CN117447944A - Aqueous adhesive for lithium ion battery - Google Patents
Aqueous adhesive for lithium ion battery Download PDFInfo
- Publication number
- CN117447944A CN117447944A CN202311193437.7A CN202311193437A CN117447944A CN 117447944 A CN117447944 A CN 117447944A CN 202311193437 A CN202311193437 A CN 202311193437A CN 117447944 A CN117447944 A CN 117447944A
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- China
- Prior art keywords
- monomer
- lithium ion
- polymer
- aqueous solution
- aqueous
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 239000000853 adhesive Substances 0.000 title claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 70
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims description 155
- 239000011230 binding agent Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000002209 hydrophobic effect Effects 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 3
- 101150065749 Churc1 gene Proteins 0.000 claims description 3
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 102100038239 Protein Churchill Human genes 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 26
- 239000002002 slurry Substances 0.000 abstract description 18
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 description 74
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- -1 N, N-dimethylamino Chemical group 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229940047670 sodium acrylate Drugs 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the technical field of aqueous adhesives, and particularly provides a lithium ion battery aqueous adhesive. The lithium ion battery aqueous adhesive is formed by mixing a first aqueous solution containing a first polymer, a second aqueous solution containing a second polymer and a third aqueous solution containing a third polymer, comprehensively exerts the different performance characteristics of the three polymers, realizes high dispersibility of active particles of a negative electrode material, and has the advantages of good stability of the obtained slurry, high adhesion to a pole piece, high cohesive force, flexible pole piece and low impedance of a final pole piece, thereby bringing low internal resistance to an electric core.
Description
Technical Field
The application relates to the technical field of aqueous adhesives, in particular to an aqueous adhesive for a lithium ion battery.
Background
The aqueous adhesive is one of key raw material components of the lithium ion battery, and realizes the functions of dispersing anode and/or cathode materials, adhering pole pieces and the like. Therefore, the performance of the aqueous adhesive, such as dispersibility and cohesive strength of the anode and cathode materials, adhesion to the pole pieces, flexibility and the like, has important influence on the electrical performance of the lithium ion battery.
The materials of the current aqueous adhesive comprise polyacrylic acid PAA, styrene-butadiene latex SBR, sodium carboxymethylcellulose CMC and the like, the PAA aqueous adhesive has good performance on pole piece adhesion, pole piece cohesion and the like, but the problems of insufficient dispersibility, insufficient flexibility and the like are also caused, and finally, the electrical performance of the lithium ion battery is poor, especially the initial effect is not high.
Disclosure of Invention
Modifying the PAA aqueous adhesive is the most main means for improving the performance of the PAA aqueous adhesive, but the PAA aqueous adhesive with better comprehensive performance is difficult to obtain by single modification, and especially for the lithium ion battery at present, low impedance becomes an increasingly important performance parameter, for example, the impedance influences the first effect of lithium ions, and the lower the impedance, the higher the first effect. In order to solve the technical problems in the prior art, the application provides a lithium ion battery water-based adhesive, wherein the effective components in the water-based adhesive are composed of three polyacrylate polymers with different functions.
The application adopts the following technical scheme:
the lithium ion battery aqueous adhesive is formed by mixing a first aqueous solution containing a first polymer, a second aqueous solution containing a second polymer and a third aqueous solution containing a third polymer;
the weight percentage content ratio of the first polymer, the second polymer and the third polymer in the lithium ion battery water-based adhesive is 1:1.5-3:1-6;
the first aqueous solution is prepared as follows: a first monomer combination consisting of a first hydrophilic monomer and a first hydrophobic monomer is polymerized for the first time in water, and then a second monomer combination consisting of a second hydrophilic monomer and a second hydrophobic monomer is added for the second polymerization, so that the polymer is obtained;
the general formula of the second polymer is shown in the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of R 5 Selected from C2-C18 alkyl, C2-C18 substituted alkyl, amino or substituted amino, R 6 Has the general formula of-R 7 CN，R 7 Is at least one of the non-existence or selected from C1-C4 alkylene, a is more than 0, b is more than or equal to 0, C is more than 0, a: b: c=2-5:0-4:2-5;
the third aqueous solution is prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a third monomer, a fourth monomer and a fifth monomer for polymerization reaction to obtain the modified polyurethane foam;
the general formula of the third monomer is CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl, M is selected from H, na + 、Li + And K + At least one of (a) and (b);
the fourth monomer at least contains a second soft monomer;
the fifth monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene.
