CN105576284A - Anode aqueous binder of lithium ion battery and preparation method thereof - Google Patents

Anode aqueous binder of lithium ion battery and preparation method thereof Download PDF

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Publication number
CN105576284A
CN105576284A CN201610090937.1A CN201610090937A CN105576284A CN 105576284 A CN105576284 A CN 105576284A CN 201610090937 A CN201610090937 A CN 201610090937A CN 105576284 A CN105576284 A CN 105576284A
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lithium ion
aqueous binder
ion battery
preparation
battery negative
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李强
白丰瑞
罗贺斌
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Fujian Lanhai Blackstone Technology Co Ltd
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Fujian Lanhai Blackstone Technology Co Ltd
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Priority to CN201610090937.1A priority Critical patent/CN105576284A/en
Publication of CN105576284A publication Critical patent/CN105576284A/en
Priority to JP2017027161A priority patent/JP6624739B2/en
Priority to KR1020170021518A priority patent/KR20170097577A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the lithium ion battery technical field, discloses an anode aqueous binder of a lithium ion battery and a preparation method thereof. The preparation method of the anode aqueous binder of the lithium ion battery comprises follow specific steps: successively adding reactivity emulsifier, water soluble acrylic acid monomers, oil soluble acrylic acid monomers and initiator solution, mixing evenly, taking the mixture as base solution, heating up to initiate polymerization, keeping stirring, dripping the mixture of the water soluble and oil soluble acrylic acid monomers and the initiator solution, reacting, thus preparing the anode aqueous binder of the lithium ion battery. According to the anode aqueous binder and the preparation method of the invention, the problems that the anode aqueous binder of the lithium ion battery is high in viscosity and low in dispersion efficiency are solved; and the anode aqueous binder of the lithium ion battery prepared by the invention is low in viscosity and dosage, has excellent dispersion performance in electrode materials such as graphite and has excellent battery capacity exerting performance and cycle performance.

Description

A kind of lithium ion battery negative aqueous binder and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery negative aqueous binder and preparation method thereof.
Background technology
New forms of energy project, as a kind of new industry, meets national energy-saving and reduces discharging and the principles and policies of sustainable development, for the industrial structure adjustment and be very helpful transition.Lithium rechargeable battery is as a very important part in New Energy Industry, particularly important in this industry at present.
Along with the development of science and technology and the raising of the people's material and cultural life level, the requirement of people to lithium ion battery is also more and more higher.Lithium rechargeable battery is widely used in the 3C Products such as mobile phone, electric motor car and automobile, its capacity and useful life most important to its large-scale promotion and application.
Lithium ion battery, normally an active material, conductive additive and the even form slurry of binder solution mixed grinding, is coated as on the Copper Foil of pole piece, aluminium foil, drying, the PROCESS FOR TREATMENT such as to roll and forms.The capacity of lithium rechargeable battery and life-span depend on the performance of the amount of active material in battery pole piece and the adhesive for bond active material and pole piece.The amount of active material means that the capacity of battery is larger more, but the more impacts on adhesion strength of active material are larger in the production process of battery.In addition, the more adhesive of application is fluoro-containing copolymer adhesive at present, and volatilization both contaminated environment of its solvent in manufacturing process, endanger again the health of operating personnel, and the solvent of fluoropolymer are expensive, add the production cost of battery.Have very important significance so develop safe, pollution-free, efficient aqueous binder for lithium ion battery.
Lithium ion battery adhesive is mainly divided into two classes, and a class is oil binder, and employing organic solvent is dispersant; One class is aqueous binder, and employing water is dispersant.Compared with oil binder, aqueous binder is dispersant with water, has solvent-free release, environmentally friendly, production cost is low, security performance advantages of higher in preparation process, becomes the important development direction of adhesive industry.The scheme that carboxycellulose sodium (CMC) and styrene-butadiene latex (SBR) are composite is generally used in the preparation process of the aqueous binder of current lithium ion battery negative electrode, described in patent CN201310322571.2, the shortcoming that the program exists is, mix with negative pole associated materials and SBR again after CMC first fully dissolves by needs and disperse, but the course of dissolution of CMC in water, speed is slow, inefficiency, and easily produce transparent particle, dispersive property is poor, affects the consistency of battery pole piece.
