CN116404162A - Adhesive, preparation method thereof, electrode plate and secondary battery - Google Patents
Adhesive, preparation method thereof, electrode plate and secondary battery Download PDFInfo
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- CN116404162A CN116404162A CN202310435510.0A CN202310435510A CN116404162A CN 116404162 A CN116404162 A CN 116404162A CN 202310435510 A CN202310435510 A CN 202310435510A CN 116404162 A CN116404162 A CN 116404162A
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- comonomer
- sulfonate
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- unsaturated
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- 239000000853 adhesive Substances 0.000 title claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 35
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 41
- 239000005416 organic matter Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- 239000002210 silicon-based material Substances 0.000 claims description 9
- -1 polyhexamethylene guanidine hydrochloride Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000003871 sulfonates Chemical class 0.000 claims description 8
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 229920002413 Polyhexanide Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 4
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NYUTUWAFOUJLKI-UHFFFAOYSA-M 3-prop-2-enoyloxypropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229960002152 chlorhexidine acetate Drugs 0.000 claims description 3
- 229960003333 chlorhexidine gluconate Drugs 0.000 claims description 3
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- RONFGUROBZGJKP-UHFFFAOYSA-N iminoctadine Chemical compound NC(N)=NCCCCCCCCNCCCCCCCCN=C(N)N RONFGUROBZGJKP-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 15
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group 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
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229920002873 Polyethylenimine Chemical group 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009966 trimming 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of secondary batteries, in particular to an adhesive, a preparation method thereof, an electrode plate and a secondary battery. An adhesive comprising a copolymer and an organic compound containing more than 2 guanidine groups; the comonomer of the copolymer comprises comonomer I and comonomer II; the comonomer I comprises at least one of unsaturated carboxylic acid, unsaturated carboxylate, unsaturated sulfonic acid and unsaturated sulfonate; the structural formula of the comonomer II is as follows:
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to an adhesive, a preparation method thereof, an electrode plate and a secondary battery.
Background
The lithium ion battery has excellent performances of high capacity, long cycle, no memory effect, less self discharge, wide use temperature range and the like, and has been widely applied to the fields of 3C products and electric automobiles. In the use process of the battery, as lithium ions are inserted and separated, the positive pole piece and the negative pole piece can expand in volume, so that the internal structure of the pole piece is damaged, and the performance of the lithium ion battery is affected. At present, how to effectively inhibit the expansion of the pole piece and improve the battery performance is one of the hot spots of research.
The negative electrode sheet mainly comprises graphite as a negative electrode active material, a silicon-based material, a binder and a conductive agent. With the pursuit of high energy density lithium ion batteries, silicon-based materials are becoming more and more important. However, during the lithium intercalation process, the silicon-based material is accompanied by serious volume expansion, so that the crushing of material particles and repeated crushing and reconstruction of SEI film seriously affect the battery performance, and the commercial application of the material is greatly limited. The expansion of the silicon-based material is restrained by the structural design and modification of the adhesive, and the method is an economic and effective means.
In the prior art, the binders used for the negative electrode material mainly include styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC) and the like, but the cohesive force of the binders is weak, and the expansion of the silicon-based material cannot be effectively inhibited. The polyacrylic acid (PAA) binder can form a large number of intermolecular hydrogen bonds, and can effectively inhibit the bulk expansion of the anode material. However, the polyacrylic acid binder is too strong in intermolecular hydrogen bond, so that the material is fragile, is unfavorable for pole piece processing and manufacturing, and lacks strong interface adhesion with the carbon-based negative electrode active material.
Therefore, the existing binder or cohesion is weak, the volume change of the anode material cannot be well restrained in the charge and discharge process, or the pole piece is fragile due to the excessively strong rigidity, and the active material is difficult to maintain effective interface combination, so that the cycle stability of the battery cannot be effectively improved.
In view of this, the present invention has been made.
Disclosure of Invention
It is an object of the present invention to provide an adhesive.
It is another object of the present invention to provide a method for preparing the binder.
It is a further object of the present invention to provide an electrode sheet containing the above binder.
It is still another object of the present invention to provide a secondary battery including the above electrode tab.