Preferably, the weight ratio of the first hydrophilic monomer in the first monomer combination is 60-100%, and the weight ratio of the second hydrophilic monomer in the second monomer combination is 0-60%.
Preferably, the first hydrophilic monomer and the second hydrophilic monomer are independently selected from the group consisting of a compound having the general formula CH 2 ＝CR 11 R 12 Wherein R is 11 Selected from H or C1-C4 alkyl, R 12 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) d H and-COO (CH) 2 ) e PO 3 H, and/or one or more of them containing-COOM, - (C) 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, d=1-18, e=1-12, M is selected from H, li + 、Na + And K + One or more of them.
Preferably, the first hydrophobic monomer and the second hydrophobic monomer are independently selected from the group consisting of a monomer of the general formula CH 2 ＝CR 13 R 14 Wherein R is 13 Selected from H or C1-C4 alkyl, R 14 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-18, m=0-6.
Preferably, the weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1.
Preferably, the conversion of the first monomer combination after the first polymerization is not less than 70%.
Preferably, the second soft monomer has the general formula CH 2 ＝CHCOOR 15 Wherein R is 15 Selected from C2-C18 alkyl or C2-C18 substituted alkyl.
Preferably, the mixed monomer is composed of 5 to 50% by weight of the third monomer, 5 to 50% by weight of the fourth monomer, and 20 to 90% by weight of the fifth monomer.
Preferably, the weight ratio of the surfactant or the protective colloid in the mixed monomer is 0-50%.
Preferably, the weight concentration of the aqueous binder of the lithium ion battery is 5-60%.
The principle of the aqueous adhesive of the present application is as follows: the first polymer has the advantages that due to the uneven distribution of hydrophilic and hydrophobic parts on the polymer chain, the hydrophobic chain segment parts are more prone to be adsorbed on the surfaces of active particles, so that the active particles are wrapped and dispersed, but the particles are dispersed and are not stably suspended in the slurry, and sufficient steric hindrance is needed to ensure that the particles are not re-agglomerated; polar groups such as carboxyl groups on the second polymer chain segments can more effectively interact with hydrophilic chain segments of the first polymer adsorbed on the surfaces of the active particles and stretched in the water phase, so that sufficient steric hindrance among the active particles is ensured, and the active particles in the slurry have high dispersion and dispersion stability; the third polymer is a branched polymer in which the molecular chains are not fully extended in the aqueous phase, but rather are dispersed in the slurry in an "agglomerated" or "swollen" state. Thus, on the one hand, while the third polymer is a "soft" polymer, containing more soft monomers, theoretically more prone to adsorb on the surface of the active particles, because of its special presence morphology (agglomeration or swelling), and because the particle surface has adsorbed the first polymer, more prone to exist between the active particles rather than on the surface of the active particles, thus effectively avoiding the effect on lithium ion conduction at the interface of the active particles and the electrolyte due to the coating of the active particles by the excessive polymer, reducing the internal resistance of the final cell; on the other hand, carboxyl and the like in the third polymer can also interact with carboxyl and the like in the second polymer through hydrogen bonds, so that the cohesive force of the pole piece is improved, the pole piece structure is ensured to be stable, meanwhile, the integral film forming process of the pole piece is participated, and soft agglomeration points are introduced into the pole piece, so that the effects of reducing the hardness of the pole piece and improving the flexibility are achieved. In addition, because of the improvement of the stability of the slurry, the proportion of the first polymer adsorbed on the surface of the active particles in the slurry can be lower, so that the influence on lithium ion conduction at the interface of the active particles and the electrolyte is reduced, and the finally manufactured battery cell has lower internal resistance. Thus, the technical effect of the aqueous adhesive of the present application is not a simple superposition of three aqueous solutions, but rather a synergy of the efficacy of the three polymers therein is achieved.
