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 PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- aqueous binder
- ion battery
- preparation
- battery negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (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
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.
Priority Applications (3)
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 |
Applications Claiming Priority (1)
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105576284A true CN105576284A (en) | 2016-05-11 |
Family
ID=55886168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610090937.1A Pending CN105576284A (en) | 2016-02-18 | 2016-02-18 | Anode aqueous binder of lithium ion battery and preparation method thereof |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6624739B2 (en) |
KR (1) | KR20170097577A (en) |
CN (1) | CN105576284A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106833448A (en) * | 2017-02-08 | 2017-06-13 | 北京蓝海黑石科技有限公司 | A kind of lithium ion cell positive aqueous binder and preparation method thereof |
CN106905475A (en) * | 2017-03-10 | 2017-06-30 | 湖南高瑞电源材料有限公司 | The ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and using the adhesive |
CN107641170A (en) * | 2017-09-27 | 2018-01-30 | 贵州理工学院 | Polymer emulsion, preparation method and the aqueous binder of preparation, method and application |
CN108767259A (en) * | 2018-05-24 | 2018-11-06 | 九江华先新材料有限公司 | A kind of aqueous binders and preparation method thereof for lithium ion battery |
CN108832125A (en) * | 2018-05-28 | 2018-11-16 | 九江华先新材料有限公司 | A kind of cathode of lithium battery aqueous binders and preparation method, electrode piece preparation method |
CN108847488A (en) * | 2018-06-14 | 2018-11-20 | 汕头市鲁汕化工原料有限公司 | Lithium ion secondary battery active material adhesive |
CN109565051A (en) * | 2016-07-29 | 2019-04-02 | 花王株式会社 | Electric energy storage device electrode resin combination |
CN110218285A (en) * | 2019-05-09 | 2019-09-10 | 福建蓝海黑石新材料科技有限公司 | A kind of aqueous binder and preparation method thereof |
CN110627945A (en) * | 2019-10-31 | 2019-12-31 | 湖南高瑞电源材料有限公司 | Acrylate adhesive modified by long-chain unsaturated carboxylic acid or derivative thereof, and preparation method and application thereof |
CN111656575A (en) * | 2018-01-26 | 2020-09-11 | 花王株式会社 | Positive electrode for lithium ion secondary battery |
CN112321761A (en) * | 2020-11-04 | 2021-02-05 | 深圳港池科技有限公司 | Preparation method of adhesive for lithium ion battery |
CN112662348A (en) * | 2020-01-21 | 2021-04-16 | 四川茵地乐科技有限公司 | Adhesive for battery, lithium ion battery negative electrode sheet and lithium ion battery |
CN112877012A (en) * | 2020-11-25 | 2021-06-01 | 湖南高瑞电源材料有限公司 | Preparation method and application of water-soluble low-modulus acrylic resin adhesive |
CN115926040A (en) * | 2022-11-30 | 2023-04-07 | 福建蓝海黑石新材料科技有限公司 | Preparation method of lithium ion battery cathode slurry |
CN116134060A (en) * | 2020-07-30 | 2023-05-16 | 大金工业株式会社 | Method for producing aqueous dispersion of fluoroelastomer, and aqueous dispersion |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7267142B2 (en) * | 2019-08-06 | 2023-05-01 | 株式会社日本触媒 | Binder for secondary battery electrode and its use |
WO2021085894A1 (en) * | 2019-10-31 | 2021-05-06 | 주식회사 엘지화학 | Anode binder material for lithium secondary battery, and anode binder comprising cured product thereof |
US20230073006A1 (en) * | 2020-03-20 | 2023-03-09 | Grst International Limited | Cathode and cathode slurry for secondary battery |
CN113801597B (en) * | 2021-10-19 | 2023-06-06 | 芜湖徽氏新材料科技有限公司 | PI adhesive tape based on lithium battery welding spot protection and preparation method thereof |