Patent CN01108511.8 discloses the preparation method of the aqueous binder of a kind of electrode material of secondary lithium ion battery and collector body, and its technical scheme is as follows: take general formula as CH 2=CR 1r 2hydrophilic monomer and lipophile monomer be starting polymerization monomer, first by one, two or more hydrophilic monomers and one, the mixing of two or more lipophile monomers, add emulsifying agent and other auxiliary agents, with the water soluble starters such as ammonium persulfate and and NaSO thereof 3and FeSO 4redox system Deng formation is initiator system, at the temperature of 30-80 DEG C, and reaction 3-24 hour, obtained aqueous binder.The binder copolymer content of gained is lower, and viscosity is higher, affects dispersion efficiency, and agents useful for same kind is more, and the reaction time is longer, adds the production cost of aqueous binder.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of lithium ion battery negative aqueous binder, its concrete steps are as follows:
Add reactive emulsifier and water-soluble acrylic monomer, oil-soluble acrylic monomer and initiator solution successively, as rebasing liquid after mixing, intensification initiated polymerization, keep rapid stirring, drip mixed liquor and the initiator solution of water-soluble and oil-soluble acrylic monomer lentamente, react under high temperature, obtained lithium ion battery negative aqueous binder solution.
The ratio of reactive emulsifier, water-soluble acrylic monomer, oil-soluble acrylic monomer and initator in described rebasing liquid is 0.5-3:20-45:15-80:0.1-10 by weight; Be preferably 1.0-2.5:25-40:25-70:1.0-8.0; More preferably 1.5:25:60:0.5;
Described rebasing liquid consumption accounts for the 10-50% (percetage by weight, lower same) of total weight, is preferably 20-40%;
Described rebasing liquid take water as decentralized medium, and above-mentioned total weight comprises the consumption of rebasing liquid, the dropping stage adds the consumption of the monomer mixed solution of reaction system and the consumption of initator, but do not comprise the consumption of water.
In described preparation method, the water-soluble acrylic monomer of use and the ratio of oil-soluble acrylic monomer are 5-40:20-80; Be preferably 20-40:30-60; More preferably 25:36;
Described initiator solution consumption accounts for the 0.5-6% of the total consumption of acrylic monomer, and described acrylic monomer comprises water-soluble acrylic monomer and oil-soluble acrylic monomer;
The solid content of described lithium ion aqueous binder is 30-60%; Be preferably 35-55%;
The time for adding of described monomer mixed solution is 1-3h, is preferably 1.5-2.5h;
Described monomer mixed solution starts to drip initiator solution after dripping 2-10min; Be preferably 5min;
Described reaction temperature is 60-90 DEG C, is preferably 70-85 DEG C;
The described reaction time is 2-6h, is preferably 3-5h; Start after adding initator initiated polymerization in described reaction time autoreaction system to calculate.
Described reactive emulsifier is the compound simultaneously comprising hydrophilic radical, lipophilic group and one or more reactive group, described reactive group is the group that can participate in polymerization reaction, as unsaturated bond ,-OH ,-COOH ,-NH such as carbon-carbon double bond, carbon carbon triple bond, carbonyls 2deng;
Preferably, described reactive emulsifier is selected from wherein one or more such as acrylamido sodium isopropyl xanthate, sodium vinyl sulfonate, 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, allyl ether hydroxypropanesulfonic acid sodium.
Described water-soluble acrylic monomer has following general formula: CH 2=CR 1r 2, wherein R 1=H ,-CH 3,-COOH, R 2=-COOH ,-CN ,-CONH 2,-COONa ,-CH 2cOOH ,-OOCCH 3,-COOCH 2cH 2oH ,-COOCH 2cH 2cH 2oH;
Preferably, described water-soluble acrylic monomer be selected from acrylic acid, methacrylic acid, acrylonitrile, acrylamide, PAA, itaconic acid, N hydroxymethyl acrylamide, hydroxy-ethyl acrylate and hydroxypropyl acrylate one or more.
Described oil-soluble acrylic monomer has following general formula: CH 2=CR 3r 4, wherein R 3=H ,-CH 3,-COOH, R 4=-COOCH 3,-COOCH 2cH 3,-COO (CH 2) 2cH 3,-COOCH 2cH (CH 2cH 3) CH 2cH 2cH 2cH 3,-COO (CH 2) 11cH 3,
Preferably, described oil-soluble acrylic monomer be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate and lauryl acrylate, isobornyl acrylate one or more.
Described initator be selected from potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, sodium sulfite, sodium hydrogensulfite, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azodiisobutyronitrile etc. one or more.
Described initiator solution is the aqueous solution of above-mentioned initator, and its mass percent is 5-20%;
The preparation of described lithium ion battery negative aqueous binder, carries out under 200-800rpm high-speed stirred, and course of reaction keeps nitrogen protection state.
