CN1195036C - Water adhesive for electrode material of secondary lithium ion battery and its preparing process - Google Patents
Water adhesive for electrode material of secondary lithium ion battery and its preparing process Download PDFInfo
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- CN1195036C CN1195036C CNB011085118A CN01108511A CN1195036C CN 1195036 C CN1195036 C CN 1195036C CN B011085118 A CNB011085118 A CN B011085118A CN 01108511 A CN01108511 A CN 01108511A CN 1195036 C CN1195036 C CN 1195036C
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Abstract
The present invention relates to a preparation method for an aqueous adhesive agent for electrode materials of lithium ion secondary batteries and electricity collection bodies. Hydrophilicity monomers and lipophilicity monomers whose general formula is CH2=CR1R2 are used as initial polymerization monomers. One, two or more kinds of hydrophilicity monomers and one, two or more kinds of lipophilicity monomers are mixed, and emulsifying agents and other auxiliary agents are added. Water solubility initiating agents, such as ammonium persulfate, etc., and a redox system which is composed of the water solubility initiating agents, NaSO3, FeSO4, etc. is used as an initiating system. At the temperature of 30 to 80DEGC, components react for 3 to 24 hours to prepare the aqueous adhesive agent. When the aqueous adhesive agent of the present invention is used, the electrode material utilization rate and the service cycle life of the lithium ion batteries can be enhanced.
Description
Technical field
The present invention relates to electrode material of secondary lithium ion battery tackiness agent and manufacture method thereof, more particularly, relate to and be used for the lithium ion secondary battery electrode active material, comprise the aqueous binder of cobalt, nickel, manganese class positive pole and various carbon element negative materials, also relate to its manufacture method and the lithium-ion secondary cell that uses this tackiness agent.
Background technology
Lithium-ion secondary cell is the high specific energy battery of a kind of novel chargeable ideal of just developing over past ten years and growing up, and is widely used in electric vehicle, aerospace, portable electronics for example mobile telephone, laptop computer, pick up camera, photographic camera, word processor etc.; This battery mainly is made up of positive electrode, negative potential, barrier film and nonaqueous electrolytic solution etc.; Positive and negative electrode is generally by the powdery electroactive material, and promptly lithium transition-metal oxide positive electrode material or carbon element negative material, tackiness agent, conductive additive and current collector are formed.The preparation method evenly becomes slurry to electroactive material, conductive additive and binder solution mixed grinding, coats on Copper Foil as current collector, the aluminium foil, and drying art breading such as rolls and forms.Using maximum tackiness agents at present is fluoro-containing copolymer adhesive.
For example: adopting the N-Methyl pyrrolidone solution of polyvinylidene difluoride (PVDF) (PVDF), poly-(biasfluoroethylene-hexafluoropropylene) is that tackiness agent, lithium nickel oxide are active substance and conductive agent, by a certain percentage by the high-speed stirring form slurry, coat on the aluminium foil, roll after drying and make the pellet electrode blank, after 200 ℃ of heat treated 1 hour and obtain anode electrode sheet finished product (JP 7220722); With the Fluorine containing olefine polymkeric substance, as the solution that contains polyvinylidene difluoride (PVDF) is the plain patent (JP778056, JP 878057) for active material manufacturing lithium ion battery carbon element negative plate of tackiness agent, KETJEN charcoal.
With the Fluorine containing olefine polymkeric substance is the tackiness agent of lithium ion battery electrode material, both contaminate environment of the volatilization of solvent in the making processes tackiness agent, the health that endangers operator again.In addition the solvent of fluoropolymer its cost an arm and a leg, increased the production cost of lithium ion battery undoubtedly.
In order to address the above problem, people also research and development water adhesive of lithium ion battery, as vinylformic acid-styrene polymer, vinylformic acid-silicon-oxygen polymer, cinnamic acrylic ester polymkeric substance (JP2000294230); Styrene butadiene polymkeric substance (JP 2000106198), butadiene-acrylonitrile polymer waterborne polymeric latex such as (EP 100905).This base polymer latex is producing certain influence to battery performance in varying degrees because of there being more emulsifying agent, and this its viscosity of base polymer latex is on the low side in addition, then is adverse factors in the cathode size and the coating process process that prepare.Above-mentioned aqueous binder has no value for use on industrial production.
