CN102473916A - Slurry for electrode mixture of lithium secondary cell, electrode using the slurry, and lithium secondary cell - Google Patents

Slurry for electrode mixture of lithium secondary cell, electrode using the slurry, and lithium secondary cell Download PDF

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Publication number
CN102473916A
CN102473916A CN2010800262748A CN201080026274A CN102473916A CN 102473916 A CN102473916 A CN 102473916A CN 2010800262748 A CN2010800262748 A CN 2010800262748A CN 201080026274 A CN201080026274 A CN 201080026274A CN 102473916 A CN102473916 A CN 102473916A
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slurry
electrode
cement
vdf
electrode composition
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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
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/052—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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  • Secondary Cells (AREA)

Abstract

Provided is an electrode mixture slurry for a lithium secondary cell. The electrode mixture slurry comprises an electrode active material, binder, and fluorine rubber particles, and is capable of improving the flexibility of the electrode without compromising the stability or cell characteristics. Also provided is an electrode which is extremely flexible and shows improved adhesion between the mixture and the collector. Further provided is a lithium secondary cell having excellent cell characteristics.

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 provide the electrode that is imbued with flexibility is with slurry, the electrode 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, in case of necessity electric conducting material, the preparation anode mixture use slurry, coat positive electrode collector after, dry 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 propylene carbonate, ethylene carbonate, diethyl carbonate or their nonaqueous electrolytic solutions such as mixture that PVdF is easy to be used in the lithium rechargeable battery.Therefore, produced following problem: when discharging and recharging repeatedly, and collector body---the cementability variation between the metal forming, its result cause 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 in the operation that electrode slice 180 degree are folding 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, can stripping in the kind of some electrolyte, thus can't accomplish its task as cement.
As same cement, to have put down in writing in the patent documentation 3 a kind of fluoro containing polymers copolymer has been used for cement, this fluoro containing polymers copolymer is made up of as main component VdF, tetrafluoroethene (TFE) and HFP and does not use PVdF.The compositing range of the copolymer of putting down in writing in its claims is following: 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 particularly has dissolubility but is difficult to by electrolyte organic solvent swelling in general solvent.Disclosed cement is that binary fluorinated copolymer and VdF50 mole %～80 moles of %, TFE17 mole %～50 moles of % and other comonomers of VdF50 mole %～80 moles % and TFE20 mole %～50 moles of % are lower than the ternary fluorinated copolymer of 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; Can contain resins such as polymethacrylates, polymethyl methacrylate, polyacrylonitrile, polyimides, polyamide, polyamidoimide, Merlon, the content of these resins in cement is below about 20 volume %.
In addition, following scheme has been proposed in the patent documentation 5: in order to improve the cycle characteristics under the high temperature,, except PVdF, also share polyimides, share aromatic polyamide in negative side at side of the positive electrode as cement.
In addition; Following method has been proposed: in order to improve the cementability between collector body and the cement in the patent documentation 6; With acrylic acid series polymeric compounds the surface of collector body is handled; And put down in writing,, can also use the mixture of the copolymer of PVdF50 weight %～95 weight % and VdF and other polymer (for example TFE, HFP, CTFE etc.) as this cement.
Though proposed the scheme of the cementability of many such raisings and collector body, mostly these schemes have been to sacrifice the flexibility of electrode.For the flexibility of improved electrode, there is document to propose to contain the rubber particle (patent documentation 7,8) of acrylic rubber, butadiene-styrene rubber.
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
Patent documentation 7: TOHKEMY 2003-331825 communique
Patent documentation 8: TOHKEMY 2006-185887 communique
Summary of the invention
In the patent documentation 7 and 8 of the flexibility that improves electrode, mixed acrylic rubber, butadiene-styrene rubber, but had following problems: the swelling of electrode in electrolyte increases, and hot properties, cycle characteristics reduce; Oxidative resistance is low, thereby the gas generation increases the cycle characteristics reduction.
The objective of the invention is in the cementability that improves with collector body, do not damage battery behavior and improve the flexibility of electrode.
That is the electrode composition that, the present invention relates to comprise the lithium secondary battery of electrode active material (A), cement (B) and fluorubber particle (C) is used slurry.
