CN114300687A - Water-based composite binder, preparation and application - Google Patents
Water-based composite binder, preparation and application Download PDFInfo
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Abstract
A water system composite binder, preparation and application thereof, wherein the preparation raw materials of the composite binder comprise: modified polybutadiene emulsion, polyvinyl alcohol; the modified polybutadiene emulsion is prepared by the steps of firstly carrying out graft copolymerization reaction on polybutadiene latex, alkyl vinyl acid ester compounds and acrylamide compounds, then crosslinking a grafted product and an unsaturated polyfunctional compound to generate a three-dimensional reticular polymer, and finally hydrolyzing the crosslinked product under the action of an alkali catalyst. The three-dimensional network polymer modified polybutadiene with both hydroxyl and amide groups, which is obtained by the invention, has stronger molecular flexibility and rebound resilience, and the binder prepared by the three-dimensional network polymer modified polybutadiene can improve the long-cycle stability of the battery.
Description
Technical Field
The invention belongs to the technical field of battery binders, and particularly relates to a water system composite binder, and preparation and application thereof.
Background
Conventional lithium ion secondary batteries using graphite as a negative electrode material have gradually approached their theoretical limit in energy density. The theoretical specific capacity of silicon (4200 mAh/g) is ten times that of graphite (372 mAh/g), and the silicon-based lithium ion battery has a lower charge-discharge voltage platform and very abundant crustal reserves, and the energy density of the lithium ion battery can be remarkably improved by replacing a graphite negative electrode with the silicon-based lithium ion battery, so that the silicon-based negative electrode is considered to be one of the most important negative electrode materials of the next generation of high-energy-density lithium ion battery. But the scale application of silicon-based anode materials also faces many challenges: the silicon-based negative electrode has great volume change in the lithium desorption process, and particularly, the repeated expansion and contraction easily cause the silicon-based particles to crack and be pulverized, and the Solid Electrolyte Interface (SEI) film to continuously crack and be recombined, and finally, the silicon-based negative electrode has poor cycle performance and the battery using the silicon-based negative electrode has short cycle life.
The binder is a part of the battery electrode, although the proportion of the binder in the electrode is less (less than 5%), the binder has the characteristics of strong binding power, good flexibility, and stable thermal performance and chemical performance, and can maintain the integrity of a silicon-based negative electrode conductive network and mechanics in the charge and discharge processes of the battery. For example, patent CN201710923090.5 discloses a method for preparing a lithium ion battery crosslinked aqueous binder, which comprises using an aqueous polymer containing organic carboxylic acid or amino group or hydroxyl group and a water-soluble small molecule crosslinker containing hydroxyl group, amino group or carboxyl group as the raw materials of the aqueous binder, and performing esterification and amidation reactions for crosslinking under the conditions of coating and drying electrode plate slurry of the lithium ion battery. Patent CN202010379538.3 discloses a method for improving electrolyte resistance of a binder in a negative electrode plate of a lithium battery by irradiation, which comprises the steps of preparing a lithium battery containing a negative electrode taking sodium carboxymethylcellulose (CMC-Na) and styrene-butadiene rubber emulsion (SBR) as binders, placing the whole battery on a beam-off device of an electron beam irradiation accelerator to irradiate the whole lithium battery, so that the irradiation dose is 10-100 kGy, the irradiation dose rate is 2-10 kGy/s, and in the negative electrode, the CMC-Na and the SBR can generate intramolecular and intermolecular chemical crosslinking.
The disclosed technology belongs to the current heat-generating point-water system cross-linking type binder, which has good flexibility and cohesiveness, enhances the volume expansibility and mechanical support of the silicon negative electrode material, and greatly improves the cycle life, but further analysis shows that the technology still has certain defects due to insufficient elasticity or non-lasting cohesive force: the silicon-based lithium ion battery can only support and circulate for 100-500 times, and the long-cycle stability is still not ideal, so how to realize the long-cycle stability of the silicon-based negative electrode is a key problem which needs to be solved urgently in order to promote further development and realize commercialization.