Summary of the invention
The object of the present invention is to provide a kind of new polymerization reaction system, be used to synthesize the aqueous binder that electrode material of secondary lithium ion battery and current collector is had good adhesive property; Replace in the present lithium ion battery process industry fluoropolymer equal solvent type tackiness agent that generally uses, to solve organic solvent healthy to the pollution of environment and protection producers.
The monomer that is used for polyreaction of the present invention, a class are hydrophilic monomer, and a class is the lipophilicity monomer.The aqueous binder of institute's synthetic lithium ion battery positive and negative electrode material, external appearance characteristic is translucent or emulsion form, and viscosity is the 200-16000 centipoise, and solid content is 5-40%.
Aqueous binder technical characterictic of the present invention:
1. do not contain thickening material in the aqueous binder of the present invention.(as sodium cellulose glycolate CMC, PVAC polyvinylalcohol etc.) in use need not add above-mentioned thickening material.
2. aqueous binder of the present invention does not contain or contains the ionic emulsifying agent less than＜0.3%.
3. the lithium ion battery plus-negative plate pole piece that aqueous binder of the present invention is prepared, positive and negative electrode active material layer and metal current collector binding property are good.
4. use the cathode pole piece of the high sub-battery of lithium of tackiness agent of the present invention to soak not swelling in electrolyte solution, not coming off to keep the dimensional stability of electrode slice for a long time.
5. use the lithium ion battery of tackiness agent of the present invention to have that internal resistance is little, polarization is low, cell container is high, reach the features such as utilization ratio height of negative electrode active material.
The objective of the invention is to realize by following technical solution:
Place reactor to mix with dispersion medium a kind of, two or more hydrophilic monomers, auxiliary agent earlier and dissolve, stirring velocity is 60-300 rev/min: in the solution with pure a kind of, the monomeric part or all of adding reactor of two or more lipophilicities, feed high pure nitrogen and drove oxygen 0.5-2 hour again; Heat temperature raising is to preset temperature and constant temperature then, and the constant temperature scope is 30-80 ℃; Add initiator system and begin polymerization, polymerization reaction time is 3-24 hour, and reaction just obtains water adhesive for electrode material of secondary lithium ion battery after finishing.
In the above-mentioned method for preparing water adhesive for electrode material of secondary lithium ion battery, said hydrophilic monomer general structure is: CH=CR
1R
2, R wherein
1=-H ,-CH
3R
2=-COOLi ,-COONa ,-COO (CH
2)
6SO
3Li ,-COO (CH
2)
6SO
3Na ,-CONH
2,-CONHCH
3,-CONHCH
2CH
3,-CON (CH
3)
2,-CON (CH
2CH
3)
2As the preparation raw material hydrophilic monomer can select wherein a kind of, two or more.Said lipophilicity monomer, its general structure is: CH
2=CR
1R
2, R wherein
1=-H ,-CH
3R
2=-C
6H
5,-OCOCH
3,-COOCH
3,-COOCH
2CH
3,-COOCH
2CH
2CH
2CH
3,-COOCH
2CH (CH
2CH
3) CH
2CH
2CH
2CH
3,-CN ,-Cl ,-F etc.; As the preparation raw material the lipophilicity monomer can select wherein a kind of, two or more.Said auxiliary agent is one or more in the emulsifying agents such as dodecylbenzene sulfonate, dodecane sulfonate, multicondensed ethylene glycol phenolic ether in the ninth of the ten Heavenly Stems.Said initiator system is initiator and and NaSO thereof such as ammonium persulphate, Potassium Persulphate, hydrogen peroxide, azo two isobutyls be fine
3And FeSO
4Deng the redox initiation system that constitutes.Range of solid content with the resulting water adhesive for electrode material of secondary lithium ion battery of above-mentioned preparation method is 5-40% (weight percentage, down together), is good with 10-20%.Reaction times 3-28 hour was good with 5-18 hour.Temperature of reaction 30-80 ℃ is the best with 40-60 ℃ again.Auxiliary dosage accounts for the 0-0.3% of whole monomer weights, and initiator amount then accounts for the 0.2-1.0% of total monomer weight.The electrode materials that lithium ion battery electrode material aqueous binder of the present invention is suitable for is coke, natural graphite, synthetic graphite, LiCoO
2, LiNiO
2, LiMnO
2, LiNi
xCo
(1-x)O
2Deng.In electrode slice, the content of aqueous binder is 2-8%, is good with 3-6%.
