CN117511459A - Water-based polymer binder and preparation method and application thereof - Google Patents
Water-based polymer binder and preparation method and application thereof Download PDFInfo
- Publication number
- CN117511459A CN117511459A CN202311607350.XA CN202311607350A CN117511459A CN 117511459 A CN117511459 A CN 117511459A CN 202311607350 A CN202311607350 A CN 202311607350A CN 117511459 A CN117511459 A CN 117511459A
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- China
- Prior art keywords
- water
- monomer
- polymer binder
- acrylate
- soluble
- 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
- 229920005596 polymer binder Polymers 0.000 title claims abstract description 63
- 239000002491 polymer binding agent Substances 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 115
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 acrylic ester Chemical class 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 238000007792 addition Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000006386 neutralization reaction Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 10
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000006255 coating slurry Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006256 anode slurry Substances 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 claims description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 claims description 2
- UWHCZFSSKUSDNV-UHFFFAOYSA-N 3-(aziridin-1-yl)propanoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OC(=O)CCN1CC1.OC(=O)CCN1CC1.OC(=O)CCN1CC1.CCC(CO)(CO)CO UWHCZFSSKUSDNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 25
- 230000005465 channeling Effects 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 10
- 239000004743 Polypropylene Substances 0.000 abstract description 9
- 230000008961 swelling Effects 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 229940119545 isobornyl methacrylate Drugs 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- CQIOFKRONDXZJC-UHFFFAOYSA-N n-methylideneprop-2-enamide Chemical compound C=CC(=O)N=C CQIOFKRONDXZJC-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction 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
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of lithium battery materials and binders, and discloses a water-based polymer binder, a preparation method and application thereof. The aqueous polymer binder is obtained by copolymerization reaction of polymerized units comprising acrylic monomers, acrylic ester monomers, oil-soluble monomers, water-soluble monomers and amphiphilic water-soluble monomers in an aqueous solvent; the mass percentage ratio of each monomer is as follows: 5 to 15 percent of acrylic monomer, 45 to 60 percent of acrylic monomer, 10 to 40 percent of oil-soluble monomer, 5 to 20 percent of water-soluble monomer and 5 to 10 percent of amphiphilic water-soluble monomer. The aqueous polymer binder is mainly applied to the binder coated on the edge of a lithium ion battery negative electrode plate, and the obtained binder has excellent PP (polypropylene) base film binding property and electrolyte swelling resistance and does not generate channeling with a negative electrode through specific comonomer composition and proportion. Has good application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium battery materials and binders, and particularly relates to a water-based polymer binder, a preparation method and application thereof.
Background
Lithium crystallization occurs in the lithium ion battery in the repeated cycling process, and the separator may be pierced to cause direct contact between the anode and the cathode, so that a short circuit occurs. An edge glue coating is required to protect it; meanwhile, in the cutting process, the equipment needs to identify and cut the edge of the polar plate, and the traditional process can lead to cutting dislocation or damage to a negative electrode material area when cutting directly, so that the normal cutting processing of the polar plate can be ensured due to the existence of side gluing; and the bonding between the pole piece and the diaphragm can ensure that the bonding between the pole piece and the diaphragm is stable, so that the risk of dislocation is avoided. The process of coating the adhesive on the edge mainly comprises the steps of mixing the adhesive with boehmite, coating the adhesive to form a film, and then carrying out hot pressing on the film by using a film to ensure that the film and the film are effectively bonded.
The water-based acrylic ester pressure-sensitive adhesive has the advantages of good light resistance, good aging resistance, no toxicity, no pollution, low cost, excellent pressure sensitivity and adhesion and stable performance, so that the water-based acrylic ester pressure-sensitive adhesive is widely applied in a plurality of fields. However, when the common acrylate binder is used for coating and protecting the edge of the negative electrode of the lithium ion battery, the following problems exist: 1. poor wettability and large surface energy gap for PP membrane lead to weak adhesion; 2. the cathode paste and the anode paste have serious material channeling problems (the material channeling refers to the interpenetration of the cathode paste and the side glue paste due to the difference of the surface tension and the properties of the side glue paste and the anode paste when the side glue paste and the anode paste are simultaneously contacted, and the two materials are not two well-defined materials, which also can cause abnormal coating, so the side glue paste has higher requirements on the material channeling performance, and the material channeling does not occur in the processing process; 3. electrolyte resistance is generally low. In addition, the existing acrylic acid pressure-sensitive adhesive is generally synthesized by emulsion under the condition of an emulsifier, and the addition of the emulsifier influences the application performance of the acrylic acid pressure-sensitive adhesive in the edge coating protection of the lithium ion battery cathode.