In order to achieve the above object of the present invention, the technical scheme of the present invention is as follows:
the invention provides a binder, which comprises a copolymer and an organic matter containing more than 2 guanidine groups;
the comonomer of the copolymer comprises comonomer I and comonomer II;
the comonomer I comprises at least one of unsaturated carboxylic acid, unsaturated carboxylate, unsaturated sulfonic acid and unsaturated sulfonate;
the structural formula of the comonomer II is as follows:
In a specific embodiment of the present invention, the comonomer I comprises:
(a) At least one of a carboxylic acid group, a carboxylate group, a sulfonic acid group, and a sulfonate group; the method comprises the steps of,
(b) Alkenyl groups.
In a specific embodiment of the present invention, the unsaturated carboxylic acid includes at least one of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid; the unsaturated carboxylic acid salt includes at least one of a lithium salt, a potassium salt, and a sodium salt of the unsaturated carboxylic acid. Further, the unsaturated carboxylic acid salt includes at least one of lithium acrylate, potassium acrylate, sodium acrylate, lithium methacrylate, potassium methacrylate, and sodium methacrylate.
In a specific embodiment of the present invention, the unsaturated sulfonate comprises at least one of sodium styrene sulfonate, sodium 3-prop-2-enoyloxy propane-1-sulfonate, potassium 3-sulfonate methacrylate, inner N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonate, inner 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate.
In a specific embodiment of the present invention, the organic matter containing 2 or more guanidine groups includes at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, chlorhexidine gluconate, chlorhexidine acetate, and iminoctadine.
In a specific embodiment of the present invention, the mass ratio of the comonomer I and the comonomer II to the organic compound containing 2 or more guanidine groups is (1 to 50):1, preferably (5 to 20):1.
In a specific embodiment of the invention, said copolymer comprises 40% to 80% of said comonomer I and 20% to 60% of said comonomer II in mass percent, based on the total amount of said copolymer. Further, the copolymer comprises 60-70% of the comonomer I and 30-40% of the comonomer II in percentage by mass.
The invention also provides a preparation method of the adhesive, which comprises the following steps:
the comonomer I and the comonomer II are polymerized in situ in a liquid system comprising an organic compound containing more than 2 guanidino groups and an initiator.
In a specific embodiment of the invention, the initiator is used in an amount of 1% to 5% by weight, preferably 2% to 4% by weight, based on the sum of the masses of the interpolymer I and of the comonomer II. Further, the initiator includes at least one of ammonium persulfate, potassium persulfate, and sodium persulfate.
In a specific embodiment of the invention, the liquid system comprises a water system.
In a specific embodiment of the present invention, the preparation method comprises:
(a) Dissolving an organic matter containing more than 2 guanidine groups in water to prepare an aqueous solution of the organic matter containing more than 2 guanidine groups;
(b) Adding the comonomer I and the comonomer II into the aqueous solution, and uniformly dispersing; heating to initiator initiation temperature under protective atmosphere, adding initiator, reacting for 2-6 h, stopping reaction, and drying to obtain the final product.
In a specific embodiment of the present invention, in the step (a), the mass fraction of the organic matter containing 2 or more guanidine groups in the aqueous solution of the organic matter containing 2 or more guanidine groups is 0.1% to 5%.
The invention also provides an electrode plate which comprises a current collector and an electrode membrane arranged on the current collector; the electrode membrane includes the binder therein.
In a specific embodiment of the invention, the electrode sheet comprises a negative electrode sheet.
In a specific embodiment of the present invention, the binder is used in an amount of 1% to 5% by mass, preferably 2% to 4% by mass, of the electrode membrane.
In a specific embodiment of the present invention, the active material in the electrode membrane comprises a silicon-based material. Further, the active material further includes a carbon material.
The invention also provides a secondary battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte; the negative electrode plate is the electrode plate.
Compared with the prior art, the invention has the beneficial effects that:
the adhesive is elastic and flexible, can effectively inhibit expansion of the pole piece material, can keep good adhesion effect with active substances in the battery cycle process, has excellent fatigue resistance, ensures that the prepared negative pole piece based on the adhesive has excellent performance, and improves the cycle performance of the battery.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the prior art, the electrode material binder cannot well inhibit the volume change of the active material in the charge-discharge process, and can induce the interface bonding contact failure of the binder and the active material and the current collector, thereby causing the problem of poor cycling stability of the battery.
