CN112151802A - Negative electrode binder for lithium ion battery, preparation method of negative electrode binder and lithium ion battery containing negative electrode binder - Google Patents
Negative electrode binder for lithium ion battery, preparation method of negative electrode binder and lithium ion battery containing negative electrode binder Download PDFInfo
- Publication number
- CN112151802A CN112151802A CN202011022988.3A CN202011022988A CN112151802A CN 112151802 A CN112151802 A CN 112151802A CN 202011022988 A CN202011022988 A CN 202011022988A CN 112151802 A CN112151802 A CN 112151802A
- Authority
- CN
- China
- Prior art keywords
- parts
- negative electrode
- lithium ion
- ion battery
- electrode binder
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 239000011883 electrode binding agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 51
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 150000003440 styrenes Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 50
- 239000011734 sodium Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 39
- -1 alkyl sodium sulfate Chemical compound 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 18
- 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 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 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 13
- 238000000034 method Methods 0.000 claims description 12
- 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 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000001530 fumaric acid Substances 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- VZTFVVBTGBLXTR-UHFFFAOYSA-M sodium;2-(prop-2-enoylamino)propane-2-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(C)(C)NC(=O)C=C VZTFVVBTGBLXTR-UHFFFAOYSA-M 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- UBTITNUVKXQFBF-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCS(O)(=O)=O UBTITNUVKXQFBF-UHFFFAOYSA-N 0.000 claims description 3
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 8
- 229940077388 benzenesulfonate Drugs 0.000 description 8
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 4
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 4
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- FBKBIOOBMXQNBA-UHFFFAOYSA-N propane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)S(O)(=O)=O FBKBIOOBMXQNBA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- IMZGHXHAVUGEMC-UHFFFAOYSA-N C(C=C)(=O)NC(C)(C)[Na] Chemical compound C(C=C)(=O)NC(C)(C)[Na] IMZGHXHAVUGEMC-UHFFFAOYSA-N 0.000 description 1
- FJSPGHNSBJVXEH-UHFFFAOYSA-N C(C=C)(=O)NOS(=O)(=O)C(C)C.[Na] Chemical compound C(C=C)(=O)NOS(=O)(=O)C(C)C.[Na] FJSPGHNSBJVXEH-UHFFFAOYSA-N 0.000 description 1
- JOSAMYTWOJERPB-UHFFFAOYSA-N C(C=C)(=O)O.C(C)[Na] Chemical compound C(C=C)(=O)O.C(C)[Na] JOSAMYTWOJERPB-UHFFFAOYSA-N 0.000 description 1
- FXPMZZAJRYLBHB-UHFFFAOYSA-N C=CC=C.C(=O)(O)C=CC1=CC=C(C=C1)Br Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=C(C=C1)Br FXPMZZAJRYLBHB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KQFAFFYKLIBKDE-UHFFFAOYSA-M sodium;ethanesulfonate Chemical compound [Na+].CCS([O-])(=O)=O KQFAFFYKLIBKDE-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/18—Chlorine
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/20—Fluorine
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/21—Bromine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a negative electrode binder for a lithium ion battery, which comprises the following components in parts by weight: 100 parts of halogenated styrene, 80-110 parts of 1, 3-butadiene, 170-220 parts of deionized water, 0.4-1.5 parts of emulsifier 1, 0.4-1.5 parts of emulsifier 2, 0.8-3 parts of initiator 1, 20-30 parts of seed emulsion, 1-9 parts of carboxylic acid monomer 1, 0.5-2 parts of molecular weight regulator 1 and 0.1-2.7 parts of alkaline substance; compared with the prior art, the halogenated styrene-butadiene rubber emulsion binder for the lithium ion battery cathode is prepared by polymerizing the halogenated styrene and the 1, 3-butadiene to form a main body and matching the main body with other components, and the halogen atoms on the benzene ring increase the polarity of a high polymer and enhance the binding property, so that the halogenated styrene-butadiene rubber emulsion binder has good mechanical property and electrochemical stability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a negative electrode binder for a lithium ion battery, a preparation method of the negative electrode binder and the lithium ion battery containing the negative electrode binder.