In summary, the present application has the following beneficial effects:
1. in the application, three acrylate polymers are adopted, the first polymer can provide good dispersing capability of active particles of the positive electrode material and/or the negative electrode material and final slurry stability, the second polymer can provide good adhesive capability between the active particles of the positive electrode material and/or the negative electrode material and copper foil and cohesive force between the active particles, the third polymer can improve the flexibility of the pole piece, meanwhile, the adhesive force and cohesive force of the active particles to the pole piece are not lost, meanwhile, the compatibility to electrolyte is improved, interface impedance is further reduced, and therefore, a low-impedance battery cell can be finally obtained. Therefore, the aqueous adhesive integrates the characteristics of three acrylate polymers, has high dispersing capability on active particles, especially active particles of a negative electrode material, and the obtained slurry has good stability, high adhesive force to a pole piece, high cohesive force, flexible pole piece and low final pole piece impedance, thereby bringing low internal resistance to an electric core.
2. According to the preparation method, three polymers with different characteristics are obtained through structural design and preparation process optimization, and can be used for performing synergistic effect, so that the lithium ion battery water-based adhesive with excellent comprehensive performance is obtained, and meanwhile, the swelling degree of electrolyte to a polar plate adhesive film and the dispersibility of electrolyte to active particles of a negative electrode material are improved, so that the impedance of a lithium ion battery can be effectively reduced, and the first effect is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
The application provides a lithium ion battery aqueous adhesive, which is formed by mixing a first aqueous solution containing a first polymer, a second aqueous solution containing a second polymer and a third aqueous solution containing a third polymer;
the weight percentage ratio of the first polymer, the second polymer and the third polymer in the aqueous binder of the lithium ion battery is 1:1.5-3:1-6.
The weight concentration of the aqueous binder of the lithium ion battery is 3-60%. For example, the weight concentration may be 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc. Further, the weight concentration of the aqueous binder for lithium ion batteries is 5-50%.
First aqueous solution
The first aqueous solution was prepared as follows: and (3) carrying out first polymerization on a first monomer combination consisting of a first hydrophilic monomer and a first hydrophobic monomer in water, and then adding a second monomer combination consisting of a second hydrophilic monomer and a second hydrophobic monomer for second polymerization to obtain the polymer.
The first aqueous solution is polymerized by combining hydrophilic monomers and hydrophobic monomers in sequence to obtain the first polymer which has better dispersibility on active particles of the anode material and/or the cathode material.
Wherein the weight ratio of the first hydrophilic monomer in the first monomer combination is 60-100%, and the weight ratio of the second hydrophilic monomer in the second monomer combination is 0-60%. After the first polymerization, the hydrophilicity of the first polymer chain segment is higher, the second polymerization is continued, the hydrophobicity of the second polymer chain segment is higher, the hydrophilic and hydrophobic characteristics of the first polymer chain segment and the second polymer chain segment and the hydrophilic and hydrophobic characteristics between the first polymer chain segment and the second polymer chain segment are provided, and the good dispersion performance of the first polymer is provided. Further, the first hydrophilic monomer may be present in the first monomer combination in an amount of 65-95% by weight, e.g., 65%, 70%, 75%, 80%, 85%, 90%, 95% by weight, etc.; further, the second hydrophilic monomer may be present in the second monomer combination in an amount of 10 to 50% by weight, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% by weight, and the like.
In the present application, the first hydrophilic monomer and the second hydrophilic monomer are independently selected from the group consisting of a monomer having the general formula CH 2 ＝CR 11 R 12 Wherein R is 11 Selected from H or C1-C4 alkyl, R 12 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) d H and-COO (CH) 2 ) e PO 3 H, and/or one or more of them containing-COOM, - (C) 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, d=1-18, e=1-12, M is selected from H, li + 、Na + And K + One or more of them. For example, the first hydrophilic monomer and the second hydrophilic monomer may be acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, acrylamide, N-methacrylamide, N-dimethylacrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyether acrylate, and the like, respectively.
In the present application, the first hydrophobic monomer and the second hydrophobic monomer are independently selected from the group consisting of monomers of the general formula CH 2 ＝CR 13 R 14 Wherein R is 13 Selected from H or C1-C4 alkyl, R 14 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-18, m=0-6. For example, the first hydrophobic monomer and the second hydrophobic monomer may be acrylonitrile, methacrylonitrile, butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, n-octyl acrylate, and the like, respectively.
In the present application, the weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1, and further, the weight ratio may be 1:7-7:1, and examples thereof may be 1:7, 2:7, 3:7, 4:7, 5:7, 6:7, 1:1, 7:7, 7:5, 7:4, 7:3, 7:2, 7:1, and the like, without particular limitation.