In addition, the invention still further relates to through coating collector body on slurry electrode composition of the present invention and carrying out the electrode of the lithium secondary battery that drying obtains; And with electrode of the present invention as positive pole and/or negative pole and possess the lithium secondary battery of nonaqueous electrolytic solution.
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 do not damage resistance to swelling in electrolyte, be imbued with the electrode of flexibility, and then use the excellent lithium secondary battery of battery behavior of this electrode composition.
Embodiment
The electrode composition of lithium secondary battery of the present invention comprises electrode active material (A), cement (B) and fluorubber particle (C) with slurry.Below, each composition is described.
(A) electrode active material
Among the present invention, can be positive active material (A1), also can be negative electrode active material (A2).
(A1) positive active material
As positive active material (A1), be 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 kind in the group of forming by Ni and Mn; M 2For being selected from least a kind in the group of forming by Co, Al and Fe) shown in lithium-contained composite metal oxide.
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 the lithium-contained composite metal oxide≤x+y+z≤1.1).
As the object lesson of the lithium-contained composite metal oxide shown in the formula (A1-1), 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 preferred LiNi 0.82Co 0.15Al 0.03O 2(NCA).
As the object lesson of the lithium-contained composite metal oxide shown in the formula (A1-2), 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 preferred LiNi 1/3Co 1/3Mn 1/3O 2(NCM).
As the object lesson of the lithium-contained composite metal oxide shown in the formula (A1-3), can enumerate for example Li 0.5MnO 2(galaxite), LiMnO 2Deng.
As the object lesson of the lithium-contained composite metal oxide shown in the formula (A1-4), 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, can also 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 comprises Si, Sn, as metal nitride, can enumerate Li 2.6Co 0.4N etc.
(B) cement
As the cement that uses among the present invention (B), preferably comprise polyvinylidene fluoride (B1) and/or composition formula (B2):
(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＜n≤0.5; 0≤l≤0.1.Wherein, the VdF/TFE shown in m+n+l=1) is fluoropolymer (B2).
(B1)PVdF
As PVdF, can directly use the PVdF that all the time in the electrode of lithium secondary battery, uses.PVdF can use separately, also can share with other cement compositions.
About the molecular weight of PVdF, preferably measure the number-average molecular weight that obtains and count 10000～500000 with the polystyrene conversion value by GPC (gel permeation chromatography).
(B2) VdF/TFE is a fluoropolymer
As stated,, also consider carrying out various exploitations, occurred 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 all the time uses, the active material that is made up of basic matterial has appearred also.
Also comprise these LiCoO 2, LiNiO 2, LiMn 2O 4Interior; Lithium-contained composite oxide is essentially alkalescence; Though its reason is confirmed as yet, had following problem: can cause gelation at the anode mixture of these lithium-contained composite oxides and PVdF perhaps many VdF based copolymer coexistence in slurry, stability of slurry is understood impaired.In negative pole, use under the situation of basic matterial as negative electrode active material, also have same tendency.
In order to tackle said tendency, in the VdF based copolymer, the VdF/TFE based copolymer of finding to make the TFE copolymerization of VdF and specified quantitative to form is all of a sudden stable for the electrode active material of alkalescence, mix and the electrode composition of preparation with slurry also homogeneous and stablize.The alkali resistance of this excellence is the characteristic of special discovery in the VdF/TFE based copolymer, and in other VdF based copolymers such as VdF/HFP based copolymer, VdF/CTFE based copolymer, does not find.
Consider from this aspect, as cement (B2), the fluoropolymer shown in the preferred above-mentioned composition formula (B2).
Wherein,, consider that (wherein, m+n+l=1) VdF/TFE is a fluorinated copolymer for 0.50≤m≤0.90,0.09≤n≤0.40 and 0≤l≤0.04 in the preferred formula (B2) from the aspect that flexibility and alkali resistance are good as fluoropolymer.
Wherein, consider (wherein, m+n=1) the VdF/TFE binary fluorinated copolymer of l=0,0.50≤m≤0.90 and 0.10≤n≤0.50 in the preferred formula (B2) from the aspect that flexibility and alkali resistance are good.And then from alkali resistance, the good aspect consideration of flexibility, preferred n (TFE) is 0.10～0.40, is preferably 0.15～0.40 especially.
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.And then from alkali resistance, the good aspect consideration of flexibility, the copolymer of preferred 0.60≤m≤0.90,0.09≤n≤0.45,0.01≤l≤0.04, the further copolymer of preferred 0.60≤m≤0.70,0.30≤n≤0.40,0.02≤l≤0.04.