Therefore, the development of the water-based polyacrylate adhesive which is applicable to the coating protection of the edge of the negative electrode of the lithium ion battery, has good adhesive force and solvent resistance, and can improve the anti-channeling performance of the negative electrode slurry has wide market prospect.
Disclosure of Invention
In view of the above drawbacks and deficiencies of the prior art, a primary object of the present invention is to provide an aqueous polymeric binder.
Another object of the present invention is to provide a method for preparing the above aqueous polymer binder.
The invention further aims to provide the application of the aqueous polymer binder in the bonding of the lithium ion battery negative electrode plate and the diaphragm.
The invention aims at realizing the following technical scheme:
a water-based polymer binder is prepared by copolymerization of polymerization units comprising acrylic monomers, acrylic ester monomers, oil-soluble monomers, water-soluble monomers and amphiphilic water-soluble monomers in an aqueous solvent; the mass percentage ratio of each monomer is as follows: 5 to 15 percent of acrylic monomer, 45 to 60 percent of acrylic monomer, 10 to 40 percent of oil-soluble monomer, 5 to 20 percent of water-soluble monomer and 5 to 10 percent of amphiphilic water-soluble monomer.
Further, the acrylic monomer is acrylic acid or methacrylic acid; the acrylic monomer is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, C13-C16 (meth) acrylate, stearyl (meth) acrylate, alkoxyphenol acrylate and glycidyl (meth) acrylate.
Further preferably, the acrylic monomer is a partially neutralized acrylic monomer, and the degree of neutralization of the partially neutralized acrylic monomer is 10% to 100%; more preferably, the neutralization degree is 40% to 100%.
Further, the oil-soluble monomer is one or more of acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, alpha-ethylacrylonitrile and styrene.
Further, the water-soluble monomer is one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-dimethylacrylamide, itaconic acid, hydroxyethyl acrylate and hydroxyethyl methacrylate.
Further, the amphiphilic water-soluble monomer is one or more of methoxy polyethylene glycol (methyl) acrylate, methoxy polypropylene glycol (methyl) acrylate, sodium p-styrenesulfonate and C2-C18 alkyl acrylamide.
Further, the polymerization unit also comprises a crosslinking monomer accounting for 0-1% of the total mass of the polymerization monomer; the crosslinking monomer is one or more of divinylbenzene, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N-methylene bisacrylamide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (3-aziridinyl propionate), polyurethane acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate and ethoxylated bisphenol A diacrylate.
The preparation method of the water-based polymer binder comprises the following preparation steps:
(1) Adding an acrylic monomer, an oil-soluble monomer, a water-soluble monomer, an amphiphilic water-soluble monomer and a crosslinking monomer into water, and uniformly stirring and mixing to obtain a phase A;
(2) Adding an initiator into water, stirring and mixing uniformly, and then heating to an initiation temperature to obtain a phase B;
(3) And (3) dropwise adding the phase A and the reducing agent into the phase B for heat preservation reaction, cooling, neutralizing, cooling and filtering after the reaction is finished, and thus obtaining the water-based polymer binder.
Further, the initiator in the step (2) is one or more of ammonium persulfate, potassium persulfate, benzoyl peroxide, azodiisobutyronitrile and azodiisoheptonitrile; the addition amount of the initiator is 0.1% -2% of the total mass of the polymerization monomers; the initiation temperature is 30-100 ℃.
Further, in the step (3), the reducing agent is one or more of sodium bisulphite and tert-butyl hydroperoxide.
Further, the time of the heat preservation reaction in the step (3) is 2-24 hours.
Further, the total amount of the water added in the step (1) and the step (2) is 0.5 to 5 times of the total mass of the polymerized monomers.