Disclosure of Invention
The invention aims to provide a water-based composite binder, preparation and application, the invention takes polybutadiene latex with small particle size as a grafting backbone, alkyl vinyl acid ester compounds and acrylamide compounds as grafting monomers, unsaturated polyfunctional compounds as a cross-linking agent to prepare a three-dimensional network polymer, and the three-dimensional network polymer is hydrolyzed under the action of alkali catalysis to obtain the three-dimensional network polymer which has hydroxyl and amide groups and has a certain distribution rule of the groups, has stronger molecular flexibility and rebound resilience, can form hydrogen bond action with a silicon negative electrode material, reduces the volume expansion and contraction change of the negative electrode material in the charge-discharge process, and improves the cycle stability and other electrochemical properties of a battery.
In order to realize the purpose, the invention adopts the following specific technical scheme:
a water-based composite binder is prepared from the following raw materials: modified polybutadiene emulsion, polyvinyl alcohol; the modified polybutadiene emulsion is prepared by the steps of firstly carrying out graft copolymerization reaction on polybutadiene latex, alkyl vinyl acid ester compounds and acrylamide compounds, then crosslinking a grafted product and a crosslinking agent to generate a three-dimensional network polymer, and finally hydrolyzing the crosslinked product under the action of an alkali catalyst; the cross-linking agent is an unsaturated polyfunctional compound.
Further, the preparation raw materials of the composite binder comprise: 100 parts of modified polybutadiene emulsion and 3-5.5 parts of polyvinyl alcohol; wherein the dosage of the vinyl alkyl acid ester compound is 5-10wt% of the polybutadiene latex, the dosage of the acrylamide compound is 10-20wt% of the polybutadiene latex, and the dosage of the cross-linking agent is 4-6wt% of the polybutadiene latex.
The unsaturated multifunctional compound comprises at least one of unsaturated triazine compounds and divinyl ether compounds. Preferably, the unsaturated polyfunctional compound is a compound of unsaturated triazine compounds and divinyl ether compounds according to the mass ratio of 1: 2-5. Further, the unsaturated triazine compound is selected from at least one of 2, 4-diallyl-6-amino-1, 3, 5-triazine and 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine; the divinyl ether compound is at least one selected from diethylene glycol divinyl ether, tri (ethylene glycol) divinyl ether and 1, 4-butanediol divinyl ether.
The unsaturated triazine compounds are geometrical structures with plane rigidity, and the unsaturated triazine compounds serving as cross-linking agents are beneficial to improving the elasticity of the binding agents and enhancing the alleviation of the volume change of the silicon-based negative electrode; on the other hand, unsaturated triazine compounds have a large conjugated system in molecules, and the rings have strong positive potential, so that the transmission of lithium ions in the negative electrode can be greatly improved.
The solid content of the polybutadiene latex is 40-50wt%, and the average particle size is 100-300 nm; the solid content of the modified polybutadiene emulsion is 40-60 wt%.
The carbon atom number of the alkyl acid in the alkyl acid vinyl ester compound is 2-6, and the alkyl acid vinyl ester compound is selected from at least one of vinyl acetate, vinyl propionate, vinyl n-butyrate and vinyl valerate; the acrylamide compound is at least one selected from acrylamide, methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-tri (hydroxymethyl) methacrylamide and N- (hydroxymethyl) acrylamide.
The initiator comprises at least one of potassium persulfate and ammonium persulfate, and the dosage of the initiator is 0.5-0.8% of the total mass of polybutadiene latex dry basis, alkyl vinyl acetate compounds and acrylamide compounds. The surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium dodecyl sulfate.
The number average molecular weight of the polyvinyl alcohol is 10-13 ten thousand.