WO2023113330A1 (en) * | 2021-12-15 | 2023-06-22 | 주식회사 엘지에너지솔루션 | Anode composition, lithium secondary battery anode comprising same, and lithium secondary battery comprising anode |
CN114478958B (en) * | 2022-01-07 | 2023-08-29 | 瑞红锂电池材料(苏州)有限公司 | Modified SBR binder and preparation method and application thereof |
CN114520334B (en) * | 2022-02-14 | 2024-03-22 | 浙江大学 | Fluorine-containing composite binder for silicon negative electrode of lithium ion battery and preparation method thereof |
CN114478898A (en) * | 2022-02-17 | 2022-05-13 | 惠州市赛力达化工有限公司 | Emulsion polymerization adhesive for replacing SBR (styrene butadiene rubber) in negative electrode of lithium battery and preparation method of emulsion polymerization adhesive |
CN115838455A (en) * | 2022-12-27 | 2023-03-24 | 华南理工大学 | Low-swelling soap-free core-shell emulsion binder and preparation method and application thereof |
CN116285785A (en) * | 2023-04-10 | 2023-06-23 | 湖南林特科技有限公司 | Adhesive for carbon-coated aluminum foil and preparation method thereof |
CN116200147B (en) * | 2023-04-27 | 2023-08-04 | 齐河力厚化工有限公司 | Water-based adhesive, preparation method thereof and application thereof in lithium battery negative electrode |
CN116462792B (en) * | 2023-06-19 | 2023-09-01 | 广州纳诺新材料技术有限公司 | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294230A (en) * | 1999-04-09 | 2000-10-20 | Hitachi Powdered Metals Co Ltd | Slurry for forming negative electrode coating film for lithium ion secondary battery and lithium ion secondary battery |
CN1328102A (en) * | 2001-06-08 | 2001-12-26 | 成都茵地乐电源科技有限公司 | Water adhesive for electrode material of secondary lithium ion battery and its preparing process |
US20020034686A1 (en) * | 2000-07-26 | 2002-03-21 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
CN104448158A (en) * | 2014-12-05 | 2015-03-25 | 北京蓝海黑石科技有限公司 | Preparation method of water-based adhesive for lithium batteries |
CN104882612A (en) * | 2015-04-07 | 2015-09-02 | 宁德新能源科技有限公司 | Adhesive and lithium ion battery using the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103003991A (en) * | 2010-07-16 | 2013-03-27 | 株式会社日本触媒 | Aqueous electrode binder for secondary battery |
JP6478310B2 (en) * | 2013-02-15 | 2019-03-06 | 国立大学法人神戸大学 | Reactive surfactant composition |
WO2014157715A1 (en) * | 2013-03-27 | 2014-10-02 | Jsr株式会社 | Binder composition for electricity storage devices |
-
2016
- 2016-02-18 CN CN201610090937.1A patent/CN105576284A/en active Pending
-
2017
- 2017-02-16 JP JP2017027161A patent/JP6624739B2/en active Active
- 2017-02-17 KR KR1020170021518A patent/KR20170097577A/en active Search and Examination
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294230A (en) * | 1999-04-09 | 2000-10-20 | Hitachi Powdered Metals Co Ltd | Slurry for forming negative electrode coating film for lithium ion secondary battery and lithium ion secondary battery |
US20020034686A1 (en) * | 2000-07-26 | 2002-03-21 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
CN1328102A (en) * | 2001-06-08 | 2001-12-26 | 成都茵地乐电源科技有限公司 | Water adhesive for electrode material of secondary lithium ion battery and its preparing process |
CN104448158A (en) * | 2014-12-05 | 2015-03-25 | 北京蓝海黑石科技有限公司 | Preparation method of water-based adhesive for lithium batteries |
CN104882612A (en) * | 2015-04-07 | 2015-09-02 | 宁德新能源科技有限公司 | Adhesive and lithium ion battery using the same |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109565051A (en) * | 2016-07-29 | 2019-04-02 | 花王株式会社 | Electric energy storage device electrode resin combination |
US11183693B2 (en) | 2016-07-29 | 2021-11-23 | Kao Corporation | Resin composition for power storage device electrode |