Application of aqueous polymer binder in bonding of lithium ion battery negative electrode plate and diaphragm
Further, the application method comprises the following steps: mixing and homogenizing a water-based polymer binder and boehmite to obtain side-coating slurry; and coating the obtained side coating slurry and the lithium ion battery negative electrode slurry on the surface of a negative electrode current collector, drying and forming a film, and then carrying out hot-press bonding with a diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The aqueous polymer binder is mainly applied to the bonding of the edge coating of the negative electrode plate, and the electrolyte resistance of the binder is improved by adding acrylic monomers and controlling the neutralization degree of the acrylic monomers; the oil-soluble monomer and the water-soluble monomer are controlled to have good bonding strength and anti-channeling performance by controlling the addition ratio of the oil-soluble monomer and the water-soluble monomer, and meanwhile, the electrolyte resistance is maintained at a higher level, so that the obtained adhesive has excellent PP (polypropylene) base film bonding performance and electrolyte swelling resistance, and meanwhile, the anti-channeling performance of the adhesive with the negative electrode slurry can be remarkably improved.
(2) The polymerization monomer ensures the stability in the processing of the water-based polymer binder through the emulsification of the partially neutralized acrylic acid and the amphiphilic water-soluble monomer, does not need to add an extra emulsifier, and ensures that the binder has good bonding strength; and the addition ratio of the amphiphilic water-soluble monomer is controlled, so that the channeling resistance and the electrolyte resistance of the water-based polymer binder are maintained at higher levels.
Drawings
FIG. 1 is an external view of the aqueous polymer binder emulsion obtained in example 1.
FIG. 2 is a thermal press bonding state diagram of the aqueous polymer binders obtained in examples 1 and 2 after mixing boehmite.
FIG. 3 is a graph showing the results of a negative electrode slurry channeling resistance test at normal temperature for 5 minutes for the aqueous polymer binder obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The product properties in the following examples were tested as follows:
(1) Peel strength test:
mixing the aqueous polymer binder with boehmite according to the mass ratio of 1:5, homogenizing, coating, drying and forming a film, then carrying out hot-press bonding with a PP diaphragm, peeling upwards at 180 ℃, and testing the peeling strength by using a universal mechanical stretcher.
(2) Negative electrode slurry channeling resistance:
and mixing the aqueous polymer binder with boehmite according to the mass ratio of 1:5, homogenizing to obtain uniform slurry, and filtering to obtain the negative electrode edge coating slurry. Adding CMC into water, stirring, dissolving uniformly, adding conductive carbon, dispersing for 2h, adding graphite negative electrode material, dispersing for 2h at high speed, reducing speed, adding SBR, and filtering to obtain negative electrode slurry. And sucking a certain negative electrode edge coating slurry and a negative electrode slurry by using a suction pipe, enabling the two slurries to be contacted together, observing the channeling permeation phenomenon of the slurries, and observing the time for which the two materials are obviously permeated.
(3) Electrolyte resistance:
and mixing the aqueous polymer binder with boehmite according to the mass ratio of 1:5, homogenizing, and filtering to obtain the cathode edge coating slurry. And (3) coating the negative electrode side coating slurry on a copper foil, drying the copper foil to form a film, and then performing hot-press bonding with a PP diaphragm to obtain a negative electrode plate. The negative electrode sheet was immersed in an electrolyte, and the mass swelling ratio (swelling ratio= (mass after swelling of the adhesive film-initial mass of the adhesive film)/initial mass of the adhesive film 100%) and the appearance of the sheet (observation of whether the adhesive film and the separator had cracking or falling off on the sheet) after immersing for 7d at 60 ℃ in the electrolyte were tested.
Example 1
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 85%), 20g of an oil-soluble monomer, 10g of methyl methacrylate, 40g of isooctyl acrylate, 10g of acrylamide, 5g of hydroxyethyl acrylate, 5g of sodium p-styrenesulfonate, and 100g of water were added to a flask and stirred at high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The different oil-soluble monomers were selected according to table 1, and the product properties were tested and the results are shown below:
TABLE 1 Properties of aqueous Polymer Adhesives from different oil-soluble monomers
As shown in the results of Table 1, the aqueous polymer binders obtained by using the different oil-soluble monomers of the present invention all have good hot press adhesion performance, channeling prevention performance and electrolyte resistance.
The appearance of the aqueous polymer binder emulsion (the oil-soluble monomer is styrene) obtained in this example is shown in FIG. 1.
The state diagram of the aqueous polymer binder (the oil-soluble monomer is styrene) obtained in this example, which is obtained by coating and drying boehmite and then performing thermocompression bonding with a PP separator, is shown in fig. 2 (left).