Water adhesive for electrode material of secondary lithium ion battery of the present invention, its bond properties, chemical property and application with method well-known in the art, promptly are assembled into test cell and carry out the charge-discharge test investigation.Preparation process is as follows:
A. will be diluted to 1 part of 5% aqueous binder and mix with 0.95 part of carbon element negative material, and fully grind to form slurry, and be uniformly coated on the clean Copper Foil, oven dry back grinding compacting promptly obtains the negative electricity pole piece.
B. will be diluted to 1 part of 5% aqueous binder and 0.85 part of positive electrode material, 0.1 part of conductive additive mixed grinding form slurry, be uniformly coated on the clean aluminium foil, after the oven dry compacting, obtain the anode electrode sheet.Make the electrode slice of various areas, after vacuum-drying under 120 ± 10 ℃ the temperature, place the glove box of dry argon gas atmosphere, dress up C/Li, Li with the metal lithium electrode matched group respectively
xMO
2(Mn) test cell or mutual matched group are dressed up lithium ion battery Li to/Li for M=Co, Ni
xMO
2/ C, electrolytic solution are 1MLiClO
4Or LiPF
6/ NSC 11801 (EC)+diethyl carbonate (DEC), EC: DEC=1: 1 (wt/wt).The battery charging and discharging mode is a galvanostatic method, and the condition of discharging and recharging is: charging current 0.3-1.1mA/cm
2Discharging current 0.5-1.1mA/cm
2Stopping potential scope 0.01-1.00V or 2.70-4.20V; Test by computer control multichannel battery auto charge and discharge tester.
Embodiment
Be embodiments of the invention below.
Embodiment one
Carry out copolymerization with hydrophilic monomer vinylformic acid (AA), acrylamide (AM) and lipophilicity monomer vinyl acetate (VAc) at aqueous phase in the present embodiment, the aqueous binder of making that is used for lithium-ion secondary cell carbon anode sheet, its copolymerization consists of AM: AA: VAc=5: 1: 4 (weight ratio, down together), multipolymer content is 10%, and product is the aqueous viscous liquid of gala.
The above-mentioned method for making that is used for the aqueous binder of lithium-ion secondary cell is: adding 15 parts of acrylamides (AM), 3 parts of vinylformic acid (AA) and 270 parts of distilled water at reaction vessel, is to dissolve under 100 rev/mins the stirring at rotating speed; Add 12 parts of vinyl acetates (VAc); Under 70 ℃, add 0.6 part of ammonium persulphate, initiation reaction; Afterreaction was finished in 8 hours, made a kind of aqueous binder of the lithium-ion secondary cell carbon negative pole of above-mentioned composition.
Embodiment two
The method for making of present embodiment tackiness agent and operational condition and embodiment one are basic identical, and only different is to add another hydrophilic monomer methacrylic acid lithium (LiMAA), and employing is redox initiation system.With 24 parts of acrylamides (AM), 18 parts of methacrylic acid lithiums (LiMAA), be dissolved in 340 parts of distilled water; Add 18 parts of vinyl acetates (VAc), add 0.4 part in ammonium sulfate then, 0.2 part of initiation reaction of S-WAT was 45 ℃ of reactions 5 hours; The copolymerization of tackiness agent consists of LiA: AM: VAc=3: 4: 3, multipolymer content was 15%, this binder product emulsion form that is white in color.
Embodiment three
The method for making of present embodiment tackiness agent is same as embodiment two, and only different is that the lipophilicity monomer was vinylbenzene (S), in 50 ℃ of reactions of temperature 15 hours.Copolymerization consists of LiMAA: AM: S=3: 4: 3, the multipolymer solid content was 15%, and product is the emulsion form viscous liquid.
Embodiment four
The method for making of present embodiment tackiness agent and embodiment three are basic identical, and only different is that the lipophilicity monomer was propylene fine (AN), adds 0.4 part of ammonium persulphate, in 58 ℃ of reactions of temperature 15 hours.The tackiness agent copolymerization consists of AM: LiMAA: AN=3: 5: 2, multipolymer content was 15%, and product is translucent viscous liquid.
Embodiment five
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=2: 3: 1, multipolymer content was 15%, and product is translucent viscous liquid.
Embodiment six
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=2: 1: 3, multipolymer content was 15%, and product is the aqueous viscous liquid of gala.
Embodiment seven
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=2: 2: 2, multipolymer content was 15%, and product is the aqueous viscous liquid of gala.