The invention provides a binder, which comprises a copolymer and an organic matter containing more than 2 guanidine groups;
the comonomer of the copolymer comprises comonomer I and comonomer II;
the comonomer I comprises at least one of unsaturated carboxylic acid, unsaturated carboxylate, unsaturated sulfonic acid and unsaturated sulfonate;
the structural formula of the comonomer II is as follows:
The comonomer I contained in the copolymer adopted in the binder has water solubility and electronegativity, can promote the stable dispersibility of the formed copolymer in a water phase system, and has a suspension dispersion effect on slurry; and, the carbonyl contained in the comonomer I can complex lithium ions, so that the dynamic performance of the battery is improved. The comonomer II contained in the copolymer contains a cyano group with a strong polar group, so that strong interfacial adhesion can be formed between the comonomer II and an active substance and a current collector, and the stability of the electrode structure in the charge and discharge process is improved; and the coordination of cyano groups and lithium ions is also beneficial to improving the transmission dynamics performance of lithium ions.
Carboxylic acid groups or sulfonic acid groups and the like contained in the monomers in the copolymer can form strong force with the cooperation of ionic bonds and hydrogen bonds between the guanidine groups, and a strong physical crosslinking effect is generated, so that the expansion of the pole piece material is effectively inhibited; in addition, the existence of the physical crosslinking effect can dissipate the stress energy of the material through the fracture of the physical crosslinking hydrogen bond and the ionic bond, thereby obtaining good flexibility.
In a specific embodiment of the present invention, the comonomer I comprises:
(a) At least one of a carboxylic acid group, a carboxylate group, a sulfonic acid group, and a sulfonate group; the method comprises the steps of,
(b) Alkenyl groups.
The comonomer I of the present invention is at least one of an alkenyl-containing carboxylic acid, an alkenyl-containing carboxylate, an alkenyl-containing sulfonic acid and an alkenyl-containing sulfonate. Alkenyl in the structure is used for polymerization reaction to form a copolymer, carboxylic acid, carboxylate, sulfonic acid, sulfonate groups and the like provide water solubility and electronegativity, promote stable dispersion of the copolymer in a water phase, realize suspension dispersion effect on slurry, and carbon groups in the copolymer can complex lithium ions, so that the dynamic performance of the battery is improved.
In a specific embodiment of the present invention, the unsaturated carboxylic acid includes at least one of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid; the unsaturated carboxylic acid salt includes at least one of a lithium salt, a potassium salt, and a sodium salt of the unsaturated carboxylic acid. Further, the unsaturated carboxylic acid salt includes at least one of lithium acrylate, potassium acrylate, sodium acrylate, lithium methacrylate, potassium methacrylate, and sodium methacrylate.
In some embodiments of the invention, the unsaturated carboxylic acid salt comprises at least one of lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate.
In actual operation, the comonomer I can comprise more than 2 of the above substances, and when the comonomer I comprises more than 2 of the above substances, the proportion of various substances can be adjusted according to actual requirements, and the total mass ratio of the comonomer I can meet the requirements.
In a specific embodiment of the present invention, the unsaturated sulfonate comprises at least one of sodium styrene sulfonate, sodium 3-prop-2-enoyloxy propane-1-sulfonate, potassium 3-sulfonate methacrylate, inner N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonate, inner 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate.
In some embodiments of the present invention, the unsaturated sulfonate comprises at least one of a potassium 3-sulfonate methacrylate salt, an inner N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonate salt, and an inner 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate salt.
In actual operation, the comonomer II can comprise more than 2 of the above substances, and when the comonomer II comprises more than 2 of the above substances, the proportion of various substances can be adjusted according to actual requirements, and the total mass ratio of the comonomer II can meet the requirements.
In a specific embodiment of the present invention, the organic matter containing 2 or more guanidine groups includes at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, chlorhexidine gluconate, chlorhexidine acetate, and iminoctadine. Wherein, more than 2 includes 2 and more than 2 cases.
In some embodiments of the invention, the organic compound containing more than 2 guanidine groups comprises polyhexamethylene guanidine hydrochloride and/or polyhexamethylene guanidine hydrochloride.