EP3581596A4 (en) * | 2017-02-08 | 2019-12-18 | Blue Ocean & Black Stone Technology Co., Ltd. (Beijing) | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR102455079B1 (en) * | 2017-02-08 | 2022-10-17 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR102508553B1 (en) * | 2017-02-08 | 2023-03-10 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous Binder for Lithium Ion Battery and Manufacturing Method Thereof |
KR20220143771A (en) * | 2017-02-08 | 2022-10-25 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
CN106833448B (en) * | 2017-02-08 | 2019-02-15 | 北京蓝海黑石科技有限公司 | A kind of lithium ion cell positive aqueous binder and preparation method thereof |
KR20230083342A (en) * | 2017-02-08 | 2023-06-09 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
CN106833448A (en) * | 2017-02-08 | 2017-06-13 | 北京蓝海黑石科技有限公司 | A kind of lithium ion cell positive aqueous binder and preparation method thereof |
KR20190117547A (en) * | 2017-02-08 | 2019-10-16 | 블루 오션 & 블랙 스톤 테크놀로지 컴퍼니 리미티드 (베이징) | Lithium Ion Battery Anode Aqueous Binder and Manufacturing Method Thereof |
KR20210147110A (en) * | 2017-02-08 | 2021-12-06 | 블루 오션 & 블랙 스톤 테크놀로지 컴퍼니 리미티드 (베이징) | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR102673575B1 (en) | 2017-02-08 | 2024-06-13 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR102545755B1 (en) * | 2017-02-08 | 2023-06-22 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR20230163001A (en) * | 2017-02-08 | 2023-11-29 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
KR102618064B1 (en) | 2017-02-08 | 2023-12-27 | 푸지엔 블루 오션 앤 블랙 스톤 테크놀로지 컴퍼니 리미티드 | Aqueous binder of lithium ion battery anode and preparation method therefor |
CN106905475B (en) * | 2017-03-10 | 2020-09-25 | 湖南高瑞电源材料有限公司 | Preparation method of fluorine-containing adhesive for lithium battery ceramic diaphragm and ceramic diaphragm prepared by using adhesive |
CN106905475A (en) * | 2017-03-10 | 2017-06-30 | 湖南高瑞电源材料有限公司 | The ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and using the adhesive |
CN107641170A (en) * | 2017-09-27 | 2018-01-30 | 贵州理工学院 | Polymer emulsion, preparation method and the aqueous binder of preparation, method and application |
CN111656575A (en) * | 2018-01-26 | 2020-09-11 | 花王株式会社 | Positive electrode for lithium ion secondary battery |
CN108767259A (en) * | 2018-05-24 | 2018-11-06 | 九江华先新材料有限公司 | A kind of aqueous binders and preparation method thereof for lithium ion battery |
CN108832125A (en) * | 2018-05-28 | 2018-11-16 | 九江华先新材料有限公司 | A kind of cathode of lithium battery aqueous binders and preparation method, electrode piece preparation method |
CN108847488A (en) * | 2018-06-14 | 2018-11-20 | 汕头市鲁汕化工原料有限公司 | Lithium ion secondary battery active material adhesive |
CN108847488B (en) * | 2018-06-14 | 2021-02-26 | 汕头市鲁汕化工原料有限公司 | Active material binder for lithium ion secondary battery |
CN110218285A (en) * | 2019-05-09 | 2019-09-10 | 福建蓝海黑石新材料科技有限公司 | A kind of aqueous binder and preparation method thereof |
CN110218285B (en) * | 2019-05-09 | 2021-09-07 | 福建蓝海黑石新材料科技有限公司 | Water-based adhesive and preparation method thereof |
CN110627945B (en) * | 2019-10-31 | 2021-11-30 | 湖南高瑞电源材料有限公司 | Acrylate adhesive modified by long-chain unsaturated carboxylic acid or derivative thereof, and preparation method and application thereof |
CN110627945A (en) * | 2019-10-31 | 2019-12-31 | 湖南高瑞电源材料有限公司 | Acrylate adhesive modified by long-chain unsaturated carboxylic acid or derivative thereof, and preparation method and application thereof |
CN112662348A (en) * | 2020-01-21 | 2021-04-16 | 四川茵地乐科技有限公司 | Adhesive for battery, lithium ion battery negative electrode sheet and lithium ion battery |