Embodiment eight
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=1: 2: 3, multipolymer content was 15%, and product is the aqueous viscous liquid of gala.
Embodiment nine
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=1: 1: 2, multipolymer content was 15%, and product is the aqueous viscous liquid of gala.
Embodiment ten
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is to react 15 hours for 63 ℃ in temperature.The tackiness agent copolymerization consists of AM: LiMAA: AN=11: 24: 45, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 11
The method for making of present embodiment tackiness agent and embodiment ten are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=1: 2: 5, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 12
The method for making of present embodiment tackiness agent and embodiment ten are basic identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN=3: 12: 25, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 13
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is to add 0.18 part emulsifying agent Witco 1298 Soft Acid lithium.The tackiness agent copolymerization consists of AM: LiMAA: AN=3: 4: 3, multipolymer content was 15%, and product is translucent viscous liquid.
Embodiment 14
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that increasing a kind of lipophilicity monomer is vinyl acetate (VAc), adds 0.4 part of ammonium persulphate, 0.2 part of S-WAT; In 40 ℃ of reactions of temperature 15 hours.The tackiness agent copolymerization consists of AM: LiMAA: AN: VAc=18: 30: 12: 5, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 15
The method for making of present embodiment tackiness agent and embodiment tetradecyl are originally identical, and only different is that the tackiness agent copolymerization consists of AM: LiMAA: AN: VAc=18: 30: 12: 9, multipolymer content was 17%, and product is the emulsion form viscous liquid.
Embodiment 16
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that hydrophilic monomer was vinyl pyrrolidone (VP) and methacrylic acid lithium (LiMAA), adds 0.4 part of ammonium persulphate, in 58 ℃ of reactions of temperature 15 hours.The tackiness agent copolymerization consists of AN: LiMAA: VP=5: 2: 1, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 17
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that increasing a kind of lipophilicity monomer was butyl methacrylate (BMA), adds 0.4 part of ammonium persulphate, in 60 ℃ of reactions of temperature 15 hours.The tackiness agent copolymerization consists of AM: LiMAA: AN: BMA=1.5: 3: 8: 1, multipolymer content was 15%, and product is the emulsion form viscous liquid.
Embodiment 18
The method for making of present embodiment tackiness agent and embodiment heptadecyl are originally identical, and only different is to add 0.05 part emulsifying agent Witco 1298 Soft Acid lithium.The tackiness agent copolymerization consists of AM: LiMAA: AN: BMA=1: 5: 10: 2, multipolymer content was 15%, and product is a white emulsion shape viscous liquid.
Embodiment 19
6 parts of butyl methacrylate (BMA), 6 parts of Isooctyl acrylate monomers (EHA), 7 parts of methacrylic acid lithiums (LiMAA), 40 fens propylene fine (AN), emulsifying agent Witco 1298 Soft Acid lithium and 340 parts of distilled water of 0.15 part are mixed, add 0.5 part in ammonium sulfate then, 60 ℃ of reactions 10 hours in batches; Multipolymer content is 15%, and product is muddy shape viscous liquid.
8 parts of butyl methacrylate (BMA), 7 parts of Isooctyl acrylate monomers (EHA), 5 parts of methacrylic acid lithiums (LiMAA), 40 parts of propylene fine (AN), emulsifying agent Witco 1298 Soft Acid lithium and 340 parts of distilled water of 0.18 part are mixed, add 0.5 part in ammonium sulfate then, 60 ℃ of reactions 10 hours in batches; Multipolymer content is 15%, and product is a white emulsion shape viscous liquid.
Embodiment 21
With 6 parts of ethyl propenoates (BA), 11 parts of Isooctyl acrylate monomers (EHA), 3 parts of methacrylic acid lithiums (LiMAA), 40 parts of propylene fine (AN), 0.08 part emulsifying agent Witco 1298 Soft Acid lithium, all the other are identical with embodiment 20.Multipolymer content is 15%, and product is a white emulsion shape viscous liquid.
Embodiment 22
9 parts of acrylamides (AM), 9 parts of Isooctyl acrylate monomers (EHA), 21 parts of butyl acrylates (BA), 21 parts of vinylbenzene (S), emulsifying agent Witco 1298 Soft Acid lithium and 240 parts of distilled water of 0.28 part are mixed, add 0.5 part in ammonium sulfate then, 60 ℃ of reactions 10 hours in batches; Multipolymer content is 20%, and product is a white emulsion shape viscous liquid.