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 is low if the content of TFE is crossed at least, flexibility reduces easily, possibly can't fully realize effect of the present invention.
About the molecular weight of VdF/TFE based copolymer, preferably measure the number-average molecular weight that obtains and count 10000～500000 with the polystyrene conversion value by GPC (gel permeation chromatography).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 (B2) 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 free radical mode then its means have no restriction, for example utilize initiations such as organic or inorganic radical polymerization initiator, heat, light or ionizing ray.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 (B2) is excellent; Certainly dissolving in the N-methyl pyrrolidone that uses as the solvent of PVdF, dimethyl formamide, dimethylacetylamide etc. nitrogenous is organic solvent; Also dissolve in normally used lower boiling general organic solvent; Also do not cause gelation even this copolymer mixes with electrode active material, and can give flexibility, and the swellability in nonaqueous electrolytic solution is also little electrode.
VdF/TFE based copolymer (B2) can use separately, also can share with PVdF (B1), other cement compositions (B3).
With PVdF (B1) when share, from keep flexibility, the good aspect of adaptation is considered, VdF/TFE based copolymer (B2) is preferably the 20 quality %～80 quality % of (B1) and (B2) total amount.
(B3) other cement compositions
As other cement compositions, but illustration goes out the solvable type thermoplastic resin of solvent, VdF/HFP based copolymer, VdF/CTFE based copolymer etc.Wherein, preferably has the solvable type thermoplastic resin of solvent that improves with the effect of the cementability of collector body.
Among the present invention; " the solvable type thermoplastic resin of solvent " is meant a kind of thermoplastic resin; This thermoplastic resin dissolves more than the 5 quality % down at 25 ℃ in organic solvent; And form uniform solution, this thermoplastic resin preference such as polyacrylic acid based polymer, polymethylacrylic acid based polymer, polyimides, polyamide, polyamidoimide etc.
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.
Use when being selected from least a in the group of forming by polyacrylic acid based polymer, polymethylacrylic acid based polymer, polyimides, polyamide and polyamidoimide as cement (B3); From keeping flexibility, the good aspect consideration of adaptation, be preferably the whole 5 quality %～50 quality % of cement (B).
When using VdF/HFP based copolymer, VdF/CTFE based copolymer,, be preferably the whole 5 quality %～50 quality % of cement (B) from keeping flexibility, the good aspect consideration of adaptation.
(C) fluorubber particle
Among the present invention, fluorubber particle (C) has the effect that electrode composition is given flexibility, particularly extensibility and given character such as caoutchouc elasticity.
As the fluorubber of fluorubber particle (C), can use existing known fluorubber.
As preferred fluorubber, consider that from obtaining having preferably comprise the construction unit from following monomer, said monomer is for example for being selected from by tetrafluoroethene, vinylidene fluoride and formula (1) as the aspect of the particle of the character of rubber elastomer:
CF 2＝CF-R f 1 (1)
(in the formula, R f 1For-CF 3Or-OR f 2(R f 2Be that carbon number is 1～5 perfluoroalkyl)) at least a monomer in the group formed of the perfluor ethylenically unsaturated compounds of expression.
As fluorubber, also preferred non-perfluor fluorubber and perfluor fluorubber.
As non-perfluor fluorubber; Can enumerate vinylidene fluoride (VdF) is that fluorubber, tetrafluoroethene (TFE)/propylene are that fluorubber, tetrafluoroethene (TFE)/propylene/vinylidene fluoride (VdF) are that fluorubber, ethene/hexafluoropropylene (HFP) are that fluorubber, ethene/hexafluoropropylene (HFP)/vinylidene fluoride (VdF) are that fluorubber, ethene/hexafluoropropylene (HFP)/tetrafluoroethene (TFE) are that fluorubber, fluorosilicone are that fluorubber or fluorine phosphine nitrile are fluorubber etc.; They can distinguish independent use, and perhaps combination in any is used in the scope of not damaging effect of the present invention.Wherein, preferred VdF/HFP copolymer rubber, VdF/HFP/TFE copolymer rubber, TFE/ propylene copolymer rubbers, TFE/HFP/ propylene copolymer rubbers, TFE/PAVE copolymer rubber.