The invention also provides a preparation method of the water-based composite adhesive, which comprises the following steps:
s1, adding polybutadiene latex into a reaction kettle in an inert atmosphere, adding water and a surfactant, stirring to form stable dispersion, heating, adding an initiator, uniformly mixing, adding a mixture of an alkyl vinyl acid ester compound and an acrylamide compound, reacting at a constant temperature, adding a cross-linking agent, continuing reacting at a constant temperature, naturally cooling to room temperature after the reaction is finished, dialyzing, and concentrating to obtain concentrated solution;
s2, adding an alcohol solution dissolved with an alkali catalyst into the concentrated product obtained in the step S1, heating, raising the temperature, performing hydrolysis reaction at a constant temperature, naturally cooling to room temperature after the reaction is finished, dropwise adding a dilute acid solution to be neutral, dialyzing, concentrating, adding polyvinyl alcohol, and stirring uniformly to obtain the water-based composite binder.
S1, adding 4-8% of the total amount of the surface active agent, namely polybutadiene latex dry base, the alkyl vinyl ester compound and the acrylamide compound, wherein the added water accounts for 60-80wt% of the stable dispersion liquid, raising the temperature to 60-90 ℃, averagely adding the mixture of the alkyl vinyl ester compound and the acrylamide compound for 2-5 times, wherein the addition interval is 20-60min each time, the constant-temperature reaction time is 2-4h before adding the cross-linking agent, and the constant-temperature reaction time is 3-5h after adding the cross-linking agent; the dialysis is to change water 2-5 times a day, the dialysis time is 3-5 days, and the concentration is to 60-80 wt%;
step S2, the alkali catalyst is selected from at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide, the dosage of the alkali catalyst is 30-50wt% of the alkyl acid vinyl ester compound, the carbon atom number of the alcohol is 1-4, the alkali catalyst is specifically selected from at least one of methanol, ethanol, propanol, butanol and tert-butanol, the catalyst accounts for 9-16wt% of the alcohol solution, the temperature is raised to 60-100 ℃, the hydrolysis time is 6-12h, and the solid content of the water system composite binder is 40-70 wt%.
The invention also provides the application of the water-based composite binder, which is characterized in that a negative active material, a conductive agent and the water-based composite binder are mixed, the solid content of the mixture is controlled by adding water, the mixture is uniformly stirred and coated on a current collector, and an electrode is obtained after drying and rolling.
The proportion of the water system composite binder in the electrode is 1-10 wt%.
The negative active material is silicon or a silicon composite material, including but not limited to at least one of silicon and silicon monoxide.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes polybutadiene latex with small particle size as grafting main latex, alkyl vinyl acid ester compounds and acrylamide compounds as grafting monomers, unsaturated polyfunctional compounds as cross-linking agents to prepare a three-dimensional network polymer, the polymer is hydrolyzed under the action of alkali catalysis to obtain the three-dimensional network polymer modified polybutadiene which has hydroxyl and amido and has certain distribution rule of the groups, the polymer has stronger molecular flexibility and rebound resilience, is rich in strong polarity and can form hydrogen bond action with silicon negative electrode materials, not only the adhesive has stronger peeling strength, but also the volume expansion and contraction change of the negative electrode materials in the charging and discharging process can be reduced, and the long cycle stability of the battery can be improved.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are all parts by weight. All reagents used are commercially available in the art.
The polybutadiene latex was purchased from Daqing petrochemical Co Ltd, had a solid content of 46wt% and an average particle diameter of 244 nm.
Polyvinyl alcohol was purchased from Shanghai division, Mirey chemical, Inc., Suzhou, and had a number average molecular weight of 11.2 ten thousand.
Silica was purchased from Beijing Yijin New energy science and technology, Inc.