Background
As a new energy product in the 21 st century, a lithium ion battery has many advantages such as high energy density, high discharge platform, long service life, no memory effect, wide use temperature range, high safety performance, environmental friendliness, and the like, and is widely applied to the fields of electric tools, smart phones, tablet computers, electric vehicles, and the like, particularly to the field of new energy electric vehicles.
The lithium ion battery is prepared by assembling a battery anode, a battery cathode and an isolating membrane, injecting electrolyte and activating. When the lithium ion battery pole piece is manufactured, a binder is needed, wherein the binder is an indispensable component without activity in the lithium ion battery, and mainly has the functions of binding electrode active substances and stabilizing the structure of the pole piece, so that the pole piece has good mechanical property and processability, and the active substances do not fall off in the charging and discharging process of the battery; another aspect is to enhance the electronic contact between the active material and the conductive agent and current collector. Therefore, the performance of the binder plays a key role in the adhesion of the positive and negative electrode slurry to the current collector. The performance of the adhesive is closely related to the cycle life of the battery, and if the mechanical property of the adhesive is poor, electrode slices are easily pulverized in the electrochemical cycle process, so that electrode materials fall off from the surface of a current collector and lose the electrochemical performance; secondly, when the electrochemical stability of the binder is not good, some functional groups of the binder can generate irreversible chemical reaction with lithium ions in the charging and discharging process of the battery, so that the reversible capacity of the battery is reduced. Some binders can also affect the mobility and the cycle performance of lithium ions, so that the influence of the binders on the electrical performance of the battery is reduced, and the improvement of the storage and cycle performance of the battery is extremely important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a negative electrode binder for a lithium ion battery, which is used for solving the problems of poor mechanical property and poor electrochemical stability of the existing binder in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme: the negative electrode binder for the lithium ion battery comprises the following components in parts by weight: 100 parts of halogenated styrene, 80-110 parts of 1, 3-butadiene, 170-220 parts of deionized water, 0.4-1.5 parts of emulsifier 1, 0.4-1.5 parts of emulsifier 2, 0.8-3 parts of initiator 1, 20-30 parts of seed emulsion, 1-9 parts of carboxylic acid monomer 1, 0.5-2 parts of molecular weight regulator 1 and 0.1-2.7 parts of alkaline substance.
Preferably, the seed emulsion comprises the following components in parts by weight: 85-95 parts of halogenated styrene, 250-381 parts of deionized water, 2-5 parts of emulsifier 3, 2-5 parts of emulsifier 4, 0.4-1 part of initiator 2, 5-15 parts of acrylate monomer, 0.2-1 part of carboxylic acid monomer 2 and 0.5-2 parts of molecular weight regulator 2.
Preferably, the emulsifier 1 and the emulsifier 3 are both anionic emulsifiers, and the anionic emulsifiers are selected from at least one of sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl diphenyl ether disulfonate, ammonium alkyl phenol ether sulfate and sodium alkyl phenol ether sulfosuccinate.
Preferably, the emulsifier 2 and the emulsifier 4 are both reactive emulsifiers, and the reactive emulsifiers are selected from at least one of sodium p-styrenesulfonate, 2-acrylamide-2, 2-dimethyl ethanesulfonate, sodium alkyl sulfosuccinate, sodium acrylamidoisopropyl sulfonate and sodium alkyl acrylate-2-ethanesulfonate.
Preferably, the initiator 1 and the initiator 2 are both selected from at least one of sodium persulfate, ammonium persulfate and potassium persulfate.
Preferably, the acrylate monomer is at least one selected from acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate and isobutyl acrylate.
Preferably, the carboxylic acid monomer 1 and the carboxylic acid monomer 2 are both selected from at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
Preferably, the molecular weight regulator 1 and the molecular weight regulator 2 are both selected from at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan and n-butyl mercaptan.
Preferably, the alkaline substance is selected from hydroxides of alkali metals.