Specifically; Above-mentioned VdF is that the preferred VdF repetitive of rubber (VdF/HFP copolymer rubber, VdF/HFP/TFE copolymer rubber etc.) is a VdF repetitive and from 20 moles of the total mole number of the repetitive of other comonomers more than the % and 90 moles below the %, and more preferably 40 moles of % are above and 85 moles below the %.Further preferably be limited to 45 moles of % down, preferably especially be limited to 50 moles of % down, further be limited to 80 moles of % on preferably.
In addition; As above-mentioned VdF is other monomers in the rubber; As long as can not limit with the VdF copolymerization is then special; For example, can enumerate TFE, HFP, PAVE, CTFE, trifluoro-ethylene, trifluoro propene, tetrafluoeopropene, five fluorine propylene, trifluoro butylene, tetrafluoro isobutene, ethylene fluoride, contain fluorochemical monomers such as iodine fluorinated vinyl ether; Non-fluorochemical monomers such as ethene (Et), propylene (Pr), alkyl vinyl ether etc. can select a kind of use or combination to use more than 2 kinds from these fluorochemical monomers and non-fluorochemical monomer.As above-mentioned PAVE, preferred perfluor (methyl vinyl ether), perfluor (propyl vinyl ether), preferred especially perfluor (methyl vinyl ether).
As above-mentioned VdF is rubber; Preferred VdF/HFP copolymer, VdF/HFP/TFE copolymer, VdF/CTFE copolymer, VdF/CTFE/TFE copolymer, VdF/PAVE copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer or VdF/Et/HFP copolymer; In addition; As other monomers; More preferably have TFE, HFP and/or PAVE, preferred especially VdF/HFP copolymer, VdF/HFP/TFE copolymer, VdF/PAVE copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer or VdF/HFP/TFE/PAVE copolymer.
The preferred VdF/HFP of VdF/HFP copolymer consists of (45～85)/(55～15) (mole %), and more preferably (50～80)/(50～20) (mole %) further is preferably (60～80)/(40～20) (mole %).
The preferred VdF/HFP/TFE of VdF/HFP/TFE copolymer consists of (30～80)/(10～35)/(4～35) (mole %).
As the VdF/PAVE copolymer, preferred VdF/PAVE consists of (65～90)/(35～10) (mole %).
As the VdF/TFE/PAVE copolymer, preferred VdF/TFE/PAVE consists of (40～80)/(3～40)/(15～35) (mole %).
As the VdF/HFP/TFE/PAVE copolymer, preferred VdF/HFP/TFE/PAVE consists of (40～90)/(0～25)/(0～40)/(3～35) (mole %), more preferably (40～80)/(3～25)/(3～40)/(3～25) (mole %).
The TFE/ propylene is that fluorubber is meant by TFE45 mole %～70 moles of fluorinated copolymers that %, 55 moles of %～30 mole % of propylene constitute.Except these two kinds the composition, can also contain the 3rd specific composition (for example PAVE) of 0 mole of %～40 mole %.
As the perfluor fluorubber, can enumerate perfluor fluorubber that constitutes by TFE/PAVE etc.The composition of TFE/PAVE is preferably (50～90)/(50～10) (mole %), and more preferably (50～80)/(50～20) (mole %) further is preferably (55～75)/(45～25) (mole %).
PAVE as this moment can enumerate for example perfluor (methyl vinyl ether), perfluor (propyl vinyl ether) etc., and they can distinguish independent use, and perhaps combination in any is used.
In addition, the fluorubber preferred number average molecular weight is 1000～1200,000, further is preferably 5000～900000 material.
More than the non-perfluor fluorubber and the perfluor fluorubber of explanation can be made through conventional methods such as emulsion polymerisation, suspension polymerisation, polymerisation in solutions.Particularly, can make the fluorubber of narrow molecular weight distribution through polymerization as the known use iodine compound of iodine (bromine) transfer polymerization.
Wherein, preferably comprise VdF/HFP copolymer rubber, VdF/HFP/TFE copolymer rubber or TFE/ propylene copolymer rubbers fluorubber as the unit.
In addition, the fluorubber particle can be uncrosslinked rubber (raw rubber) particle, also can be crosslinked rubber grain, considers preferred cross-linked rubbery particle from the aspect that solvent resistance (resistance to swelling) is good.The crosslinked of fluorubber gets final product according to known conventional method.