In the present application, the conversion of the first monomer combination after the first polymerization is not less than 70%. The conversion of the first monomer combination is in the above range, with less effect on the proportions of the various monomers in the second monomer combination. Further, the conversion of the first monomer combination is not less than 75%, or, still further, not less than 80%.
Second aqueous solution
The general formula of the second polymer in the second aqueous solution is shown in the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of (a) and (b); r is R 5 Different from R 4 And R is 6 ，R 5 May be selected from C2-C18 alkyl, C2-C18 substituted alkyl, amino or substituted amino, and for example, substituted amino may be N, N-dimethylamino, N-methylamino, N-diethylamino, N-ethylamino, N-methylolamino, N-hydroxyethylamino, etc.; r is R 6 Has the general formula of-R 7 CN，R 7 Is at least one of C1-C4 alkylene, a > 0, b > 0, C > 0, a:b:c=2-5:0-4:2-5.
For example, the monomer CH corresponding to a in the second polymer 2 ＝CR 1 COOR 4 Sodium acrylate, acrylic acid, methacrylic acid, sodium methacrylate, and the like; b corresponds to the monomer CH 2 ＝CR 2 COOR 5 With or without the first soft monomer. In the present application, the soft monomer means that the glass transition temperature Tg of a homopolymer obtained by homopolymerization of the monomer is lower than 0℃or further, tg is not more than-10℃and, for example, the first soft monomer may be ethyl acrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like. Monomer CH 2 ＝CR 2 COOR 5 Can be a combination of acrylic ester monomer and acrylamide monomer according to the weight ratio of 1:1-10:1 or can be independent propyleneThe amide-based monomer may be ethyl acrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., and the acrylamide-based monomer may be acrylamide, N-dimethylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-methylolacrylamide, N-diethylacrylamide, etc., without particular limitation. c monomer CH corresponding to 2 ＝CR 3 COOR 6 Can be acrylonitrile, methacrylonitrile, 3-butenenitrile, and the like.
The second polymer may be polymerized by free radical polymerization methods, as is well known to those skilled in the art. For example, one polymerization method is: heating water to polymerization reaction temperature, dropwise adding a monomer mixture composed of three monomers, simultaneously dropwise adding a water-soluble initiator solution, synchronously finishing dropwise adding the monomer mixture and the water-soluble initiator solution within 1-6 hours, and continuously performing constant-temperature reaction for 0-8 hours to obtain the catalyst. Or the polymerization method may be: adding a monomer mixture consisting of three monomers into water, heating to the polymerization reaction temperature, dropwise adding a water-soluble initiator solution within 10min-4h, and continuing to react at constant temperature for 0-8 h to obtain the catalyst.
Third aqueous solution
The third aqueous solution was prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a third monomer, a fourth monomer and a fifth monomer for polymerization reaction to obtain the modified polyurethane foam;
wherein the general formula of the third monomer is CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl, M is selected from H, na + 、Li + And K + At least one of (a) and (b); for example, the third monomer may be acrylic acid, sodium acrylate, sodium methacrylate, sodium acrylate, or the like.
Wherein the fourth monomer at least contains a second soft monomer; the general formula of the second soft monomer is CH 2 ＝CHCOOR 15 Wherein R is 15 Selected from C2-C18 alkyl or C2-C18 substituted alkyl, the second soft monomer may be selected from butyl acrylate, iso-butyl acrylate, for exampleOctyl ester, octyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, lauryl acrylate, stearic acrylate, and the like. Or the fourth monomer is CH as described above 2 ＝CHCOOR 15 The combination of the monomer and the acrylamide monomer in a weight ratio of 1:1 to 10:1 is exemplified by acrylamide, N-dimethylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-methylolacrylamide, N-diethylacrylamide, etc., without particular limitation. Further, the weight ratio of the second soft monomer in the fourth monomer is not less than 50%.
Wherein the fifth monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene. For example, the fifth monomer may be selected from acrylonitrile, 3-butenenitrile, and the like.