The invention also adopts the following technical scheme: a preparation method of a negative electrode binder for a lithium ion battery comprises the following steps:
step one, adding deionized water, emulsifier 1, emulsifier 2, initiator 1 and seed emulsion after vacuumizing a polymerization kettle, starting stirring and heating to 70-90 ℃;
step two: dropwise adding a mixture solution of halogenated styrene, 1, 3-butadiene, carboxylic acid monomer 1 and molecular weight regulator 1 into the heated mixed solution for free radical emulsion polymerization, wherein the reaction time is 3-6h, and keeping the temperature for 2h after heating to 90 ℃;
step three: and cooling the mixed solution subjected to heat preservation in the step two, adjusting the pH value to be 5-9 by using an alkaline substance after cooling, and filtering to obtain the negative electrode binder for the lithium ion battery.
Preferably, the preparation method of the seed emulsion comprises the following steps:
vacuumizing a polymerization kettle, adding deionized water, an emulsifier 3, an emulsifier 4 and an initiator 2, stirring, heating to 70-90 ℃, dropwise adding a mixture solution of halogenated styrene, an acrylate monomer, a carboxylic acid monomer 2 and a molecular weight regulator 2 for free radical emulsion polymerization, reacting for 3-6 hours, heating to 90 ℃, preserving heat for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
The invention also adopts the following technical scheme: the lithium ion battery comprises the negative electrode binder for the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the halogenated styrene-butadiene rubber emulsion binder for the lithium ion battery cathode is prepared by polymerizing the halogenated styrene and the 1, 3-butadiene to form a main body and matching the main body with other components, and the presence of halogen atoms on a benzene ring increases the polarity of a high polymer and enhances the binding property, so that the halogenated styrene-butadiene rubber emulsion binder has good mechanical property and electrochemical stability;
2. when the negative electrode binder for the lithium ion battery is matched with sodium carboxymethylcellulose for use, the addition amount is small, so that the negative electrode active substance can be firmly adhered to a current collector copper foil by the addition amount not more than 1%, the negative electrode active substance is not easy to fall off, and the bonding force is strong.
3. The addition amount of the negative electrode binder for the lithium ion battery is small when the negative electrode binder is used as the negative electrode binder of the lithium ion battery, so that the content of the negative electrode active substance is increased, the volumetric specific energy of the lithium ion battery is indirectly improved, and the internal resistance of the battery is reduced.
4. The lithium ion battery prepared by the negative electrode binder for the lithium ion battery has the advantages that the negative electrode is not easy to fall off powder in the charge-discharge cycle use process, and the service life of the battery is long.
Detailed Description
The present invention will be described in further detail below by way of specific embodiments:
the halogenated styrene in this scheme has the following structural formula:
wherein, X is halogen atom (F, Cl, Br, I); the weight average molecular weight of the polymer of the halogenated styrene and the 1, 3-butadiene is 30-35 ten thousand, and the number average molecular weight is 20-30 ten thousand.
Example 1
The seed emulsion comprises the following components in parts by weight:
deionized water: 250 parts of (A); sodium alkyl sulfate: 1 part; sodium alkyl sulfonate: 1 part; 2 parts of sodium p-styrene sulfonate; sodium persulfate: 0.4 part; 4-F-styrene: 85 parts of a mixture; acrylonitrile: 5 parts of a mixture; acrylic acid: 0.2 part; n-dodecyl mercaptan: 0.5 part.
The preparation method of the seed emulsion comprises the following steps: vacuumizing a polymerization kettle, adding deionized water, sodium alkyl sulfate, sodium alkyl sulfonate, sodium p-styrene sulfonate and sodium persulfate, starting stirring, heating to 70 ℃, dropwise adding a mixture of 4-F-styrene, acrylonitrile, acrylic acid and n-dodecyl mercaptan for free radical emulsion polymerization, reacting for 3 hours, heating to 90 ℃, preserving heat for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
The negative electrode binder for the lithium ion battery comprises the following components in parts by weight:
deionized water: 170 parts of a mixture; sodium alkyl diphenyl ether disulfonate: 0.4 part; 2-acrylamide-2, 2-dimethylethanesulfonic acid sodium salt: 0.4 part; sodium persulfate: 0.8 part; seed emulsion: 20 parts of (1); 4-F-styrene: 100 parts of (A); 1, 3-butadiene: 80 parts of a mixture; acrylic acid: 1 part; n-dodecyl mercaptan: 0.5 part; sodium hydroxide solution (10% concentration): 1 part.