In some embodiments of the invention, the polyhexamethylene guanidine hydrochloride has a number average molecular weight of 8000 to 12000; the number average molecular weight of the polyhexamethylene biguanide hydrochloride is 2000-5000.
As in the various embodiments, the number average molecular weight of the polyhexamethylene guanidine hydrochloride can be 8000, 8500, 9000, 9500, 10000, 10500, 11000, 11500, 12000, or a range consisting of any two thereof; the polyhexamethylene biguanide hydrochloride may have a number average molecular weight in the range of 2000, 2500, 3000, 3500, 4000, 4500, 5000, or any two of these.
When R is H, the comonomer II is acrylonitrile; when R is methyl, the comonomer II is methacrylonitrile. I.e. the comonomer ii comprises at least one of methacrylonitrile and acrylonitrile.
In a specific embodiment of the present invention, the mass ratio of the comonomer I and the comonomer II to the organic compound containing 2 or more guanidine groups is (1 to 50):1, preferably (5 to 20):1. When the organic matter containing more than 2 guanidine groups is too much and the comonomer is too little, the suspension dispersion effect of the binder on the slurry is reduced, and the inhibition effect on the expansion of the electrode sheet material is reduced; when the organic matter containing more than 2 guanidine groups is too little and the comonomer is too much, high elastic modulus can be provided, but the physical crosslinking effect between the copolymer and the guanidine groups is weakened, the dissipation effect of stress energy received by the pole piece material through the fracture of the physical crosslinking hydrogen bond and the ionic bond is weakened, and the flexibility is insufficient. The invention further controls the mass of the comonomer I and the comonomer II and the mass ratio of the comonomer I and the comonomer II to the organic matter containing more than 2 guanidine groups within the above range, and ensures the high elastic modulus and flexibility of the adhesive, thereby effectively inhibiting the expansion of the pole piece material; and the uniform and stable dispersion of the active substances is facilitated, and the interfacial adhesion to the active substances and the current collector is ensured.
In various embodiments, the mass ratio of the comonomer I and the comonomer II to the organic compound containing 2 or more guanidine groups may be 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, or a range of any two of them.
In a specific embodiment of the invention, said copolymer comprises 40% to 80% of said comonomer I and 20% to 60% of said comonomer II in mass percent, based on the total amount of said copolymer. Further, the copolymer comprises 60-70% of the comonomer I and 30-40% of the comonomer II in percentage by mass. When the amount of the comonomer I in the copolymer is too small, the formed copolymer has insufficient stable dispersibility in an aqueous phase system, the suspension dispersion effect on slurry is poor, and the physical crosslinking effect formed between the copolymer and the guanidine group is weakened; when the amount of the comonomer II in the copolymer is too small, the interfacial adhesion between the formed copolymer and the active material and the current collector is insufficient, and the stability is not easy to maintain in the charge and discharge process. The invention further controls the dosage of the comonomer I and the comonomer II within the range, and ensures the suspension dispersion effect on the sizing agent, effectively inhibits the expansion of the pole piece material and ensures the formation of strong interface bonding with the active substance and the current collector.
As in the various embodiments, the mass percent of the comonomer i in the copolymer may be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or a range of any two thereof, based on the total amount of the copolymer; the mass percent of the comonomer II can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or any two of these ranges.
The invention also provides a preparation method of the adhesive, which comprises the following steps:
the comonomer I and the comonomer II are polymerized in situ in a liquid system comprising an organic compound containing more than 2 guanidino groups and an initiator.
The adhesive is prepared by in-situ polymerization, and the copolymer and the organic matter containing more than 2 guanidine groups can form an interpenetrating network, so that the inhibition effect on the expansion of the pole piece material is further improved.
In a specific embodiment of the invention, the initiator is used in an amount of 1% to 5% by weight, preferably 2% to 4% by weight, based on the sum of the masses of the interpolymer I and of the comonomer II. Further, the initiator includes at least one of ammonium persulfate, potassium persulfate, and sodium persulfate.
As in the various embodiments, the initiator may be used in an amount ranging from 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or any two of these, based on the mass sum of the interpolymer I and the comonomer II.
In a specific embodiment of the invention, the liquid system comprises a water system.