From can take into account the dispersiveness resin and improve film-strength aspect consider that the particle diameter of fluorubber particle (C) is preferably 0.1～2.0 μ m in average primary particle diameter, further is preferably 0.15～1.5 μ m, is preferably especially about 0.2～1.0 μ m.
The combined amount of fluorubber particle (C) is a cement (B) with more than the 0.1 quality % of the total amount of fluorubber particle (C), is preferably more than the 0.5 quality %, is preferably especially more than the 1 quality %.If very few, then has the tendency that the raising effect of the flexibility of electrode composition, particularly extensibility diminishes.The upper limit is preferably 50 quality %, further is preferably 30 quality %.If the combined amount of fluorubber particle (C) is too much, then have the dispersed bad tendency in cement (B), have the tendency that the swelling under the high temperature increases in addition.Be limited to 20 quality % on preferred especially.
Electrode composition of the present invention with slurry be through with electrode active material (A), cement (B) and rubber grain (C) and after the electrode material mixed and dispersed such as electric conducting material stated in solvent (D), obtain.
As solvent (D), can be organic solvent (D1), also can be aqueous solvent (D2), consider preferred organic solvent (D1) from the aspect of stability of slurry, coating.
As organic solvent (D1), be the organic solvent except N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide etc. are nitrogenous, can also 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 preferred 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 (D1) is very important.That is, making moisture is that the alkalescence that is produced by alkaline electrode active material manifests lessly, can suppress gelation below the 100ppm and then for below the 40ppm, in particular for 35ppm when following.
As aqueous solvent (D2), water is typical example, under the situation aspect safety-sensitive, the cost, can adopt.
(E) 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 solvent (D), in resulting solution, makes electrode active material (A), fluorubber particle (C), electric conducting material (E) etc. disperse to mix with slurry.In addition, after also can the powder of for example cement (B), fluorubber particle (C), electrode active material (A), electric conducting material (E) being pre-mixed each other, add solvent (D) and the preparation slurry.
Electrode composition of the present invention is with in the slurry; The combined amount of electrode active material (A) is the 70 quality %～98 quality % in the solid constituent (electrode active material (A), cement (B), fluorubber particle (C), electric conducting material (E) etc.), is preferably 90 quality %～97 quality %.About the mixed proportion of cement (B), negative or positive electrode no matter, cement (B) is the 0.1 quality %～20 quality % in the solid constituent, is preferably 1 quality %～10 quality %.The combined amount of fluorubber particle (C) is the 0.1 quality %～20 quality % in the solid constituent, is preferably 0.5 quality %～10 quality %.The combined amount of the electric conducting material (E) during hybrid conductive material (E) is the 1 quality %～20 quality % in the solid constituent, is preferably 2 quality %～10 quality %.As the solid component concentration of slurry, consider from operation property, coating, the good aspect of stability of slurry, be preferably 40 quality %～70 quality %.
Electrode composition of the present invention with slurry be not gelation and stablize, the stream material of homogeneous, through coat collector body and dry, roll, 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 provides the fluorubber particle (C) of flexibility through mixing; Even be processed into the electrode of coiling (spiral) type or folded form; Do not produce the crackle of electrode composition layer yet or peel off, in addition, owing to be difficult for swelling in nonaqueous electrolytic solution; 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, as negative pole, can use the electrode of the present invention that comprises the negative electrode active material that is made up of basic matterials such as alloys, also can be with the negative pole of known material with carbon element as negative electrode active material.Use cathode of carbon material to make as follows: utilize material known and method, the cement that uses 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, thereby produces the use cathode of carbon material.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 unit volume is big, preferred thermally decomposed carbon class, coke class (petroleum coke, pitch coke, coal coke etc.), carbon black (acetylene black etc.), vitreous 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 electrolyte dissolution.
Use organic solvent as electrolyte dissolution; 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 depends on that also dissolving electrolyte salt uses organic solvent, 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)
Each target electrode material shown in the weighing table 1, feasible positive active material (A1) by quality ratio: cement (B1)+(B2): fluorubber particle (C): electric conducting material (E) is 92: 4: 1: 3.Cement (B) is dissolved in the N-methyl pyrrolidone (NMP), and making concentration is 10 quality %, in the nmp solution of this cement, adds positive active material (A1), fluorubber particle (C) and the electric conducting material (E) of scheduled volume then, and fully mixes with mixer.Append NMP one by one while stirring, to solid component concentration be 50 quality %, the preparation anode mixture use slurry.