In one embodiment of the invention, the preparation method of described lithium ion battery negative aqueous binder, its concrete steps are as follows:
Add reactive emulsifier and water-soluble acrylic monomer successively, after oil-soluble acrylic monomer, stir under 200-800rpm, logical nitrogen, in system, temperature is 70-80 DEG C, add initator, as rebasing liquid after mixing, reactive emulsifier in rebasing liquid, water-soluble acrylic monomer, the ratio of oil-soluble acrylic monomer and initator, be 1.5:25:60:0.5 by weight, rebasing liquid consumption accounts for the 20-40% of total weight, after reaction 0.5-1.5h, under agitation drip water-soluble and mixed liquor that is oil-soluble acrylic monomer, monomer mixed solution starts to drip initiator solution after dripping 2-10min, time for adding is 1.5-2.5h, dropping terminates rear rising temperature of reaction system to 70-85 DEG C and is incubated 0.5-1.5h, obtained lithium ion battery negative aqueous binder, the water-soluble acrylic monomer used in whole preparation process and the ratio of oil-soluble acrylic monomer are 25:36, the solid content of lithium ion aqueous binder is 35-55%.
Another aspect of the present invention is to provide a kind of lithium ion battery negative aqueous binder, adopts above-mentioned preparation method to obtain, and outward appearance is emulsion form viscous liquid, and its range of solid content is 30-60%, preferred 35-55%; Its range of viscosities is 500-8000mpa.s, is preferably 500-5000mpa.s.
The electrode material that lithium ion battery negative aqueous binder of the present invention is suitable for is coke, native graphite, Delanium, LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4, Ni, Co, Mn ternary compound oxides etc.
Another aspect of the present invention is to provide a kind of lithium ion cell electrode sheet, it is characterized in that, use above-mentioned aqueous binder and electrode active material hybrid modulation form slurry, coat drying on collector body and form, in wherein said slurry, the content of aqueous binder is 1-8%, is preferably 2-6%.
Another aspect of the present invention is to provide a kind of lithium ion battery, comprises positive pole, negative pole, electrolyte, barrier film, it is characterized in that, positive pole wherein and/or negative pole are above-mentioned lithium ion cell electrode sheet.
The preparation method of lithium ion battery negative aqueous binder provided by the invention, operating procedure is simple, reaction time is shorter, react more abundant, obtained lithium ion battery negative aqueous binder is emulsion form viscous liquid, have the advantages that solid content is higher, adhesive property is excellent, good mechanical stability, there will not be the demulsifying phenomenon such as reunion in dispersion process; Surface tension is lower, is more beneficial to the dispersion to conductive agent and electrode material, greatly improves dispersion efficiency and film forming; Simultaneously the adhesive pliability made of the method is good, and good fluidity, film forming is soft, and the battery pole piece prepared is smooth, consistency is good, the good cycle of the battery utilizing this pole piece to prepare, adopts 0.5c to circulate after 450 times battery capacity conservation rate more than 90%.
Accompanying drawing explanation
Figure 1 shows that the TG-DSC spectrogram of the lithium ion battery negative aqueous binder that the embodiment of the present invention 4 provides.
Figure 2 shows that the charging and discharging curve of the lithium ion test cell that embodiment 5 provides, the aqueous binder utilizing embodiment 2 to prepare makes cathode pole piece, and proportioning anode pole piece prepares above-mentioned lithium ion battery; Wherein, ordinate is cell voltage (V), and abscissa is capacity (mAh); 1 is charging curve, and 2 is discharge curve.
Figure 3 shows that the cyclic voltammogram of the lithium ion test cell that embodiment 5 provides, the aqueous binder utilizing embodiment 2 to prepare makes cathode pole piece, and proportioning lithium metal anode pole piece prepares above-mentioned lithium ion battery; Wherein, ordinate is electric current (mA), and abscissa is current potential (v).
Figure 4 shows that the charge and discharge cycle graph of the lithium ion test cell that embodiment 5 provides, the aqueous binder utilizing embodiment 2 to prepare makes cathode pole piece, and proportioning anode pole piece prepares above-mentioned lithium ion battery; Wherein, ordinate is capability retention, and abscissa is charge and discharge cycles number of times (secondary).
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
In the present embodiment, adopt sodium vinyl sulfonate, acrylic acid and ethyl acrylate to be reactive emulsifier, hydrophilic acrylic's monomer and lipophile acrylic monomer respectively, in whole preparation process, the ratio of three is 0.5:25:60.