Preparation of aqueous composite binder
Example 1
S1, adding 100 parts of polybutadiene latex into a reaction kettle in a nitrogen atmosphere, adding 54 parts of water and 4 parts of sodium dodecyl benzene sulfonate, stirring to form a stable dispersion liquid, heating to 80 ℃, adding 0.4 part of potassium persulfate, uniformly mixing, adding a mixture of 10 parts of vinyl propionate and 10 parts of acrylamide in an average manner for 2 times at an interval of 40min, keeping a constant temperature reaction for 3 hours, finally adding 2 parts of 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine and a cross-linking agent compounded by 4 parts of diethylene glycol divinyl ether, continuing the constant temperature reaction for 4 hours, naturally cooling to room temperature after the reaction is finished, transferring the mixture in the reaction kettle into a dialysis bag, immersing the dialysis bag into water for dialysis until the electrical conductivity of a dialysate is not changed, and taking out and concentrating until the solid content is 60 wt%;
s2, adding 50 parts of 10wt% sodium hydroxide solution into the concentrated product obtained in the step S1, heating to 100 ℃ with ethanol as a solvent, carrying out hydrolysis reaction for 7 hours at a constant temperature, naturally cooling to room temperature after the reaction is finished, dropwise adding a dilute acid solution to neutrality, transferring the product into a dialysis bag, immersing the dialysis bag into water for dialysis until the conductivity of the dialysate is not changed, concentrating the product until the solid content is 60wt%, taking out 100 parts, adding 5.5 parts of polyvinyl alcohol, and stirring uniformly to obtain the water-based composite binder.
Example 2
The procedure of example 1 was repeated, except that 2, 4-diamino-6-diallylamino-1, 3, 5-triazine was used in an amount of 1 part and diethylene glycol divinyl ether was used in an amount of 5 parts.
Example 3
The procedure of example 1 was repeated, except that 3 parts of 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 3 parts of diethylene glycol divinyl ether were used.
Example 4
The procedure of example 1 was repeated, except that 2, 4-diamino-6-diallylamino-1, 3, 5-triazine was used in an amount of 0.5 part and diethylene glycol divinyl ether was used in an amount of 5.5 parts.
Example 5
The rest of the components are the same as the components in the example 1, except that the compound crosslinking agent is 4 parts and consists of diamino-6-diallyl-amino-1, 3, 5-triazine and diethylene glycol divinyl ether according to the weight ratio of 1: 2.
Example 6
The procedure was as in example 1 except that vinyl propionate was used in an amount of 5 parts and acrylamide was used in an amount of 20 parts.
Example 7
The procedure is as in example 1 except that 5 parts of 2, 4-diamino-6-diallylamino-1, 3, 5-triazine are used as the crosslinking agent and diethylene glycol divinyl ether is not used.
Example 8
The same as in example 1 was repeated, except that 6 parts of diethylene glycol divinyl ether was used as the crosslinking agent and that 2, 4-diamino-6-diallylamino-1, 3, 5-triazine was not used.
Comparative example 1
The rest was the same as example 1 except that no crosslinking agent was used.
Comparative example 2
The procedure of example 1 was repeated, except that 20 parts of ethyl acrylate was used and acrylamide was not used.
Comparative example 3
The procedure of example 1 was repeated, except that 20 parts of acrylamide was used and ethyl acrylate was not used.
Preparation of a Battery
Application examples 1 to 8, comparative application examples 1 to 3
The aqueous composite binders prepared in examples 1 to 8 and comparative examples 1 to 3, the negative electrode active material, and the conductive agent were mixed, respectively, and the solid content of the mixture was controlled to 45% by adding water, and the negative electrode active material was a mixture of silica and graphite in a ratio of 90:10, in which the negative electrode active material: Super-P: water system composite adhesiveUniformly stirring and coating the dry basis of the binding agent at a ratio of 95:1:4 on a copper foil current collector, drying the pole piece at 120 ℃ for 12 hours in vacuum, rolling, and cutting the pole piece into a circular pole piece with the diameter of 10 mm, wherein the loading capacity of the active substance is 3.0mg/cm2(ii) a Adopting a metal lithium sheet as a counter electrode and adopting 1 mol/L LiPF6(the solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1, 5% by volume of fluoroethylene carbonate (FEC) is added) as an electrolyte, and a polypropylene microporous diaphragm (Celgard) is assembled into a 2032 type button cell in a glove box in an argon atmosphere. In each of application examples 1 to 8 and comparative application examples 1 to 3, the water-based composite binders prepared in examples 1 to 8 and comparative examples 1 to 3 were used.