(anodal making)
Prepared above-mentioned anode mixture is carried out sieving with slurry through nickel screen cloth (200 order), make the particle diameter homogenizing of solid constituent.Then, the anode mixture after the sieving being implemented vacuum defoamation with slurry handles.Anode mixture utilizes spreader at collector plate after accomplishing with the deaeration of slurry---thickness be 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.
Positive active material (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): PVdF (KF1120 that Wu Yu KCC makes)
Cement (B2)
(B2-1): VdF/TFE copolymer (VdF/TFE=80/20 mole % ratio)
(B2-2): VdF/TFE/HFP copolymer (VdF/TFE/HFP=65/32.5/2.5 mole % ratio)
Fluorubber particle (C)
(C-1): crosslinked VdF/HFP (78/22 mole of % ratio) copolymer rubber.Average primary particle diameter 0.3 μ m)
(C-2): crosslinked TFE/VdF/HFP (30/48/22 mole of % ratio) copolymer rubber.Average primary particle diameter 0.2 μ m)
(C-3): examining to acrylic rubber, shell is rubber grain (the crosslinked) (EXL2313 of Rohm and Haas Japan manufactured of polymethyl methacrylate.Average primary particle diameter 0.6 μ m)
(C-4) nuclear is rubber grain (the crosslinked) (BTA772 of Rohm and Haas Japan manufactured of polymethyl methacrylate for butadiene-styrene rubber, shell.Average primary particle diameter 0.8 μ m)
Solvent (D)
(D-1): N-methyl pyrrolidone (moisture 30ppm)
Utilize following method to measure the density of the positive pole of made.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 doubling (180 ° of folding り put ん だ), launch then, through the Visual Confirmation positive pole flawless is arranged.The result lists in table 1.
(swelling ratio in electrolyte)
Electrode impregnated in LiPF 6Ethylene carbonate/methyl ethyl carbonate (3/7 volume ratio) electrolyte of 1M concentration in, measure Thickness Variation at 90 ℃ after keeping 24 hours down, calculate the swelling ratio (%) [preceding thickness * 100 of=(thickness before the thickness-dipping behind the dipping)/dipping)] of electrode.
Figure BDA0000119461120000141
Result by table 1 can know that when comparing with the example of unmixed fluorubber particle, through mixing the fluorubber particle, flexibility improves, anodal crackle is suppressed.In addition, when using as the acrylic rubber particle (C-3) of non-fluorubber particle and butadiene-styrene rubber particle (C-4), the swelling ratio in electrolyte is big.
Embodiment 2
As fluorubber particle (C), use (C-1) of the amount shown in the table 2 with (C-5), in addition likewise make positive pole with embodiment 1, having or not of density and crackle studied.The result lists in table 2.
Fluorubber particle (C-5): crosslinked TFE/ propylene (50/50 mole of % ratio) copolymer rubber.Average primary particle diameter 0.3 μ m)
Figure BDA0000119461120000161
Result by table 2 can know that even change the kind and the amount of fluorubber particle, flexibility is also high, also is difficult to crack.
Embodiment 3
As cement (B3), use the resin shown in the table 3 with the ratio shown in the table 3, in addition likewise makes positive pole with embodiment 1, having or not of density and crackle investigated.The result lists in table 3.
Cement (B3)
(B3-1): polymethyl methacrylate (PMMA) (manufacturing of Aldrich society)
(B3-2): methyl methacrylate (MMA)/methacrylic acid (MA) (MMA/MA=1: 0.016 mol ratio) (manufacturing of Aldrich society)
(B3-3): polyamidoimide (PAI) (HPC7200 that Hitachi Chemical Co., Ltd. makes)
(B3-4): polyimides (PI) (HCI-7000 that Hitachi Chemical Co., Ltd. makes)
(B3-5): polyacrylic acid (manufacturing of Aldrich society)
Figure BDA0000119461120000181
Result by table 3 can know, share cement (B1) and (B3) time flexibility also high, also be difficult to crack.
Embodiment 4
Use the positive pole shown in the table 4, make lithium secondary battery (laminated cell) through following method.For these lithium secondary batteries, according to following main points research multiplying power property and cycle characteristics.