In a specific embodiment of the present invention, the preparation method comprises:
(a) Dissolving an organic matter containing more than 2 guanidine groups in water to prepare an aqueous solution of the organic matter containing more than 2 guanidine groups;
(b) Adding the comonomer I and the comonomer II into the aqueous solution, and uniformly dispersing; heating to initiator initiation temperature under protective atmosphere, adding initiator, reacting for 2-6 h, stopping reaction, and drying to obtain the final product.
In actual operation, the protective atmosphere comprises nitrogen; the initiation temperature refers to the temperature at which the initiator initiates the polymerization of the monomer through thermal decomposition, and can be adjusted according to the condition of the initiator.
In a specific embodiment of the present invention, the drying treatment comprises spray drying. The binder powder is obtained by means of conventional spray drying.
As in the various embodiments, the reaction time may be 2h, 3h, 4h, 5h, 6h, or a range of any two of these. After the reaction is finished, the temperature of the reaction system is reduced to room temperature to stop the reaction.
In a specific embodiment of the present invention, in the step (a), the mass fraction of the organic matter containing 2 or more guanidine groups in the aqueous solution of the organic matter containing 2 or more guanidine groups is 0.1% to 5%.
As in the various embodiments, the mass fraction of the organic containing more than 2 guanidino groups in the aqueous solution may be 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or a range consisting of any two thereof.
The invention also provides an electrode plate which comprises a current collector and an electrode membrane arranged on the current collector; the electrode membrane includes the binder therein.
The adhesive is elastic and flexible, can keep good adhesion effect with active substances in the battery cycle process, and has excellent fatigue resistance, so that the prepared negative electrode plate based on the adhesive has excellent performance.
In a specific embodiment of the invention, the electrode sheet comprises a negative electrode sheet.
In a specific embodiment of the present invention, the binder is used in an amount of 1% to 5% by mass, preferably 2% to 4% by mass, of the electrode membrane. So as to ensure the inhibition effect of the binder on the volume expansion of the electrode material, the energy density of the battery and the like.
As in the various embodiments, the binder may be used in an amount ranging from 1%, 2%, 3%, 4%, 5% or any two of the mass of the electrode membrane.
In a specific embodiment of the present invention, the active material in the electrode membrane comprises a silicon-based material. Further, the active material further includes a carbon material.
As in various embodiments, the silicon-based material comprises at least one of a silicon oxygen compound, a silicon carbon compound, silicon, and a silicon alloy; the carbon material includes at least one of natural graphite, artificial graphite, or mesophase carbon microbeads.
The invention also provides a secondary battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte; the negative electrode plate is the electrode plate.
Examples 1 to 15
Examples 1 to 15 provide binders and preparation methods thereof, and the types and amounts of raw materials used in examples 1 to 15 are specifically shown in table 1, and the specific preparation methods include:
(1) Weighing organic matters containing more than 2 guanidine groups, adding the organic matters into 2kg of deionized water, and stirring to fully dissolve the organic matters to prepare corresponding aqueous solution;
(2) Adding a comonomer I and a comonomer II into the aqueous solution, and stirring to uniformly disperse the comonomers I and the comonomers II to form a dispersion system; under the protection of nitrogen atmosphere, slowly heating to 80 ℃, adding ammonium persulfate (the ammonium persulfate dosage is 3% of the mass sum of the comonomer I and the comonomer II), uniformly stirring, and continuing to react for 4 hours. And cooling the reaction solution to room temperature to stop the reaction, and performing spray drying on the solution to obtain the binder.
TABLE 1 raw material types and amounts of the binders of examples 1 to 15
The preparation of the lithium ion battery comprises the following steps:
(1) Preparing a negative electrode plate: mixing graphite, a silicon oxide, carbon black and a binder material in a weight ratio of 72:24:1:3, and dispersing in deionized water to form a uniform slurry; and casting the slurry on a copper foil by a doctor blade method, drying at 70 ℃, cold pressing, trimming, cutting pieces, and drying at 100 ℃ under vacuum for 12 hours to obtain the negative electrode plate.
(2) 2025-type button half cell was assembled in a glove box filled with inert gas, wherein H 2 O and O 2 The content of (2) is less than 0.1ppm. The metal lithium sheet is used as a counter electrode, the PP/PE is used as a diaphragm, and 1M LiPF is used 6 (EC: EMC: dmc=1:1:1 vol%) +3% FEC (fluoroethylene carbonate) was used as the electrolyte.