In this application, the mixed monomer may be composed of 5 to 50% by weight of the third monomer, 5 to 50% by weight of the fourth monomer, and 20 to 90% by weight of the fifth monomer. Further, it may be composed of 10 to 40% of the third monomer, 10 to 40% of the fourth monomer and 40 to 80% of the fifth monomer, for example, 20% of the third monomer, 20% of the fourth monomer and 60% of the fifth monomer, 20% of the third monomer, 30% of the fourth monomer and 50% of the fifth monomer, 15% of the third monomer, 15% of the fourth monomer and 70% of the fifth monomer, 40% of the third monomer, 10% of the fourth monomer and 50% of the fifth monomer, etc.
In the present application, the weight ratio of the surfactant and/or the protective colloid in the mixed monomer is 0-50%. The surfactant may be an anionic surfactant or a nonionic surfactant, or a combination of two or more thereof, and for example, the surfactant may be AEO-3, AEO-9, tween 20, tween 80, span 20, span 80, span 60, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, or the like. Further, the weight ratio of the surfactant in the mixed monomer may be 0 to 5%, or still further, may be 0.5 to 5%, for example, may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc. The protective colloid can be polyvinyl alcohol PVA, polyethylene glycol PEG, polyvinylpyrrolidone PVP, sodium carboxymethyl cellulose, sodium hydroxypropyl cellulose, etc. Further, the weight ratio of the protective colloid in the mixed monomer may be 0 to 10%, or still further, may be 0.5 to 10%, for example, 0.5%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc.
The technical scheme of the application is described in detail below with reference to examples and comparative examples. Unless otherwise indicated, the parts in the examples and comparative examples below are parts by weight.
PREPARATION EXAMPLES 1-3 preparation of first aqueous solution
Preparation example 1
400 parts of water is added into a reaction kettle, a first monomer combination consisting of 45 parts of methacrylic acid, 15 parts of acrylamide, 10 parts of hydroxypropyl acrylate and 30 parts of acrylonitrile monomer and 5 parts of sodium bicarbonate are added under stirring at 180rpm, the mixture is uniformly mixed, the temperature is raised to 75 ℃,10 parts of aqueous solution containing 0.2 part of ammonium persulfate is dropwise added within 30min, and the reaction is carried out for 90min after the dropwise addition; the stirring rotation speed is regulated to 250rpm, a second monomer combination consisting of 5 parts of methacrylic acid and 30 parts of acrylonitrile and 20 parts of water are continuously added into a reaction kettle, the mixture is fully mixed, 10 parts of aqueous solution containing 0.3 part of ammonium persulfate is added, the temperature is kept for 180 minutes, the temperature is reduced to below 40 ℃, a certain amount of sodium bicarbonate and water are added, the pH is regulated to 7.0-7.5, the solid content is 8wt%, and the first aqueous solution is obtained.
Preparation example 2
The differences between preparation 2 and preparation 1 are: in preparation example 1, in the first monomer composition, 45 parts of methacrylic acid was adjusted to 50 parts, 15 parts of acrylamide was adjusted to 25 parts, and 30 parts of acrylonitrile was adjusted to 15 parts. The remaining steps remain unchanged.
Preparation example 3
The differences between preparation 3 and preparation 1 are: in preparation example 1, in the second monomer combination, 5 parts of methacrylic acid and 30 parts of acrylonitrile were adjusted to 10 parts of methacrylic acid and 60 parts of acrylonitrile. The remaining steps remain unchanged.
PREPARATION EXAMPLES 4-6 preparation of second aqueous solution
Preparation example 4
Adding 500 parts of water into a reaction vessel, adding 36 parts of methacrylic acid, 10.7 parts of butyl acrylate and 35.3 parts of acrylonitrile (the molar ratio of the butyl acrylate to the acrylonitrile is 3:0.5:4), adding 4 parts of sodium bicarbonate, uniformly mixing, heating to 73 ℃, adding 10 parts of aqueous solution containing 0.3 part of ammonium persulfate within 30min, continuing to carry out heat preservation reaction for 180min after the addition, cooling to below 40 ℃, adding a certain amount of sodium bicarbonate and water, and regulating the pH to 7.0-7.5, wherein the solid content is 10wt%, thus obtaining a second aqueous solution.
Preparation example 5
The differences between preparation 5 and preparation 4 are: in preparation example 4, 10.7 parts of butyl acrylate was adjusted to 11.8 parts of acrylamide. The remaining steps remain unchanged.