The result lists in table 4.
(making of lithium secondary battery (laminated cell))
(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 size that the microporous polyethylene film of 20 μ m cuts into 78mm * 46mm is processed barrier film with thickness, with the mode of clamping barrier film positive pole and negative pole are set, and they are put into the long-pending packaging material of aluminium lamination.Then, in packaging material, add 2ml electrolyte (is the material that forms with the concentration dissolving LiPF6 of 1 mol in 3/7 the solvent in the volume ratio of ethylene carbonate (EC) and methyl ethyl carbonate (EMC)) and sealing respectively, the making capacity is the laminated cell of 72mAh.
(multiplying power property)
Use this laminated cell, charging to charging current with 0.5C, 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 0.5C, 4.2V is 1/10C, to 3.0V, obtains discharge capacity with the current discharge that is equivalent to 5C.By estimating multiplying power property with discharge capacity under this 5C condition and ratio with the discharge capacity under the above-mentioned 0.2C condition.About multiplying power property, the value that will obtain according to following calculating formula is as multiplying power property.
Multiplying power property (%)=5C discharge capacity (mAh)/0.2C discharge capacity (mAh) * 100
(cycle characteristics)
When representing charging and discharging currents, as 1C, measure following discharging and recharging under the condition determination with 72mA with C.
Discharge and recharge condition
Charging: being retained to charging current with 0.5C, 4.2V is 1/10C (constant-current constant-voltage charging)
Discharge: 1C, 2.5Vcut (constant-current discharge).
About cycle characteristics, discharge and recharge under the condition at this above-mentioned laminated cell is discharged and recharged test, measure the discharge capacity of 100 circulations.About cycle characteristics, the value that will obtain according to following calculating formula is as the presented higher holdup.
Presented higher holdup (%)=100 time cyclic discharge capacity (mAh)/1 time cyclic discharge capacity (mAh) * 100
Table 4
Figure BDA0000119461120000201
Result by table 4 can know that even use the positive pole that has mixed fluorubber particle (C), battery behavior is also kept.Can know on the other hand, use mixed the mixture (1-10) of acrylic rubber particle with the situation of the mixture (1-11) that has mixed the butadiene-styrene rubber particle under, possibly be the influence of gas generation, cycle characteristics is poor.
Embodiment 5
Utilize disperser with Si (negative electrode active material.Fuji Silysia Chemical Ltd. makes), acetylene black (DENKABLACK that Deuki Kagaku Kogyo Co., Ltd makes) and the mixture shown in the table 5, prepare cathode agent and use slurry in N-methyl pyrrolidone (moisture 30ppm) with 45: 45: 10 ratio dispersing and mixing of mass ratio.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.
Anodal A1-2 (the LiNi that uses 1/3Co 1/3Mn 1/3O 2) as positive active material, in addition likewise make with embodiment 1.
Use this negative pole and positive pole, likewise make lithium secondary battery (laminated cell), likewise measure cycle characteristics with embodiment 4 with embodiment 4.The result lists in table 5.
Table 5
Figure BDA0000119461120000211
Result by table 5 can know that when using basic matterial as negative electrode active material, cycle characteristics is also kept.
Embodiment 6
Among the embodiment 1, use the mix paste of the composition shown in the table 6, in addition likewise make anodal, to density, crackle have or not and swelling ratio in electrolyte is studied.The result lists in table 6.
Positive active material (A1)
(A1-3)：Li 2Mn 2O 4
(A1-4)：LiNi 0.8Mn 0.2O 2
(A1-5)：LiFe 1/3Co 1/3Mn 1/3O 2
Cement (B2)
(B2-3): TFE/VdF copolymer (TFE/VdF=33/67 mole % ratio)
(B2-4): TFE/VdF copolymer (TFE/VdF=38/62 mole % ratio)
(B2-5): TFE/VdF copolymer (TFE/VdF=8/92 mole % ratio)
Fluorubber particle (C)
(C-1): crosslinked VdF/HFP (78/22 mole of % ratio) copolymer rubber.Average primary particle diameter 0.3 μ m)
Figure BDA0000119461120000221
Embodiment 7
Among the embodiment 4; The NMP that uses during as the slurry of preparation mixture No.1-1; Use moisture as the NMP of 100ppm, moisture as the NMP of 500ppm and moisture as the NMP of 1000ppm and make water; In addition likewise make lithium secondary battery (laminated cell), multiplying power property and cycle characteristics are investigated.The result lists in table 7.