Embodiment 23
5 parts of methacrylic acid lithiums (LiMAA), 15 parts of butyl acrylates (BA), 40 parts of propylene fine (AN), emulsifying agent Witco 1298 Soft Acid lithium and 240 parts of distilled water of 0.28 part are mixed, add 0.5 part in ammonium sulfate then, in batches 60 ℃ of reactions 10 hours; Multipolymer content is 20%, and product is translucent viscous liquid.
Embodiment 24
The method for making of present embodiment tackiness agent and embodiment four are basic identical, and only different is that hydrophilic monomer is vinylformic acid lithium (LiAA); Add 0.4 part of ammonium persulphate, in 58 ℃ of reactions of temperature 15 hours in batches.The tackiness agent copolymerization consists of AN: LiAA: AM=5: 2: 1, multipolymer content was 15%, and product is translucent viscous liquid.
Embodiment 25
The method for making of present embodiment tackiness agent and embodiment tetracosyl are originally identical, and only different is that increasing a kind of hydrophilic monomer is methacrylic acid lithium (LiMAA); Add 0.3 part of ammonium persulphate then, in 59 ℃ of reactions of temperature 18 hours in batches.The tackiness agent copolymerization consists of AN: LiMAA: AM: LiAA=5: 2: 1: 0.08, multipolymer content was 15%, and product is translucent viscous liquid.
Embodiment 26
The method for making of present embodiment tackiness agent and embodiment tetracosyl are originally identical, and only different is that the tackiness agent copolymerization consists of AN: LiMAA: AM: LiAA=5: 2: 1: 0.3, multipolymer content was 15%, and product is translucent viscous liquid.
The application of aqueous binder of the present invention in lithium-ion secondary cell
Embodiment 28
With the modified graphite is negative material, and obtaining emulsion among the embodiment four is tackiness agent, makes by preceding art method and consists of 95% graphite, the carbon negative plate of 5% tackiness agent; With LiCoO
2Be positive electrode material, the emulsion that embodiment four obtains is a tackiness agent, cooperates conductive agent, makes and consists of 85%LiCoO
2, 10% conductive agent, the positive plate of 5% tackiness agent; The coupling positive and negative plate has been assembled into the lithium ion test cell and has carried out the constant current charge-discharge test; Battery diaphragm is Cellgard-2400, and electrolytic solution is 1.0MLiClO
4/ EC+DEC (1: 1), discharging and recharging final voltage is the 2.70-4.20 volt.The result shows: test cell loading capacity first can reach more than the 320mAh/g, and efficiency for charge-discharge is greater than 88%, and the discharge curve platform stable; Capability retention after 40 circulations still can be more than 85%.Compare with the PVDF Solvent Adhesive, every performance index that aqueous binder of the present invention showed are not a halfpenny the worse, and are wherein, also quite a lot of aspect this important indicator of loading capacity first.As Fig. 1 and Fig. 2.
Embodiment 29
Present embodiment test and embodiment octacosyl are originally identical, and only different is is negative pole with the metallic lithium, and charging current is 0.34mA/cm
2, discharging current is 0.51mA/cm
2The result shows: utilize the sticking and LiCoO of aqueous binder of the present invention
2The positive electrode material of forming is assembled into the test lithium cell when carrying out the constant current charge-discharge test, and the utilization ratio of its positive electrode active materials almost reaches theoretical value, and after carrying out 15 charge and discharge cycles, its capability retention does not still significantly descend.As Fig. 3 and Fig. 4.
Present embodiment test and embodiment nonacosyl are originally identical, and only different is to form positive electrode material with modified graphite and aqueous binder of the present invention, are assembled into the test lithium cell and carry out the constant current charge-discharge test, and charging current is 0.31mA/cm
2, discharging current is 0.46mA/cm
2The result shows: loading capacity is 347mAh/g first, and discharging efficiency can reach 91% first.Having illustrated by the bonding battery electrode material of aqueous binder of the present invention, carried out in the charge and discharge process at the composition battery, chemical reaction does not almost take place, therefore, is ideal lithium ion battery tackiness agent, as Fig. 5.