Preparation example 6
The differences between preparation 6 and preparation 4 are: in preparation example 4, acrylonitrile was adjusted from 35.3 parts to 17.7 parts. The remaining steps remain unchanged.
PREPARATION EXAMPLES 7-9 preparation of third aqueous solution
Preparation example 7
10 parts of PVABP-17 and 350 parts of water are added into a reaction kettle, the temperature is increased to 90 ℃ until BP-17 is completely dissolved, the temperature is reduced to below 50 ℃, 20 parts of acrylic acid, 30 parts of isooctyl acrylate, 10 parts of methyl acrylate and 40 parts of acrylonitrile are sequentially added, the temperature is increased to 75 ℃, 50 parts of aqueous solution containing 0.3g of ammonium persulfate is dropwise added, the dropwise addition is completed for 120 minutes, the heat preservation reaction is continued for 100 minutes, the temperature is reduced to below 40 ℃, sodium bicarbonate and water are added, the pH value is regulated to 7.0-7.5, the solid content is 16wt%, and a third aqueous solution is obtained.
Preparation example 8
The differences between preparation 8 and preparation 7 are: in preparation example 7, isooctyl acrylate was adjusted from 30 parts to 20 parts and acrylonitrile was adjusted from 40 parts to 50 parts. The remaining steps remain unchanged.
Preparation example 9
The differences between preparation 9 and preparation 7 are: in preparation example 7, BP-17 was adjusted from 10 parts to 2 parts. The remaining steps remain unchanged.
Example 1
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 1, the second aqueous solution of preparation example 4 and the third aqueous solution of preparation example 7 in a weight ratio of 1:2:1.
Example 2
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 2, the second aqueous solution of preparation example 5 and the third aqueous solution of preparation example 7 in a weight ratio of 1:2:1.
Example 3
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 3, the second aqueous solution of preparation example 6 and the third aqueous solution of preparation example 7 in a weight ratio of 1:2:1.
Example 4
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 1, the second aqueous solution of preparation example 4 and the third aqueous solution of preparation example 8 in a weight ratio of 1:2:1.
Example 5
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 1, the second aqueous solution of preparation example 5 and the third aqueous solution of preparation example 9 in a weight ratio of 1:2:1.
Example 6
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 2, the second aqueous solution of preparation example 4 and the third aqueous solution of preparation example 7 in a weight ratio of 2:2:1.
Example 7
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 2, the second aqueous solution of preparation example 5 and the third aqueous solution of preparation example 8 in a weight ratio of 2:2:3.
Example 8
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 3, the second aqueous solution of preparation example 6 and the third aqueous solution of preparation example 9 in a weight ratio of 1:1:2.
Example 9
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 3, the second aqueous solution of preparation example 4 and the third aqueous solution of preparation example 8 in a weight ratio of 1:2:3.
Comparative example 1
The first aqueous solution of preparation example 1.
Comparative example 2
The second aqueous solution of preparation 4.
Comparative example 3
The third aqueous solution of preparation 7.
Comparative example 4
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 1 and the second aqueous solution of preparation example 4 in a weight ratio of 1:2.
Comparative example 5
An aqueous binder for lithium ion batteries was prepared by mixing the first aqueous solution of preparation example 1 and the third aqueous solution of preparation example 7 in a weight ratio of 1:1.
Comparative example 6
An aqueous binder for lithium ion batteries was prepared by mixing the second aqueous solution of preparation example 4 and the third aqueous solution of preparation example 7 in a weight ratio of 2:1.
The preparation process of the graphite negative electrode plate comprises the following steps: dispersing the water-based adhesive to be tested and 50% of water for 15 minutes at 1000rpm, adding the conductive agent SP conductive carbon black to wet for 12 minutes, and stirring at a high speed of 1600rpm for 120 minutes; the negative electrode material S360-L2-H and the remaining 50% of water were added and stirring was continued at 1600rpm for 120 minutes at high speed. After the dispersion is finished, the viscosity (23 ℃) is regulated to be 2500-2700 mPa.s, and the mixture is filtered by a 150-mesh filter screen to finish discharging. Placing copper foil on a coater, adjusting the scale of a scraper of a wet film preparation device, uniformly pouring the filtered slurry, sending into 100 ℃ environment, blowing and baking until the slurry is dried, cutting the slurry into a specification of 12.5cm multiplied by 5cm, and enabling the single-sided surface density to be 100-110g/m 2 Is a pole piece.