Wherein, lithium ion batteries 1# to 15# respectively adopt the binder materials prepared in examples 1 to 15.
Comparative examples 1 to 4
Comparative examples 1 to 4 provide binders and a preparation method thereof, and the types and amounts of raw materials used in comparative examples 1 to 4 are specifically shown in table 2, and the specific preparation method comprises:
(1) Weighing the organic matter B, adding the organic matter B into 2kg of deionized water, and stirring to fully dissolve the organic matter B to prepare a corresponding aqueous solution;
(2) Adding a comonomer I and a comonomer II into the aqueous solution, and stirring to uniformly disperse the comonomers I and the comonomers II to form a dispersion system; under the protection of nitrogen atmosphere, slowly heating to 80 ℃, adding ammonium persulfate (the ammonium persulfate dosage is 3% of the mass sum of the comonomer I and the comonomer II), uniformly stirring, and continuing to react for 4 hours. And cooling the reaction solution to room temperature to stop the reaction, and performing spray drying on the solution to obtain the binder.
TABLE 2 raw material types and amounts of the binders of comparative examples 1 to 4
The reference examples of the preparation method of the lithium ion battery are different in that:
the lithium ion batteries of comparative examples 1 to 4 were respectively prepared using the binder materials of comparative examples 1 to 4.
Experimental example
Cycle performance test
Each of the above-prepared batteries was taken 3 pieces each, and the battery was repeatedly charged and discharged through the following steps, and the discharge capacity retention rate of the battery was calculated.
First, in an environment of 25 ℃, 0.5C was discharged to 5V, 0.05C was discharged to 5V, 0.02C was discharged to 5V, 0.01C was discharged to 5mV, and then 0.1C was charged to 1.5V, and the charge specific capacity of the first cycle was recorded. Then, 200 cycles of discharging and charging were performed, and the specific charge capacity at the 200 th cycle was recorded. According to the following formula:
cyclic capacity retention = 200 th cyclic charge specific capacity/first cyclic charge specific capacity 100%
The average capacity retention after cycling of each group of cells was calculated as shown in table 3.
Thickness expansion rate test for fully embedded state of negative pole piece
The thickness of the negative electrode plate before the assembled battery is measured and recorded as D 0 . The assembled battery was first discharged to 5mV at 0.1C and 5mV at 0.02C in a 25℃environment, leaving the negative electrode tab in a fully embedded state. Disassembling the battery, testing the thickness of the fully embedded negative electrode plate, and marking as D 1 . According to the following formula:
thickness expansion ratio= (D 1 -D 0 )/D 0 *100％
The thickness expansion rate of the negative electrode sheet in the fully embedded state was calculated as shown in table 3.
Table 3 results of performance tests of different batteries
From the above results, it is understood that the binder prepared in the examples of the present invention has both high elastic modulus and flexibility, and can effectively suppress expansion of the anode active material, compared with the comparative examples. In addition, the binder of the embodiment also contributes to uniform and stable dispersion of the anode active material, maintains good adhesion with the anode active material, and has excellent fatigue resistance, thereby greatly improving the performance of the battery.
As can be seen from examples 1 and examples 2 to 7, the present invention further improves the performance of the battery by further optimizing the comonomer constituting the copolymer and the organic matter containing 2 or more guanidine groups, and further balancing the mechanical properties of the binder, so that the anode tab prepared based thereon obtains an optimal expansion suppressing effect.
From examples 1 and 8 to 15, it is apparent that when the ratio of the comonomer I to the comonomer II of the synthetic copolymer is different and the ratio of the total amount of the comonomer to the organic matter having 2 or more guanidine groups is different, the expansion inhibition of the electrode plate and the cycle performance influence on the battery cell are also different. When the proportion of the comonomer I and the comonomer II and the proportion of the total amount of the comonomer and the organic matters containing more than 2 guanidine groups are in a certain range, the prepared adhesive is used for the battery pole piece, so that the expansion of the pole piece can be further inhibited and the cycle performance can be improved.