CN116134060A (en) * | 2020-07-30 | 2023-05-16 | 大金工业株式会社 | Method for producing aqueous dispersion of fluoroelastomer, and aqueous dispersion |
CN112321761A (en) * | 2020-11-04 | 2021-02-05 | 深圳港池科技有限公司 | Preparation method of adhesive for lithium ion battery |
CN112877012A (en) * | 2020-11-25 | 2021-06-01 | 湖南高瑞电源材料有限公司 | Preparation method and application of water-soluble low-modulus acrylic resin adhesive |
CN115926040A (en) * | 2022-11-30 | 2023-04-07 | 福建蓝海黑石新材料科技有限公司 | Preparation method of lithium ion battery cathode slurry |
Also Published As
Publication number | Publication date |
---|---|
KR20170097577A (en) | 2017-08-28 |
JP2017174804A (en) | 2017-09-28 |
JP6624739B2 (en) | 2019-12-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105576284A (en) | Anode aqueous binder of lithium ion battery and preparation method thereof | |
CN106833448B (en) | A kind of lithium ion cell positive aqueous binder and preparation method thereof | |
CN109722190B (en) | Preparation method of lithium battery silicon-based negative electrode binder and binder thereof | |
CN104953128B (en) | Water-based adhesive, preparation method thereof, and electrode plate, isolating membrane and battery using water-based adhesive | |
CN107384261A (en) | A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications | |
CN103370816A (en) | Slurries obtained using binder for cell electrodes, electrodes obtained using slurries, and lithium-ion secondary cell obtained using electrodes | |
CN105261759A (en) | Aqueous adhesive for lithium battery and preparation method of aqueous adhesive, and lithium battery plate | |
CN106281147A (en) | A kind of water base binders for electrodes and preparation method | |
CN103633367A (en) | Gel polymer electrolyte, polymer lithium ion battery and making method of polymer lithium ion battery | |
CN108470884A (en) | A kind of lithium ion cell electrode prepared by water based adhesive | |
CN110034288A (en) | A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method | |
CN111554880B (en) | Negative plate, negative electrode slurry, preparation method of negative electrode slurry and battery | |
CN110364735A (en) | A kind of lithium ion battery silicon-carbon cathode adhesive, preparation and its application | |
CN107325225A (en) | Negative electrode of lithium ion battery aqueous binder and preparation method thereof | |
CN105018001A (en) | Aqueous binder used for lithium ion batteries, positive and negative electrode plates and coating membrane | |
CN105336960B (en) | A kind of preparation method of ion polymer type aqueous binders for lithium ion battery electrode material | |
CN106340649A (en) | Preparation method of lithium ferric phosphate cathode slurry | |
CN106784842A (en) | A kind of preparation method of lithium battery aqueous, environmental protective binding agent | |
CN113788907B (en) | 3D network quasi-solid electrolyte, quasi-solid lithium ion battery and preparation method thereof | |
CN103915623B (en) | The preparation method of nano porous metal sulfide rechargeable magnesium cell anode material | |
CN107641170A (en) | Polymer emulsion, preparation method and the aqueous binder of preparation, method and application | |
CN109935830B (en) | Preparation method of lithium ion battery silicon-carbon negative electrode plate based on modified gelatin binder | |
CN115911386A (en) | Self-crosslinking lithium ion battery anode water-based adhesive and preparation method thereof | |
CN102443236A (en) | Polymer electrolyte membrane, preparation method thereof and polymer lithium-ion battery | |
CN115386033A (en) | Binder for lithium ion battery and lithium ion battery using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160511 |