The preparation method of the negative electrode binder for the lithium ion battery comprises the following steps:
vacuumizing a polymerization kettle, adding deionized water, sodium alkyl diphenyl ether disulfonate, 2-acrylamide-2, 2-dimethyl ethanesulfonate, sodium persulfate and seed emulsion, starting stirring and heating to 70 ℃; dropwise adding a mixture of 4-F-styrene, 1, 3-butadiene, acrylic acid and n-dodecyl mercaptan into the mixture to perform free radical emulsion polymerization, reacting for 3 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 5 by using a 10% sodium hydroxide aqueous solution, and filtering to obtain the carboxyl 4-F-styrene 1, 3-butadiene polymer emulsion, namely the negative electrode binder for the lithium ion battery.
Manufacturing a battery negative plate:
the active material graphite, carbon black, the carboxyl 4-F-styrene 1, 3-butadiene polymer emulsion binder prepared in the example and sodium carboxymethyl cellulose were mixed according to the mass ratio of 96.6:1:1:1.4, and the process was as follows:
96.6 parts by mass of graphite, 1 part by mass of carbon black and 1.4 parts by mass of sodium carboxymethylcellulose dry powder are mixed for 30 minutes, 110 parts by mass of deionized water are added and stirred uniformly, and finally 1 part by mass of the binder prepared in the embodiment is added and stirred uniformly. And coating the prepared negative electrode slurry on a copper foil, drying and preparing a sheet.
The negative electrode sheet obtained above was randomly cut into a shape of 100mm in length and 10mm in width. A clean glass plate with the width of 30mm is taken, a double-sided adhesive tape (with the width of 12mm) is pasted on the double-sided adhesive tape on the glass plate, and a 2000g compression roller is used for rolling the surface of the plate back and forth for 3 times (300 m/min). The pole piece is bent by 180 degrees in the width direction, the pole piece is manually peeled by 25mm, a sample is fixed on a testing machine, the peeling surface is kept consistent with the force line of the testing machine, the testing machine continuously peels at the speed of 300mm/min to obtain a peeling curve, the average value of the stable sections is taken as the peeling force F, the adhesive force of the tested negative pole piece is F1 which is 100F (N/m), and the measured result is shown in table 1.
Manufacturing a lithium ion battery:
the lithium nickel cobalt manganese oxide is used as a positive active material, the carbon nano tube is used as a conductive agent, the PVDF is used as a binder, and the NMP is used as a solvent to prepare a positive plate, and the lithium nickel cobalt manganese oxide is used as a solute, and the lithium nickel cobalt manganese oxide is used as an electrolyte of the solvent to assemble and prepare the 2Ah cylindrical lithium ion battery.
Testing the internal resistance of the battery: the battery internal resistance test is carried out on the prepared battery by using a voltage internal resistance instrument, and the result is shown in the table I.
Capacity retention test after 500 cycles: the prepared battery is placed on a cycle test cabinet for experiments to perform normal-temperature charge-discharge cycle test at a rate of 1C, and the test result of the capacity retention rate of the battery after 500 cycles is shown in Table 1.
Example 2
The seed emulsion comprises the following components in parts by weight:
deionized water: 289 parts; sodium alkyl sulfonate: 3 parts of a mixture; sodium alkyl benzene sulfonate: 2 parts of (1); 3 parts of sodium p-styrene sulfonate; sodium acrylamidoisopropyl sulfonate: 2 parts of (1); ammonium persulfate: 1 part; 4-Cl-styrene: 95 parts of (C); n-butyl acrylate: 10 parts of (A); isobutyl acrylate: 5 parts of a mixture; maleic acid: 1 part; tertiary dodecyl mercaptan: and 2 parts.