The graph of the test result of the anode slurry channeling resistance at normal temperature for 5min of the water-based polymer binder (the oil-soluble monomer is styrene) obtained in this example is shown in fig. 3 (the left side of the graph is the glue-coated slurry, and the right side is the anode slurry).
Example 2
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 85%), 20g of styrene, 10g of methyl methacrylate, 40g of isooctyl acrylate, 15g of a water-soluble monomer, 5g of methoxypolyethylene glycol monomethacrylate, 0.45g of polyethylene glycol diacrylate, 100g of water were added to a flask and stirred at high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The different water-soluble monomers were selected according to Table 2, and the product properties were tested and the results were as follows:
TABLE 2 Properties of aqueous Polymer Adhesives from different Water-soluble monomers
As can be seen from the results in Table 2, the aqueous polymer binders obtained by using the different water-soluble monomers of the present invention all have good hot press adhesion, channeling prevention and electrolyte resistance.
The state diagram of the aqueous polymer binder (the oil-soluble monomer is styrene) obtained in this example, which is obtained by coating and drying boehmite and then performing thermocompression bonding with a PP separator, is shown in fig. 2 (right).
Example 3
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 75%), 20g of styrene, 10g of methyl methacrylate, 40g of isooctyl acrylate, 10g of acrylamide, 5g of isobornyl methacrylate, 5g of an amphiphilic water-soluble monomer, 0.45g of N, N-methylenebisacrylamide and 100g of water were added to a flask and stirred at high speed to obtain a uniform A phase.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The properties of the products were tested by selecting different amphiphilic water-soluble monomers according to table 3, and the results are shown below:
TABLE 3 Properties of aqueous Polymer binders obtained from different amphiphilic Water-soluble monomers
As shown in the results of Table 3, the aqueous polymer binders obtained by using the different amphiphilic water-soluble monomers of the invention have good hot-press bonding performance, channeling-preventing performance and electrolyte resistance.
Example 4
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid with different degrees of neutralization, 20g of styrene, 10g of methyl methacrylate, 30g of isooctyl acrylate, 10g of lauryl methacrylate, 5g of acrylamide, 5g of isobornyl methacrylate, 5g of sodium p-styrenesulfonate, 0.45g of N, N-methylenebisacrylamide and 100g of water are added into a flask and stirred at a high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
Acrylic acid with different neutralization degrees was selected according to table 4, and the product properties were tested, and the results are shown below:
TABLE 4 Properties of aqueous Polymer Adhesives obtained from acrylic acids of different degrees of neutralization
As shown in the results of Table 4, with the increase of the neutralization degree of the acrylic acid, the adhesive property and the channeling resistance of the obtained aqueous polymer adhesive show a trend of increasing and then decreasing, and the electrolyte resistance shows a trend of increasing, so that the better hot-press adhesive property, the channeling resistance and the electrolyte resistance can be achieved within the neutralization degree of 40-100%.
Example 5
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) Acrylic acid of different mass (degree of neutralization 75%), 20g of styrene, 10g of methyl methacrylate, 20g of isooctyl acrylate, 20g of lauryl methacrylate, 5g of acrylamide, 5g of isobornyl methacrylate, 5g of methoxypolyethylene glycol acrylate, 0.45g of polyethylene glycol diacrylate, 100g of water were added to a flask and stirred at high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
Acrylic acid of different quality was selected according to table 5 and the product properties were tested and the results are shown below:
TABLE 5 Properties of aqueous Polymer binders obtained with different acrylic additions
As is clear from the results in Table 5, the adhesive properties, the channeling resistance and the electrolyte resistance of the obtained aqueous polymer adhesive were significantly reduced without adding an acrylic monomer, and the aqueous polymer adhesive did not meet the use requirements. With the increase of the addition amount of the acrylic acid monomer, the peel strength of the obtained aqueous polymer adhesive has the trend of increasing firstly and then decreasing, and the channeling resistance and the electrolyte resistance have the trend of increasing. The acrylic monomer has better hot-pressing viscosity performance, channeling resistance and electrolyte resistance in the addition range of 5-15%.