And (3) performance testing:
the following performance tests were performed on the water-based composite binders prepared in the above examples and comparative examples, and the results are shown in table 1:
adhesive property: the aqueous composite binder, the negative electrode active material and the conductive agent prepared in the above examples and comparative examples were mixed by using a GBH-1 electron tensile tester, and the solid content of the mixture was controlled to 45% by adding water, and the negative electrode active material was a mixture of silica and graphite in a ratio of 90:10, in which the negative electrode active material: Super-P: the dry basis of the water system composite binder is 95:1:4, the mixture is uniformly stirred and coated on a copper foil current collector, then the pole piece is dried for 12 hours under the vacuum condition of 120 ℃, rolled and cut into a test sample with the size of 20 x 100mm (the active substance loading is 3.0 mg/cm)2) One side of the sample coated with electrode materials such as adhesive is fixed on a stainless steel plate of a testing machine by double faced adhesive tape, one end of the sample which is stripped is bent reversely by 180 degrees and fixed on a tension probe, and 180 degrees of stripping is carried out at a constant speed of 50mm/min, so as to test the stripping strength of the sample.
The following performance tests were performed on the batteries prepared in the above application examples and comparative application examples, and the results are shown in table 2:
and (3) cyclic stability: and a blue test system is adopted to carry out charge and discharge tests on the battery at 0.5C, wherein the cycle times are 100 and 1000.
TABLE 1 Performance test results for aqueous composite Binders
TABLE 2 Battery Performance test results
The results in tables 1 and 2 show that the binder prepared by the invention has stronger peel strength, can reduce the volume expansion and contraction change of the negative electrode material in the charging and discharging processes, and greatly improves the long-cycle stability of the battery.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. The water-based composite binder is characterized in that the preparation raw materials of the composite binder comprise: modified polybutadiene emulsion, polyvinyl alcohol; the modified polybutadiene emulsion is prepared by the steps of firstly carrying out graft copolymerization reaction on polybutadiene latex, alkyl vinyl acid ester compounds and acrylamide compounds, then crosslinking a grafted product and a crosslinking agent to generate a three-dimensional network polymer, and finally hydrolyzing the crosslinked product under the action of an alkali catalyst; the cross-linking agent is an unsaturated polyfunctional compound.
2. The water-based composite binder according to claim 1, wherein the composite binder is prepared from the following raw materials: 100 parts of modified polybutadiene emulsion and 3-5.5 parts of polyvinyl alcohol; wherein the dosage of the vinyl alkyl acid ester compound is 5-10wt% of the polybutadiene latex, the dosage of the acrylamide compound is 10-20wt% of the polybutadiene latex, and the dosage of the cross-linking agent is 4-6wt% of the polybutadiene latex.
3. The aqueous composite binder according to claim 1, wherein the unsaturated polyfunctional compound is a mixture of an unsaturated triazine compound and a divinyl ether compound in a mass ratio of 1: 2-5.
4. The aqueous composite binder according to claim 3, wherein the unsaturated triazine compound is at least one selected from the group consisting of 2, 4-diallyloxy-6-amino-1, 3, 5-triazine, and 2, 4-diamino-6-diallylamino-1, 3, 5-triazine; the divinyl ether compound is at least one selected from diethylene glycol divinyl ether, tri (ethylene glycol) divinyl ether and 1, 4-butanediol divinyl ether.
5. The aqueous composite binder as claimed in claim 1, wherein the polybutadiene latex has a solid content of 40 to 50wt%, an average particle diameter of 100 to 300 nm; the solid content of the modified polybutadiene emulsion is 40-60 wt%.
6. The aqueous composite binder according to claim 1, wherein the alkyl acid vinyl ester compound is at least one selected from the group consisting of vinyl acetate, vinyl propionate, vinyl n-butyrate, and vinyl valerate; the acrylamide compound is at least one selected from acrylamide, methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-tri (hydroxymethyl) methacrylamide and N- (hydroxymethyl) acrylamide.
7. The aqueous composite binder according to claim 1, wherein the polyvinyl alcohol has a number average molecular weight of 10 to 13 ten thousand.