The preparation method of the seed emulsion comprises the following steps: vacuumizing a polymerization kettle, adding deionized water, sodium alkylsulfonate, sodium alkyl benzene sulfonate, sodium p-styrene sulfonate, acrylamide isopropyl sulfonate and ammonium persulfate, starting stirring, heating to 90 ℃, dropwise adding a mixture of 4-Cl-styrene, n-butyl acrylate, isooctyl acrylate, maleic acid and tert-dodecyl mercaptan, carrying out free radical emulsion polymerization for 6 hours, heating to 90 ℃, keeping the temperature for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
The negative electrode binder for the lithium ion battery comprises the following components in parts by weight:
deionized water: 211.4 parts of a binder; sodium alkyl sulfonate: 1 part; sodium alkyl benzene sulfonate: 0.5 part; sodium p-styrenesulfonate: 1 part; sodium acrylamidoisopropyl sulfonate: 0.5 part; ammonium persulfate: 3 parts of a mixture; seed emulsion: 30 parts of (1); 4-Cl-styrene: 100 parts of (A); 1, 3-butadiene: 110 parts of (A); maleic acid: 5 parts of a mixture; itaconic acid: 4 parts of a mixture; tertiary dodecyl mercaptan: 2 parts of (1); sodium hydroxide solution (10% concentration): 9 parts.
The preparation method of the negative electrode binder for the lithium ion battery comprises the following steps:
and (2) after the polymerization kettle is vacuumized, adding deionized water, sodium alkylsulfonate, sodium alkyl benzene sulfonate, sodium p-styrene sulfonate, acrylamide isopropyl sulfonate, ammonium persulfate and seed emulsion, starting stirring, heating to 90 ℃, dropwise adding a mixture of 4-Cl-styrene, 1, 3-butadiene, maleic acid, itaconic acid and tert-dodecyl mercaptan, carrying out free radical emulsion polymerization, reacting for 6 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 7 by using a 10% sodium hydroxide solution, and filtering to obtain the carboxyl 4-Cl-styrene 1, 3-butadiene polymer emulsion, namely the negative electrode binder for the lithium ion battery.
Manufacturing a battery negative plate:
the formulation and procedure were as in example 1.
The adhesion of the negative electrode sheet to the copper foil was tested in the same manner as in example one.
Manufacturing a lithium ion battery:
a lithium ion battery was produced in the same manner as in example 1, and the internal resistance and the capacity retention rate after 500 cycles of the battery were measured, and the results are shown in table one.
Example 3
The seed emulsion comprises the following components in parts by weight:
ionized water: 255.5 parts; sodium alkyl benzene sulfonate: 2 parts of (1); sodium alkylphenol ether sulfosuccinate: 1.5 parts; sodium alkyl sulfosuccinate: 2 parts of (1); sodium 2-ethanesulfonate alkyl acrylate: 1.5 parts; potassium persulfate: 0.7 part; 4-Br-styrene: 90 parts of a mixture; methyl acrylate: 10 parts of (A); methacrylic acid: 0.6 part; n-butylmercaptan: 1.2 parts.
The preparation method of the seed emulsion comprises the following steps: and (2) vacuumizing a polymerization kettle, adding deionized water, sodium alkyl benzene sulfonate, sodium alkylphenol ether sulfosuccinate, sodium allyl succinic acid alkyl ester sulfonate, alkyl acrylic acid-2-sodium ethanesulfonate and potassium persulfate, starting stirring, heating to 80 ℃, dropwise adding a mixture of 4-Br-styrene, methyl acrylate, methacrylic acid and n-butyl mercaptan, carrying out free radical emulsion polymerization for 4.5 hours, heating to 90 ℃, keeping the temperature for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
The negative electrode binder for the lithium ion battery comprises the following components in parts by weight:
deionized water: 192 parts of; sodium alkyl benzene sulfonate: 0.5 part; sodium alkylphenol ether sulfosuccinate: 0.5 part; sodium alkyl sulfosuccinate alkyl ester: 0.5 part; sodium 2-ethanesulfonate alkyl acrylate: 0.5 part; potassium persulfate: 2 parts of (1); seed emulsion: 25 parts of (1); 4-Br-styrene: 100 parts of (A); 1, 3-butadiene: 95 parts of (C); methacrylic acid: 3 parts of a mixture; itaconic acid: 2 parts of (1); n-butylmercaptan: 1 part; sodium hydroxide solution (10% concentration): 5 parts of the raw materials.
