m+n+l=1.
13. manufacturing approach as claimed in claim 12, wherein, the moisture of organic solvent (C) is below the 30ppm.
14. like claim 12 or 13 described manufacturing approaches, wherein, organic solvent (C) is the N-methyl pyrrolidone.
15. the electrode composition of a lithium secondary battery is used slurry, its each described manufacturing approach through claim 12～14 obtains.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103515612A (en) * 2012-06-26 2014-01-15 日立麦克赛尔株式会社 Non-aqueous electrolyte secondary battery and manufacturing method thereof
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WO2023178470A1 (en) * 2022-03-21 2023-09-28 宁德新能源科技有限公司 Electrochemical device and electronic device

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US9583757B2 (en) 2010-12-22 2017-02-28 Enevate Corporation Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1213393A (en) * 1996-01-22 1999-04-07 埃尔夫阿托化学有限公司 Method for adhesion of fluorinated resins to metals
JPH11135121A (en) * 1997-10-27 1999-05-21 Toray Ind Inc Manufacture of mix for electrode
CN1240053A (en) * 1996-12-16 1999-12-29 大金工业株式会社 Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same
CN1770542A (en) * 2001-08-24 2006-05-10 索尼株式会社 Battery

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09199134A (en) * 1996-01-22 1997-07-31 Elf Atochem Japan Kk Electrode and secondary battery using it
JPH09199132A (en) * 1996-01-22 1997-07-31 Elf Atochem Japan Kk Electrode and secondary battery using it
JP3356021B2 (en) * 1996-12-16 2002-12-09 ダイキン工業株式会社 Non-aqueous electrolyte secondary battery binder and battery electrode mixture using the same
JPH1131513A (en) * 1997-05-13 1999-02-02 Sony Corp Nonaqueous electrolyte secondary battery
JP4253051B2 (en) * 1997-12-26 2009-04-08 株式会社クレハ Nonaqueous battery electrode mixture and nonaqueous battery
JP2971451B1 (en) * 1998-06-30 1999-11-08 株式会社東芝 Lithium secondary battery
US6759164B2 (en) * 2000-11-29 2004-07-06 Wilson Greatbatch Ltd. Use of heat-treated electrodes containing a polyamic acid-PVDF binder mixture
JP4361241B2 (en) * 2002-04-26 2009-11-11 株式会社クレハ Non-aqueous secondary battery electrode binder composition, electrode mixture composition, electrode and secondary battery
JP4752243B2 (en) * 2004-11-05 2011-08-17 ソニー株式会社 Negative electrode and battery, and method for producing the same
JP4859373B2 (en) * 2004-11-30 2012-01-25 パナソニック株式会社 Non-aqueous electrolyte secondary battery
JP2007305495A (en) * 2006-05-12 2007-11-22 Sony Corp Manufacturing method of battery, and manufacturing method of electrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1213393A (en) * 1996-01-22 1999-04-07 埃尔夫阿托化学有限公司 Method for adhesion of fluorinated resins to metals
CN1240053A (en) * 1996-12-16 1999-12-29 大金工业株式会社 Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same
JPH11135121A (en) * 1997-10-27 1999-05-21 Toray Ind Inc Manufacture of mix for electrode
CN1770542A (en) * 2001-08-24 2006-05-10 索尼株式会社 Battery

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US9941517B2 (en) 2013-01-31 2018-04-10 Mitsui Chemicals, Inc. Electrode for lithium battery and production process thereof, and lithium battery
CN104956524B (en) * 2013-01-31 2018-11-27 三井化学株式会社 Lithium battery electrode and its manufacturing method and lithium battery
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CN114830379A (en) * 2019-12-18 2022-07-29 大金工业株式会社 Slurry for solid secondary battery, method for forming layer for solid secondary battery, and solid secondary battery
CN112703621A (en) * 2020-03-20 2021-04-23 广东省皓智科技有限公司 Cathode for secondary battery and cathode slurry
CN114361452A (en) * 2021-12-15 2022-04-15 电子科技大学中山学院 Adhesive, electrode slurry, and manufacturing method and application thereof
CN114361452B (en) * 2021-12-15 2023-09-19 电子科技大学中山学院 Adhesive, electrode slurry, and manufacturing method and application thereof
WO2023178470A1 (en) * 2022-03-21 2023-09-28 宁德新能源科技有限公司 Electrochemical device and electronic device

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