Example 6
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 75%), various amounts of oil-soluble monomers, 10g of methyl methacrylate, 20g of isooctyl acrylate, 20g of butyl acrylate, 5g of acrylamide, 5g of isobornyl methacrylate, 5g of methoxypolyethylene glycol acrylate, 0.45g of N, N-methyleneacrylamide, 100g of water were added to a flask and stirred at high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The oil-soluble monomers were selected in different amounts according to Table 6, and the properties of the products were tested and the results were as follows:
TABLE 6 Properties of aqueous Polymer Adhesives obtained with different amounts of oil-soluble monomer added
As is clear from the results in Table 6, the adhesive properties of the resulting aqueous polymer adhesive were significantly lowered without the addition of the oil-soluble monomer. With the increase of the addition amount of the oil-soluble monomer, the peel strength and electrolyte resistance of the obtained aqueous polymer adhesive show a trend of increasing and then decreasing, and the channeling resistance shows a trend of decreasing. The oil-soluble monomer has better hot-pressing viscosity performance, channeling resistance and electrolyte resistance under the addition range of 10-40%.
Example 7
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 75%), 10g of styrene, 10g of acrylonitrile, 10g of methyl methacrylate, 20g of isooctyl acrylate, 20g of butyl acrylate, 5g of isobornyl methacrylate, different amounts of water-soluble monomers, 5g of methoxypolyethylene glycol acrylate, 0.45g of N, N-methyleneacrylamide, 100g of water were added to the flask and stirred at high speed to obtain a homogeneous phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The water-soluble monomers were selected in different amounts according to Table 7, and the properties of the products were tested, and the results are shown below:
TABLE 7 Properties of aqueous Polymer Adhesives obtained from Water-soluble monomers at different addition levels
As is clear from the results in Table 7, the adhesive properties, the channeling resistance and the electrolyte resistance of the obtained aqueous polymer adhesive were significantly reduced without adding a water-soluble monomer, and the aqueous polymer adhesive was not satisfactory. With the increase of the addition amount of the water-soluble monomer, the peel strength and electrolyte resistance of the obtained aqueous polymer adhesive show a trend of increasing and then decreasing, and the channeling resistance shows a trend of increasing. The acrylamide has a thermal crosslinking effect, can strengthen the network structure of the polymer, and improves the electrolyte swelling resistance of the material; the acrylamide has strong polar bonds, so that the adhesive property of the acrylamide can be improved; however, too much acrylamide may cause excessive cohesion of the adhesive film and hardening of the adhesive film due to its high Tg, thereby causing deterioration of adhesive properties. The water-soluble monomer has better hot-pressing viscosity performance, channeling resistance and electrolyte resistance under the addition range of 5-20%.
Example 8
The aqueous polymer binder of the embodiment is prepared by the following method:
(1) 5g of acrylic acid (neutralization degree: 75%), 20g of styrene, 20g of methyl methacrylate, 40g of isooctyl acrylate, 10g of acrylamide, 5g of hydroxyethyl acrylate, different addition amounts of amphiphilic water-soluble monomer methoxy polyethylene glycol acrylate, 0.45g of trimethylolpropane triacrylate and 100g of water are added into a flask and stirred at a high speed to obtain a uniform phase A.
(2) Adding 200g of water and 0.5g of ammonium persulfate into a beaker, uniformly stirring, and heating to 60 ℃ to obtain a phase B;
(3) Simultaneously dropwise adding the phase A and 0.2g of reducing agent sodium bisulphite into the phase B for 2 hours, and continuously preserving heat for reaction for 4 hours after the completion of dropwise adding; then heating to 80 ℃, adding 0.1g of initiator ammonium persulfate, continuing to react for 2 hours, cooling after the reaction is finished, neutralizing with alkali, cooling and filtering to obtain the water-based polymer binder.
The amphiphilic water-soluble monomers with different addition amounts are selected according to the table 8 respectively, and the performance of the product is tested, and the results are shown as follows:
TABLE 8 Properties of aqueous Polymer binders obtained from amphiphilic Water-soluble monomers at different addition levels
As can be seen from the results of Table 8, too low or too high an addition of the amphiphilic water-soluble monomer results in a significant decrease in both the channeling resistance and the electrolyte resistance of the aqueous polymer binder. The amphipathic water-soluble monomer has excellent hot-pressing viscosity performance, channeling resistance and electrolyte resistance in the addition range of 5% -10%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (14)
1. The water-based polymer binder is characterized by being obtained by copolymerization of polymerization units comprising acrylic monomers, acrylic ester monomers, oil-soluble monomers, water-soluble monomers and amphiphilic water-soluble monomers in a water solvent; the mass percentage ratio of each monomer is as follows: 5 to 15 percent of acrylic monomer, 45 to 60 percent of acrylic monomer, 10 to 40 percent of oil-soluble monomer, 5 to 20 percent of water-soluble monomer and 5 to 10 percent of amphiphilic water-soluble monomer.