The preparation method of the negative electrode binder for the lithium ion battery comprises the following steps:
and (2) after the polymerization kettle is vacuumized, adding deionized water, sodium alkyl benzene sulfonate, sodium alkylphenol ether sulfosuccinate, sodium allyl succinic acid alkyl ester sulfonate, sodium alkyl acrylate-2-ethanesulfonate, potassium persulfate and seed emulsion, starting stirring, heating to 80 ℃, dropwise adding a mixture of 4-Br-styrene, 1, 3-butadiene, methacrylic acid, itaconic acid and n-butyl mercaptan, carrying out free radical emulsion polymerization, reacting for 4.5 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 9 by using a 10% sodium hydroxide solution, and filtering to obtain a carboxyl 4-Br-styrene 1, 3-butadiene polymer emulsion, namely the negative electrode binder for the lithium ion battery.
Manufacturing a battery negative plate:
the formulation and procedure were as in example 1.
The adhesion of the negative electrode sheet to the copper foil was tested in the same manner as in example one.
Manufacturing a lithium ion battery:
a lithium ion battery was produced in the same manner as in example 1, and the internal resistance and the capacity retention rate after 500 cycles of the battery were measured, and the results are shown in table one.
Example 4
The seed emulsion comprises the following components in parts by weight:
deionized water: 331 parts of; sodium alkyl sulfate: 3 parts of a mixture; ammonium alkylphenol ether sulfate: 2 parts of (1); 2 parts of sodium p-styrene sulfonate; ammonium persulfate: 0.8 part; 4-I-styrene: 95 parts of (C); ethyl acrylate: 5 parts of a mixture; n-butyl acrylate: 5 parts of a mixture; isobutyl acrylate: 5 parts of a mixture; fumaric acid: 0.8 part; methacrylic acid: 0.2 part; n-butylmercaptan: 0.8 part; n-dodecyl mercaptan: 1 part; 0.2 part of tertiary dodecyl mercaptan.
The preparation method of the seed emulsion comprises the following steps: vacuumizing a polymerization kettle, adding deionized water, sodium alkyl sulfate, ammonium alkylphenol ether sulfate, sodium p-styrenesulfonate and ammonium persulfate, starting stirring, heating to 80 ℃, dropwise adding a mixture of 4-I-styrene, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, fumaric acid, methacrylic acid, n-butyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, carrying out free radical emulsion polymerization for 4 hours, heating to 90 ℃, keeping the temperature for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
Deionized water: 193.7 parts; sodium alkyl sulfate: 1.5 parts; sodium p-styrenesulfonate: 0.4 part; ammonium persulfate: 2 parts of (1); sodium persulfate: 0.5 part; seed emulsion: 30 parts of (1); 4-I-styrene: 100 parts of (A); 1, 3-butadiene: 110 parts of (A); fumaric acid: 5 parts of a mixture; acrylic acid: 2 parts of (1); n-butylmercaptan: 0.5 part; n-dodecyl mercaptan: 1 part; sodium hydroxide solution (10% concentration): 7 parts.
The preparation method of the negative electrode binder for the lithium ion battery comprises the following steps:
and (2) vacuumizing a polymerization kettle, adding deionized water, sodium alkyl sulfate, sodium p-styrene sulfonate, ammonium persulfate, sodium persulfate and seed emulsion, stirring, heating to 85 ℃, dropwise adding a mixture of 4-I-styrene, 1, 3-butadiene, fumaric acid, acrylic acid, n-butyl mercaptan and n-dodecyl mercaptan, carrying out free radical emulsion polymerization, reacting for 5 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 6 by using a 10% sodium hydroxide solution, and filtering to obtain the carboxyl 4-I-styrene 1, 3-butadiene polymer emulsion, namely the negative electrode binder for the lithium ion battery.