From example 1 and comparative examples 1 to 2, it is understood that when the comonomer i in the preparation of the adhesive is replaced with methyl acrylate containing no carboxylic acid group or sulfonic acid group, or an organic substance containing 2 or more guanidine groups is replaced with 1, 6-hexanediol containing no guanidine groups, the adhesive cannot effectively suppress the rebound expansion of the pole piece due to the inability to form strong physical cross-links of the carboxylic acid group or sulfonic acid group with the guanidine groups. As is clear from example 1 and comparative examples 3 to 4, when the organic matter having more than 2 guanidine groups is replaced with diethylenetriamine and polyethyleneimine having amine groups, the ability of the adhesive to suppress rebound swelling of the pole piece is significantly reduced because only weak physical cross-links can be formed between the carboxylic acid groups or the sulfonic acid groups and the amine groups.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An adhesive, characterized by comprising a copolymer and an organic substance containing more than 2 guanidine groups;
the comonomer of the copolymer comprises comonomer I and comonomer II;
the comonomer I comprises at least one of unsaturated carboxylic acid, unsaturated carboxylate, unsaturated sulfonic acid and unsaturated sulfonate;
the structural formula of the comonomer II is as follows:
2. The binder of claim 1 wherein the unsaturated carboxylic acid comprises at least one of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; the unsaturated carboxylic acid salt includes at least one of lithium salt, potassium salt and sodium salt of the unsaturated carboxylic acid;
the unsaturated sulfonate comprises at least one of sodium styrene sulfonate, sodium 3-prop-2-enoyloxy propane-1-sulfonate, potassium 3-sulfonate of methacrylic acid, inner N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonate and inner 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate;
preferably, the unsaturated carboxylic acid salt comprises at least one of lithium acrylate, sodium acrylate, lithium methacrylate and sodium methacrylate;
preferably, the unsaturated sulfonate includes at least one of a potassium salt of 3-sulfopropyl methacrylate, an inner salt of N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonate, and an inner salt of 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate.
3. The binder of claim 1 wherein the organic matter containing 2 or more guanidine groups comprises at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, chlorhexidine gluconate, chlorhexidine acetate, and iminoctadine;
preferably, the organic matter containing more than 2 guanidine groups comprises polyhexamethylene guanidine hydrochloride and/or polyhexamethylene biguanide hydrochloride.
4. The binder of claim 1 wherein the mass sum of said comonomer i and said comonomer ii to the mass ratio of said organic containing 2 or more guanidino groups is from (1 to 50):1;
preferably, the mass ratio of the mass of the comonomer I and the mass of the comonomer II to the mass of the organic compound containing more than 2 guanidine groups is (5-20):1.
5. The binder according to claim 1, wherein the copolymer comprises 40-80% by mass of the comonomer i and 20-60% by mass of the comonomer ii, based on the total amount of the copolymer;
preferably, the copolymer comprises 60-70% of the comonomer I and 30-40% of the comonomer II in percentage by mass.
6. The method for preparing the adhesive according to any one of claims 1 to 5, comprising the steps of:
the comonomer I and the comonomer II are polymerized in situ in a liquid system comprising an organic compound containing more than 2 guanidino groups and an initiator.
7. The method for preparing the adhesive according to claim 6, comprising:
(a) Dissolving an organic matter containing more than 2 guanidine groups in water to prepare an aqueous solution of the organic matter containing more than 2 guanidine groups;
(b) Adding the comonomer I and the comonomer II into the aqueous solution, and uniformly dispersing; heating to initiator initiation temperature under protective atmosphere, adding initiator, stopping reaction after 2-6 h, and drying to obtain binder;
preferably, in the step (a), the mass fraction of the organic matter containing more than 2 guanidine groups in the aqueous solution of the organic matter containing more than 2 guanidine groups is 0.1% -5%.
8. The electrode plate is characterized by comprising a current collector and an electrode membrane arranged on the current collector; the electrode membrane comprises the binder of any one of claims 1 to 5 or the binder prepared by the preparation method of any one of claims 6 to 7.
9. The electrode pad of claim 8, wherein the electrode pad comprises a negative electrode pad;
preferably, the amount of the binder is 1% -5% of the mass of the electrode membrane;
preferably, the active material in the electrode membrane comprises a silicon-based material;
more preferably, the active substance further comprises a carbon material.
10. The secondary battery is characterized by comprising a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte; the negative electrode sheet is the electrode sheet of claim 8 or 9.
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