The pole piece stripping force testing method comprises the following steps: sending the cut pole pieces into a 35% RH thermostatic chamber for 30 minutes, attaching the two pole pieces with the coating surface facing outwards and the copper foil surface facing inwards, and sending the pole pieces into an electric roller press to roll the pole pieces to 1.6g/cm 3 After rolling, placing for 30min, selecting five stainless steel plates with the specification of 12.5×5cm, sticking double faced adhesive tape with corresponding specification on the steel plates, and coatingLaminating the pole piece on a double-sided adhesive tape in a layer-down mode, then adhering a piece of masking paper tape with the width of 2.5cm on the copper foil, rolling the pole piece steel plate back and forth by an electric rolling roller for one circle under a certain pressure, and then using an electronic stripping machine to test the adhesive force of the pole piece; in the same way, the cohesive force of the pole piece can be tested by only changing the way that the pole piece is attached to the double-sided adhesive tape in an upward coating way.
The pole piece flexibility test method comprises the following steps: the softness tester ITM-RRD01 was used for the test.
The method for testing the swelling rate of the adhesive film electrolyte comprises the following steps: cutting edge part of bubble-free adhesive film, cutting into 1×4cm, oven drying in 105 deg.C air drying oven for 4 hr, and taking out weighing record M 1 Is put into a container filled with electrolyte (1M LiPF 6 in EC: DMC: EMC=1:1:1), soaking in the vial at constant temperature for 48 hr, taking out, wiping the surface electrolyte with filter paper, controlling wiping and weighing process within 1min, and weighing M 2 The swelling ratio of the adhesive film is (M 2 -M 1 )/M 1 ×100％。
The buckling assembly sequence is from bottom to top: negative electrode shell-elastic sheet-gasket-lithium sheet-electrolyte-diaphragm-electrolyte-pole piece-positive electrode shell; the first coulombic efficiency and impedance test is as follows:
first effect test 0.1C,0.005-1.5V charge and discharge; the impedance sweep was from 100kHz to 0.1Hz.
The results are shown in Table 1 below.
TABLE 1 Performance test results
Therefore, as can be seen from the data in the table above, the aqueous adhesive of the present application contains three polymers, and can realize the comprehensive characteristics of dispersibility, cohesion, flexibility, low impedance and good compatibility with the adhesive film.
The dispersion stability of the slurry obtained according to the preparation of the graphite negative electrode plate is tested: 90g of the freshly prepared slurry was placed in a 100ml transparent PET bottle (specification: diameter of main body 46mm, caliber 28mm, height 94mm, wall thickness 1 mm), and the upper layer was taken outThe slurry was tested for solids content and designated H 0 The method comprises the steps of carrying out a first treatment on the surface of the Standing the slurry for 48 hours, taking the upper slurry to test the solid content, and marking as H 1 Solid content change Δh=h 0 -H 1 .5 samples were taken for each test and the average was calculated. The results are shown in Table 2 below. The smaller the change in solids content, the more stable the slurry prepared, and the better the dispersibility.
TABLE 2 dispersion stability
As can be seen from the data in table 2, the aqueous binder of the present application was used to prepare active particle slurry of the negative electrode material, and the dispersion stability was good.