Prepare the emulsion of lithium ion battery negative aqueous binder according to the following steps: by weight, add in reactor successively: sodium vinyl sulfonate 1.5 parts, 25 parts, acrylic acid, ethyl acrylate 60 parts and water, be uniformly mixed, and rotating speed is 200rpm.Logical nitrogen, 72 DEG C of constant temperature, add the ammonium persulfate aqueous solution of 0.5 part 10%, initiated polymerization, reaction time 50min; Slowly drip 50 parts of acrylic acid, the aqueous solution of 120 parts of ethyl acrylates and the ammonium persulfate aqueous solution of 10 part 10% (mass percent) again, time for adding is 3h, during dropping, in system, temperature is 75 DEG C, dropping terminates rear raised temperature to 80 DEG C insulation 60min, i.e. obtained water adhesive for lithium ion battery emulsion.
Obtained aqueous binder is milky viscous liquid, and its solid content is 40%, and viscosity is 800mpa.s.
Embodiment 2:
In the present embodiment, the component added in reactor successively and ratio are: sodium vinyl sulfonate 1.5 parts, 12.5 parts, acrylic acid, ethyl acrylate 30 parts and water; The component dripped and ratio are: 62.5 parts, acrylic acid, ethyl acrylate 150 parts; All the other steps are with embodiment 1.
Obtained aqueous binder is emulsion form viscous liquid, and its solid content is 40%, and viscosity is 1000-1500mpa.s.
Embodiment 3:
In the present embodiment, water-soluble acrylic monomer and oil-soluble acrylic monomer are respectively hydroxy-ethyl acrylate and butyl acrylate, and all the other steps are with embodiment 1.
Obtained aqueous binder is emulsion form viscous liquid, and its solid content is 50%, and viscosity is 1500mpa.s.
Embodiment 4:
In the present embodiment, allyl ether hydroxypropanesulfonic acid sodium, acrylamide, lauryl acrylate and azodiisobutyronitrile is adopted to be reactive emulsifier, hydrophilic acrylic's monomer, lipophile acrylic monomer and initator respectively; In rebasing liquid, the proportion of reactive emulsifier, water-soluble acrylic monomer, oil-soluble acrylic monomer and initator is 0.6:20:80:10; Rebasing liquid accounts for 30% of total weight, and all the other steps are with embodiment 1.
Obtained aqueous binder is emulsion form viscous liquid, and its solid content is 40%, and viscosity is 1000mpa.s, good mechanical stability, adopts 5000rpm to disperse in dispersion process, can stable existence.
As shown in Figure 1, by the excellent heat stability of spectrogram this aqueous binder known, decomposition temperature is higher than 270 DEG C for the TG-DSC spectrogram of above-mentioned aqueous binder.
Embodiment 5
With BTR518 Delanium for negative material, adopt the aqueous binder agent emulsion of the 2-in-1 one-tenth of embodiment, prepare cathode size.In whole cathode size, the proportioning of material is: aqueous binder, 3.5%; BTR518 Delanium, 95.5%; Conductive agent S-P, 1%.
The solid content of above-mentioned obtained cathode size is 58%, and viscosity is 3000mpa.s.The cathode pole piece made of slurry is level and smooth thus, and consistency is good, and surface density is high.
Above-mentioned cathode pole piece coupling LiMn2O4 (BN-M01) active material is assembled into lithium ion test cell, and carry out application test, result as in Figure 2-4.Fig. 2 is the charging and discharging curve of above-mentioned lithium ion test cell, and as shown in Figure 2, the discharge and recharge final voltage of test cell is 3.10-4.20V; Fig. 3 is the cyclic voltammogram of above-mentioned lithium ion test cell; Fig. 4 is the charge and discharge cycle graph of above-mentioned lithium ion test cell, and as shown in Figure 4, test cell first charge-discharge capacity is greater than 96%, capacity plays excellent, discharge curve platform stable, adopts 0.5c to circulate after 200 times, battery capacity conservation rate does not significantly decrease, and substantially remains on more than 97.0%; Battery capacity conservation rate is more than 90% to adopt 0.5c to circulate after 450 times, and capacity attenuation is little.
Embodiment 6
With graphite Q10 for negative material, select the aqueous binder agent emulsion of the 2-in-1 one-tenth of embodiment, prepare cathode size.In whole cathode size, the proportioning of material is: aqueous binder, 3.5%; Graphite Q10,95.5%; Conductive agent S-P, 1%.
The solid content of above-mentioned obtained cathode size is 48%, and slurry viscosity is 3400 centipoises.The cathode pole piece made of slurry is level and smooth thus, and consistency is good.
Above-mentioned cathode pole piece coupling LiMn2O4 (BN-M01) active material is assembled into lithium ion test cell 2, and be numbered battery 1 and 2 respectively, the cycle performance carrying out battery detects and drop test, and result is as shown in table 1-2.