Claims (3)
1, a kind of preparation method who is used for the aqueous binder of electrode material of secondary lithium ion battery and current collector is characterized in that: it is to be CH with the general formula
2=CR
1R
2Hydrophilic monomer and lipophilicity monomer be polymerization single polymerization monomer, with a kind of, two or more hydrophilic monomers, auxiliary agent, dispersion medium and a kind of, two or more lipophilicity monomers place reactor together, stirring velocity is 60-300 rev/min, feeding high pure nitrogen drove oxygen 0.5-2 hour, under 30-80 ℃ temperature, add initiator system and begin polymerization, the initiator of adding gradation in reaction process adds, and polymerization reaction time is 3-24 hour, after finishing, reaction just obtains the lithium ion aqueous binder of certain viscosity, wherein, in the monomer general formula, R
1And R
2Be respectively:
Hydrophilic monomer:
R
1＝-H、-CH
3；
R
2＝-H、-COOLi、-COONa、-CONH
2、-CONHCH
3、-CONHCH
2CH
3、-CON(CH
3)
2、-CON(CH
2CH
3)
2，
The lipophilicity monomer:
R
1＝-H、-CH
3；
R
2＝-C
6H
5、-OCOCH
3、-COOCH
3、-COOCH
2CH
3、-COOCH
2CH
2CH
2CH
3、-COOCH
2CH(CH
2CH
3)CH
2CH
2CH
2CH
3、-CN，
The aqueous binder range of solid content is the 5-40% of gross weight, and the monomeric weight ratio of hydrophilic monomer and lipophilicity is 0.01-0.8: 1, and auxiliary dosage accounts for the 0-0.3% of whole monomer weights, and initiator amount accounts for the 0.2-1.0% of gross weight.
2, according to the described preparation method who is used for the aqueous binder of electrode material of secondary lithium ion battery and current collector of claim 1, it is characterized in that: described polymer monomer is following compound:
H
2C＝CH-COOH、H
2C＝CH-COONa、H
2C＝CH-COOLi、H
2C＝CH-CONH
2、
H
2C＝CH-CONHCH
3、H
2C＝CH-CONHCH
2CH
3、H
2C＝CH-CON(CH
2CH
3)
2、
H
2C＝CH-CON(CH
3)
2、H
2C＝CCH
3-COOH、H
2C＝CCH
3-CONH
2、
H
2C＝CCH
3-COONa、H
2C＝CCH
3-COOLi、H
2C＝CCH
3-CONHCH
3、
H
2C＝CCH
3-CON(CH
3)
2、H
2C＝CCH
3-CONHC
2H
5、H
2C＝CCH
3-CON(C
2H
5)
2、
H
2C＝CH-CN、H
2C＝CH-OCOCH
3、H
2C＝CH-C
6H
6、H
2C＝CH-COOCH
3、
H
2C＝CH-COOC
2H
5、H
2C＝CH-COOC
4H
9、H
2C＝CH-COOC
8H
17、
H
2C＝CCH
3-COOC
2H
5、H
2C＝CCH
3-COOCH
3、H
2C＝CCH
3-COOC
4H
9。
3, the preparation method of the aqueous binder of electrode material of secondary lithium ion battery according to claim 1 and current collector is characterized in that described viscosity is the 200-16000 centipoise.
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|---|---|---|---|
| CNB011085118A CN1195036C (en) | 2001-06-08 | 2001-06-08 | Water adhesive for electrode material of secondary lithium ion battery and its preparing process |
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|---|---|---|---|
| CNB011085118A CN1195036C (en) | 2001-06-08 | 2001-06-08 | Water adhesive for electrode material of secondary lithium ion battery and its preparing process |
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|---|---|
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| CN1195036C true CN1195036C (en) | 2005-03-30 |
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| CN101260282B (en) * | 2008-03-18 | 2010-08-11 | 成都中科来方能源科技有限公司 | Water adhesive for lithium ion battery, preparation method thereof and lithium ion battery positive plate |
| JPWO2011089722A1 (en) * | 2010-01-22 | 2013-05-20 | トヨタ自動車株式会社 | Positive electrode and manufacturing method thereof |
| CN102746813A (en) * | 2012-07-03 | 2012-10-24 | 张倩 | Preparation method for aqueous binder used for lithium ion battery |
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2001
- 2001-06-08 CN CNB011085118A patent/CN1195036C/en not_active Expired - Lifetime
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|---|---|---|---|---|
| CN112467133A (en) * | 2020-03-30 | 2021-03-09 | 万向一二三股份公司 | Lithium ion battery cathode slurry and preparation method thereof |
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| CN1328102A (en) | 2001-12-26 |
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