8. The method for preparing the water-based composite binder according to any one of claims 1 to 7, comprising the steps of:
s1, adding polybutadiene latex into a reaction kettle in an inert atmosphere, adding water and a surfactant, stirring to form stable dispersion, heating, adding an initiator, uniformly mixing, adding a mixture of an alkyl vinyl acid ester compound and an acrylamide compound, reacting at a constant temperature, adding a cross-linking agent, continuing reacting at a constant temperature, naturally cooling to room temperature after the reaction is finished, dialyzing, and concentrating to obtain concentrated solution;
s2, adding an alcohol solution dissolved with an alkali catalyst into the concentrated product obtained in the step S1, heating, raising the temperature, performing hydrolysis reaction at a constant temperature, naturally cooling to room temperature after the reaction is finished, dropwise adding a dilute acid solution to be neutral, dialyzing, concentrating, adding polyvinyl alcohol, and stirring uniformly to obtain the water-based composite binder.
9. The use of the aqueous composite binder according to any one of claims 1 to 7 in an electrode, wherein a negative electrode active material, a conductive agent and the aqueous composite binder are mixed, the solid content of the mixture is controlled by adding water, the mixture is uniformly stirred and coated on a current collector, and the electrode is obtained after drying and rolling.
10. The use of the aqueous composite binder according to claim 9 for an electrode, wherein the proportion of the aqueous composite binder in the electrode is 1 to 10wt%, and the negative electrode active material is silicon or a composite material of silicon.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001015116A (en) * | 1999-07-01 | 2001-01-19 | Nippon Zeon Co Ltd | Binder for lithium ion secondary battery electrode and its utilization |
| CN101457131A (en) * | 2009-01-12 | 2009-06-17 | 成都茵地乐电源科技有限公司 | Water binding agent for lithium ionic cell electric pole material and preparation method thereof |
| CN104356979A (en) * | 2014-10-28 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | Polyacrylate water-based adhesive for electrode materials of lithium ion battery, preparation method of adhesive and electrode plates of lithium ion battery |
| CN105914377A (en) * | 2016-06-28 | 2016-08-31 | 中国科学院广州能源研究所 | Multielement functional modified polymer binder for lithium ion battery and application of binder in electrochemical energy storage device |
| CN107793967A (en) * | 2017-09-30 | 2018-03-13 | 中国科学院广州能源研究所 | A kind of preparation method of the crosslinking type aqueous binding agent of lithium ion battery |
| CN108987751A (en) * | 2017-05-31 | 2018-12-11 | 宁德时代新能源科技股份有限公司 | Binder and secondary battery thereof |
| CN111116832A (en) * | 2020-01-08 | 2020-05-08 | 万华化学集团股份有限公司 | Polybutadiene graft copolymer and preparation method and application thereof |
-
2022
- 2022-03-07 CN CN202210217411.0A patent/CN114300687B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001015116A (en) * | 1999-07-01 | 2001-01-19 | Nippon Zeon Co Ltd | Binder for lithium ion secondary battery electrode and its utilization |
| CN101457131A (en) * | 2009-01-12 | 2009-06-17 | 成都茵地乐电源科技有限公司 | Water binding agent for lithium ionic cell electric pole material and preparation method thereof |
| CN104356979A (en) * | 2014-10-28 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | Polyacrylate water-based adhesive for electrode materials of lithium ion battery, preparation method of adhesive and electrode plates of lithium ion battery |
| CN105914377A (en) * | 2016-06-28 | 2016-08-31 | 中国科学院广州能源研究所 | Multielement functional modified polymer binder for lithium ion battery and application of binder in electrochemical energy storage device |
| CN108987751A (en) * | 2017-05-31 | 2018-12-11 | 宁德时代新能源科技股份有限公司 | Binder and secondary battery thereof |
| CN107793967A (en) * | 2017-09-30 | 2018-03-13 | 中国科学院广州能源研究所 | A kind of preparation method of the crosslinking type aqueous binding agent of lithium ion battery |
| CN111116832A (en) * | 2020-01-08 | 2020-05-08 | 万华化学集团股份有限公司 | Polybutadiene graft copolymer and preparation method and application thereof |
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