2. An aqueous polymeric binder according to claim 1 wherein the acrylic monomer is acrylic acid or methacrylic acid; the acrylic monomer is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, C13-C16 (meth) acrylate, stearyl (meth) acrylate, alkoxyphenol acrylate and glycidyl (meth) acrylate.
3. An aqueous polymer binder according to claim 2 wherein the acrylic monomer is a partially neutralized acrylic monomer and the degree of neutralization of the partially neutralized acrylic monomer is from 10% to 100%.
4. A waterborne polymer binder according to claim 3, wherein the degree of neutralization of the partially neutralized acrylic monomer is from 40% to 100%.
5. An aqueous polymer binder according to claim 1 wherein the oil soluble monomer is one or more of acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, α -ethylacrylonitrile, styrene.
6. The aqueous polymer binder of claim 1 wherein the water-soluble monomer is one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-dimethylacrylamide, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate.
7. The aqueous polymer binder of claim 1 wherein the amphiphilic water-soluble monomer is one or more of methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, sodium p-styrenesulfonate, and C2-C18 alkyl acrylamide.
8. An aqueous polymer binder according to any one of claims 1 to 7 wherein the polymerized units further comprise 0 to 1% by weight of the total polymerized monomer of a crosslinking monomer; the crosslinking monomer is one or more of divinylbenzene, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N-methylene bisacrylamide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (3-aziridinyl propionate), polyurethane acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate and ethoxylated bisphenol A diacrylate.
9. A method of preparing an aqueous polymeric binder as defined in claim 8, comprising the steps of:
(1) Adding an acrylic monomer, an oil-soluble monomer, a water-soluble monomer, an amphiphilic water-soluble monomer and a crosslinking monomer into water, and uniformly stirring and mixing to obtain a phase A;
(2) Adding an initiator into water, stirring and mixing uniformly, and then heating to an initiation temperature to obtain a phase B;
(3) And (3) dropwise adding the phase A and the reducing agent into the phase B for heat preservation reaction, cooling, neutralizing, cooling and filtering after the reaction is finished, and thus obtaining the water-based polymer binder.
10. The method of preparing an aqueous polymer binder according to claim 9, wherein the initiator in step (2) is one or more of ammonium persulfate, potassium persulfate, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; the addition amount of the initiator is 0.1% -2% of the total mass of the polymerization monomers; the initiation temperature is 30-100 ℃.
11. The method of preparing an aqueous polymer binder according to claim 9, wherein the reducing agent in step (3) is one or more of sodium bisulphite and t-butyl hydroperoxide; the time of the heat preservation reaction is 2-24 hours.
12. The method for preparing an aqueous polymer binder according to claim 9, wherein the total amount of water added in the step (1) and the step (2) is 0.5 to 5 times the total mass of the polymerized monomers.
13. The use of an aqueous polymer binder as claimed in claim 8 for binding a negative electrode sheet of a lithium ion battery with a separator.
14. The application of the aqueous polymer binder in the bonding of the lithium ion battery negative electrode plate and the diaphragm according to claim 13, wherein the application method is as follows: mixing and homogenizing a water-based polymer binder and boehmite to obtain side-coating slurry; and coating the obtained side coating slurry and the anode slurry on the surface of a negative current collector of the lithium ion battery, drying the surface to form a film, and then carrying out hot-press bonding with a diaphragm.
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| CN117720869A (en) * | 2024-02-07 | 2024-03-19 | 深圳市研一新材料有限责任公司 | Water-soluble binder, battery pole piece and application thereof |
| CN117777904A (en) * | 2024-02-27 | 2024-03-29 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117720869A (en) * | 2024-02-07 | 2024-03-19 | 深圳市研一新材料有限责任公司 | Water-soluble binder, battery pole piece and application thereof |
| CN117777904A (en) * | 2024-02-27 | 2024-03-29 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
| CN117777904B (en) * | 2024-02-27 | 2024-05-28 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
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