Table 1 cycle performance testing result
Battery 1 and 2 is respectively 99.6% and 99.7% (standard >=96%) with 0.5C 20 the capacity/initial capacities that circulate, and is respectively 99.2% and 99.2% (standard >=95%), meets standard with 1C 20 the capacity/initial capacities that circulate.
Table 2 drop test result
Test result: battery is not smoldered, not on fire, do not explode, no leakage; At normal temperatures with the capability retention of battery 1 and 2 after 1C current charge-discharge electricity circulation 3 times all more than 95%, namely its capability retention is all greater than 85%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a preparation method for lithium ion battery negative aqueous binder, its concrete steps are as follows:
Add reactive emulsifier and water-soluble acrylic monomer, oil-soluble acrylic monomer and initiator solution successively, as rebasing liquid after mixing, intensification initiated polymerization, keep stirring, drip mixed liquor and the initiator solution of water-soluble and oil-soluble acrylic monomer, react, obtained lithium ion battery negative aqueous binder.
2. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, described reactive emulsifier be selected from acrylamido sodium isopropyl xanthate, sodium vinyl sulfonate, 2-allyl ether 3-hydroxy propane-1-sodium sulfonate, allyl ether hydroxypropanesulfonic acid sodium one or more.
3. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, described water-soluble acrylic monomer has following general formula: CH 2=CR 1r 2, wherein R 1=H ,-CH 3,-COOH, R 2=-COOH ,-CN ,-CONH 2,-COONa ,-CH 2cOOH ,-OOCCH 3,-COOCH 2cH 2oH ,-COOCH 2cH 2cH 2oH; And/or,
Described oil-soluble acrylic monomer has following general formula: CH 2=CR 3r 4, wherein R 3=H ,-CH 3,-COOH, R 4=-COOCH 3,-COOCH 2cH 3,-COO (CH 2) 2cH 3,-COOCH 2cH (CH 2cH 3) CH 2cH 2cH 2cH 3,-COO (CH 2) 11cH 3,
4. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 3, it is characterized in that, described water-soluble acrylic monomer be selected from acrylic acid, methacrylic acid, acrylonitrile, acrylamide, PAA, itaconic acid, N hydroxymethyl acrylamide, hydroxy-ethyl acrylate and hydroxypropyl acrylate one or more; And/or,
Described oil-soluble acrylic monomer be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate and lauryl acrylate, isobornyl acrylate one or more.
5. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, described initator be selected from potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, sodium sulfite, sodium hydrogensulfite, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azodiisobutyronitrile one or more.
6. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, the ratio of reactive emulsifier, water-soluble acrylic monomer, oil-soluble acrylic monomer and initator in described rebasing liquid, is: 0.5-3:20-45:15-80:0.1-10 by weight; Described rebasing liquid consumption accounts for the 10-50% of total weight; The solid content of described lithium ion battery negative aqueous binder is 30-60%.
7. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, in described preparation method, the water-soluble acrylic monomer of use and the ratio of oil-soluble acrylic monomer are 5-40:20-80; And/or described monomer mixed solution starts to drip initiator solution after dripping 2-10min; And/or the consumption of described initiator solution accounts for the 0.5-6% of the total consumption of acrylic monomer.
8. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, it is characterized in that, the time for adding of described monomer mixed solution is 1-3h; And/or described reaction temperature is 60-90 DEG C; And/or the reaction time is 2-6h.
9. the preparation method of lithium ion battery negative aqueous binder as claimed in claim 1, is characterized in that, described lithium ion battery negative aqueous binder be prepared in the stirring of 200-800rpm under carry out, keep nitrogen protection state in course of reaction.
10. a lithium ion battery negative aqueous binder, it is characterized in that, described lithium ion battery negative aqueous binder is obtained by the preparation method of the lithium ion battery negative aqueous binder described in any one of claim 1-9, its solid content is 30-60%, and range of viscosities is 500-8000mpa.s.
CN201610090937.1A 2016-02-18 2016-02-18 Anode aqueous binder of lithium ion battery and preparation method thereof Pending CN105576284A (en)

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Application Number Priority Date Filing Date Title
CN201610090937.1A CN105576284A (en) 2016-02-18 2016-02-18 Anode aqueous binder of lithium ion battery and preparation method thereof
JP2017027161A JP6624739B2 (en) 2016-02-18 2017-02-16 Aqueous binder for negative electrode of lithium ion battery and method for preparing the same
KR1020170021518A KR20170097577A (en) 2016-02-18 2017-02-17 Aqueous binder for negative electrode of lithium ion battery and the preparation method thereof

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Application publication date: 20160511