Therefore, the water-based adhesive has better comprehensive performance and good dispersibility on the anode particle active material, and can obtain a battery cell with lower impedance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The lithium ion battery aqueous adhesive is characterized by being prepared by mixing a first aqueous solution containing a first polymer, a second aqueous solution containing a second polymer and a third aqueous solution containing a third polymer;
the weight percentage content ratio of the first polymer, the second polymer and the third polymer in the lithium ion battery water-based adhesive is 1:1.5-3:1-6;
the first aqueous solution is prepared as follows: a first monomer combination consisting of a first hydrophilic monomer and a first hydrophobic monomer is polymerized for the first time in water, and then a second monomer combination consisting of a second hydrophilic monomer and a second hydrophobic monomer is added for the second polymerization, so that the polymer is obtained;
the general formula of the second polymer is shown in the following formula (1),
wherein R is 1 、R 2 And R is 3 Independently selected from H or C1-C4 alkyl, R 4 Selected from H, na + 、Li + And K + At least one of R 5 Selected from C2-C18 alkyl, C2-C18 substituted alkyl, amino or substituted amino, R 6 Has the general formula of-R 7 CN，R 7 Is at least one of the non-existence or selected from C1-C4 alkylene, a is more than 0, b is more than or equal to 0, C is more than 0, a: b: c=2-5:0-4:2-5;
the third aqueous solution is prepared as follows: adding a surfactant and/or a protective colloid into water, and then adding a mixed monomer consisting of a third monomer, a fourth monomer and a fifth monomer for polymerization reaction to obtain the modified polyurethane foam;
the general formula of the third monomer is CH 2 ＝CR 8 COOM, wherein R 8 Selected from H or C1-C4 alkyl, M is selected from H, na + 、Li + And K + At least one of (a) and (b);
the fourth monomer at least contains a second soft monomer;
the fifth monomer is selected from R 9 CH＝CHR 10 CN, wherein R 9 Selected from H or methyl, R 10 Is absent or at least one selected from C1-C4 alkylene.
2. The aqueous binder for lithium ion batteries according to claim 1, wherein the weight ratio of said first hydrophilic monomer in said first monomer combination is 60-100%, and the weight ratio of said second hydrophilic monomer in said second monomer combination is 0-60%.
3. The aqueous binder for lithium ion batteries according to claim 1, wherein said first hydrophilic monomer and said second hydrophilic monomer are independently selected from the group consisting of a compound having the general formula CH 2 ＝CR 11 R 12 Wherein R is 11 Selected from H or C1-C4 alkyl, R 12 Selected from-CONH 2 、-CONHCH 3 、-CONHCH 2 CH 3 、-CON(CH 3 ) 2 、-CON(CH 2 CH 3 ) 2 、-CONHCH 2 OH、-CONHCH 2 CH 2 OH、-COOCH 2 CH 2 OH、-COOCH 2 CH 2 CH 2 OH、-COOCH 2 CHCH 3 OH、-COOCH 2 CH 2 CH 2 CH 2 OH、-COO(CH 2 CH 2 O) d H and-COO (CH) 2 ) e PO 3 H, and/or one or more of them containing-COOM, - (C) 6 H 5 )COOM、-SO 3 M and- (C) 6 H 5 )SO 3 One or more of the organic structures of the M functional group, d=1-18, e=1-12, M is selected from H, li + 、Na + And K + One or more of them.
4. The aqueous binder for lithium ion batteries according to claim 1, wherein said first hydrophobic monomer and said second hydrophobic monomer are independently selected from the group consisting of a polymer having the general formula CH 2 ＝CR 13 R 14 Wherein R is 13 Selected from H or C1-C4 alkyl, R 14 Selected from-COOC n H 2n+1 and-C m H 2m One or more of CN, n=1-18, m=0-6.
5. The aqueous binder for lithium ion batteries according to claim 1, wherein the weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1.
6. The aqueous binder for lithium ion batteries according to claim 1, wherein after said first polymerization, the conversion of said first monomer combination is not lower than 70%.
7. The aqueous binder for lithium ion batteries according to claim 1, wherein said second soft monomer has the general formula CH 2 ＝CHCOOR 15 Wherein R is 15 Selected from C2-C18 alkyl or C2-C18 substituted alkyl.
8. The aqueous binder for lithium ion batteries according to claim 1, wherein said mixed monomer is composed of 5 to 50% by weight of said third monomer, 5 to 50% by weight of said fourth monomer and 20 to 90% by weight of said fifth monomer.
9. The aqueous binder for lithium ion batteries according to claim 1, wherein the weight ratio of the surfactant and/or the protective colloid in the mixed monomer is 0-50%.
10. The aqueous binder for lithium ion batteries according to claim 1, wherein the aqueous binder for lithium ion batteries has a weight concentration of 5-60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311193437.7A CN117447944A (en) | 2023-09-15 | 2023-09-15 | Aqueous adhesive for lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311193437.7A CN117447944A (en) | 2023-09-15 | 2023-09-15 | Aqueous adhesive for lithium ion battery |
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| CN202311193437.7A Pending CN117447944A (en) | 2023-09-15 | 2023-09-15 | Aqueous adhesive for lithium ion battery |
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