Manufacturing a battery negative plate:
the formulation and procedure were as in example 1.
The adhesion of the negative electrode sheet to the copper foil was tested in the same manner as in example one.
Manufacturing a lithium ion battery:
a lithium ion battery was produced in the same manner as in example 1, and the internal resistance and the capacity retention rate after 500 cycles of the battery were measured, and the results are shown in table one.
Example 5
The seed emulsion comprises the following components in parts by weight:
deionized water: 381 parts of; sodium alkyl sulfate: 2 parts of (1); ammonium alkylphenol ether sulfate: 2 parts of (1); alkylphenol ether sulfosuccinate sodium salt: 1 part; sodium alkyl sulfosuccinate alkyl ester: 2 parts of (1); sodium acrylamidoisopropyl sulfonate: 2 parts of (1); 2-ethanesulfonic acid sodium salt of alkylacrylic acid: 1 part; ammonium persulfate: 0.8 part; potassium persulfate: 0.2 part; 4-I-styrene: 95 parts of (C); ethyl acrylate: 5 parts of a mixture; n-butyl acrylate: 5 parts of a mixture; isobutyl acrylate: 5 parts of a mixture;
fumaric acid: 0.8 part; methacrylic acid: 0.2 part;
n-butylmercaptan: 1 part; n-dodecyl mercaptan: 1 part.
The preparation method of the seed emulsion comprises the following steps: vacuumizing a polymerization kettle, adding deionized water, sodium alkyl sulfate, ammonium alkylphenol ether sulfate, sodium alkylphenol ether sulfosuccinate, sodium allyl succinic acid alkyl ester sulfonate, acrylamido isopropyl sodium sulfonate, alkyl acrylic acid-2-ethyl sodium sulfonate, ammonium persulfate and potassium persulfate, starting stirring, heating to 80 ℃, dropwise adding a mixture of 4-I-styrene, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, fumaric acid, methacrylic acid, n-butyl mercaptan and n-dodecyl mercaptan, carrying out free radical emulsion polymerization for 4 hours, heating to 90 ℃, keeping the temperature for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
The negative electrode binder for the lithium ion battery comprises the following components in parts by weight:
deionized water: 220 parts of (1); sodium alkyl sulfate: 1 part; sodium alkyl diphenyl ether disulfonate: 0.5 part; sodium p-styrenesulfonate: 0.4 part; sodium alkyl sulfosuccinate alkyl ester: 0.5 part; sodium acrylamidoisopropyl sulfonate: 0.6 part; ammonium persulfate: 2 parts of (1); sodium persulfate: 0.5 part; potassium persulfate: 0.5 part; seed emulsion: 30 parts of (1); 4-I-styrene: 100 parts of (A); 1, 3-butadiene: 110 parts of (A); fumaric acid: 5 parts of a mixture; acrylic acid: 2 parts of (1); maleic acid: 2 parts of (1); tertiary dodecyl mercaptan: 1 part; n-dodecyl mercaptan: 1 part; sodium hydroxide solution (10% concentration): 27 parts of (A).
The preparation method of the negative electrode binder for the lithium ion battery comprises the following steps:
after a polymerization kettle is vacuumized, adding deionized water, sodium alkyl sulfate, sodium alkyl diphenyl ether disulfonate, sodium p-styrene sulfonate, sodium allyl succinic acid alkyl ester sulfonate, sodium acrylamido isopropyl sulfonate, ammonium persulfate, sodium persulfate, potassium persulfate and a seed emulsion, starting stirring, heating to 85 ℃, dropwise adding a mixture of 4-I-styrene, 1, 3-butadiene, fumaric acid, acrylic acid, maleic acid, tertiary dodecyl mercaptan and n-dodecyl mercaptan, carrying out free radical emulsion polymerization for 5 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 8 by using a 10% sodium hydroxide solution, and filtering to obtain a carboxyl 4-I-styrene 1, 3-butadiene polymer emulsion, namely the negative electrode binder for the lithium ion battery.