Table 7
Embodiment 8
Among the embodiment 5, use SiO as negative electrode active material 2Or Sn and replace Si, in addition likewise make negative pole.
Anodal A1-2 (the LiNi that uses 1/3Co 1/3Mn 1/3O 2) as positive active material, in addition likewise make with embodiment 1.
Use this negative pole and positive pole, likewise make lithium secondary battery (laminated cell), likewise measure cycle characteristics with embodiment 4 with embodiment 4.The result lists in table 8.
Table 8
Figure BDA0000119461120000232

Claims (17)

1. the electrode composition of a lithium secondary battery is used slurry, and it comprises electrode active material (A), cement (B) and fluorubber particle (C).
2. electrode composition as claimed in claim 1 is used slurry, and wherein, the fluorubber particle comprises the copolymer rubber unit of vinylidene fluoride and hexafluoropropylene; The copolymer rubber unit of tetrafluoroethene, vinylidene fluoride and hexafluoropropylene; Or the copolymer rubber unit of tetrafluoroethene and propylene.
3. according to claim 1 or claim 2 electrode composition is used slurry, and wherein, fluorubber particle (C) is crosslinked fluorubber particle.
4. use slurry like each described electrode composition of claim 1～3, wherein, the average primary particle diameter of fluorubber particle (C) is 0.1 μ m～2.0 μ m.
5. use slurry like each described electrode composition of claim 1～4, wherein, cement (B) comprises the fluoropolymer (B2) shown in polyvinylidene fluoride (B1) and/or the composition formula (B2),
Composition formula (B2):
(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＜n≤0.5; 0≤l≤0.1, wherein, m+n+l=1.
6. electrode composition as claimed in claim 5 is used slurry, and wherein, cement (B2) comprises the fluorinated copolymer that the middle m of formula (B2), n and l are respectively 0.50≤m≤0.90,0.09≤n≤0.50 and 0≤l≤0.08, wherein, and m+n+l=1.
7. electrode composition as claimed in claim 5 is used slurry, the binary fluorinated copolymer that wherein, cement (B2) comprises that l in the formula (B2) is 0, m and n are respectively 0.50≤m≤0.90 and 0.10≤n≤0.50, wherein, m+n=1.
8. electrode composition as claimed in claim 5 is used slurry, and wherein, cement (B2) comprises the fluorinated copolymer that the middle m of formula (B2), n and l are 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 5～8, wherein, cement (B) also comprises except that polyvinylidene fluoride (B1) and the solvable type thermoplastic resin of the solvent the fluoropolymer (B2) (B3).
10. electrode composition as claimed in claim 9 is used slurry, and wherein, cement (B3) is for being selected from least a kind of cement in the group of being made up of polyacrylic acid based polymer, polymethylacrylic acid based polymer, polyimides, polyamide and polyamidoimide.
11. each the described electrode composition like claim 1～10 is used slurry, wherein, electrode active material (A) is positive active material (A1), and comprises the lithium-contained composite metal oxide shown in the formula (A1),
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 kind in the group of forming by Ni and Mn; M 2For being selected from least a kind in the group of forming by Co, Al and Fe.
12. each the described electrode composition like claim 1～10 is used slurry, wherein, electrode active material (A) is negative electrode active material (A2), and this negative electrode active material (A2) comprises the basic matterial that contains Si and/or Sn.
13. each the described electrode composition like claim 1～12 is used slurry, it also comprises organic solvent.
14. electrode composition as claimed in claim 13 is used slurry, wherein, organic solvent is that moisture is the organic solvent below the 100ppm.
15. each the described electrode composition like claim 1～14 is used slurry; Wherein, comprise the electrode active material (A) of 70 quality %～98 quality %, the cement (B) of 0.1 quality %～20 quality % and the fluorubber particle (C) of 0.1 quality %～20 quality % in the solid constituent.
16. the electrode of a lithium secondary battery, it obtains through each described electrode composition of claim 1～15 is coated on the collector body with slurry and carried out drying.
17. a lithium secondary battery, it as positive pole and/or negative pole, and possesses nonaqueous electrolytic solution with the described electrode of claim 16.
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