Manufacturing a battery negative plate:
the formulation and procedure were as in example 1.
The adhesion of the negative electrode sheet to the copper foil was tested in the same manner as in example one.
Manufacturing a lithium ion battery:
a lithium ion battery was produced in the same manner as in example 1, and the internal resistance and the capacity retention rate after 500 cycles of the battery were measured, and the results are shown in table one.
Comparative example 1:
the preparation method is similar to the negative electrode preparation method in the first embodiment in that graphite, carbon black, commercially available styrene butadiene rubber emulsion and sodium carboxymethylcellulose are prepared according to the mass ratio of 95.6:1:2: 1.4.
The adhesion between the negative electrode sheet and the copper foil was measured in the same manner as in example 1, and the results are shown in Table 1.
The same method as in example 1 was used to fabricate a battery, and the internal resistance of the battery was measured, and the results of capacity retention after 500 cycles of the battery are shown in table 1.
TABLE 1
As can be seen from Table 1, the 4-X-styrene 1, 3-butadiene polymer emulsion prepared by the invention is applied to the lithium ion battery, although the usage amount of the binder is reduced by half compared with the commercial styrene-butadiene rubber emulsion, the 4-X-styrene 1, 3-butadiene polymer emulsion still has the same binding power as the commercial styrene-butadiene rubber emulsion, reduces the internal resistance of the battery, and obviously improves the cycle performance of the battery. The negative electrode binder used in the invention has the advantages of small usage amount and strong binding power, so that the usage amount of the binder can be reduced, more active substances can be used for the negative electrode plate with the same weight, the energy density of the battery is improved, and the internal resistance of the battery is reduced.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. The negative electrode binder for the lithium ion battery is characterized by comprising the following components in parts by weight: 100 parts of halogenated styrene, 80-110 parts of 1, 3-butadiene, 170-220 parts of deionized water, 0.4-1.5 parts of emulsifier 1, 0.4-1.5 parts of emulsifier 2, 0.8-3 parts of initiator 1, 20-30 parts of seed emulsion, 1-9 parts of carboxylic acid monomer 1, 0.5-2 parts of molecular weight regulator 1 and 0.1-2.7 parts of alkaline substance.
2. The negative electrode binder for a lithium ion battery according to claim 1, characterized in that: the seed emulsion comprises the following components in parts by weight: 85-95 parts of halogenated styrene, 250-381 parts of deionized water, 2-5 parts of emulsifier 3, 2-5 parts of emulsifier 4, 0.4-1 part of initiator 2, 5-15 parts of acrylate monomer, 0.2-1 part of carboxylic acid monomer 2 and 0.5-2 parts of molecular weight regulator 2.
3. The negative electrode binder for a lithium ion battery according to claim 2, characterized in that: the emulsifier 1 and the emulsifier 3 are both anionic emulsifiers, and the anionic emulsifiers are selected from at least one of alkyl sodium sulfate, alkyl sodium sulfonate, alkyl diphenyl ether disulfonate, alkyl phenol ether ammonium sulfate and alkyl phenol ether sulfosuccinate sodium salt.
4. The negative electrode binder for a lithium ion battery according to claim 2, characterized in that: the emulsifier 2 and the emulsifier 4 are reactive emulsifiers, and the reactive emulsifiers are selected from at least one of sodium p-styrene sulfonate, 2-acrylamide-2, 2-dimethyl ethyl sulfonate, sodium alkyl allyl succinate sulfonate, sodium acrylamidoisopropyl sulfonate and sodium alkyl acrylate-2-ethyl sulfonate.
5. The negative electrode binder for a lithium ion battery according to claim 2, characterized in that: the initiator 1 and the initiator 2 are both selected from at least one of sodium persulfate, ammonium persulfate and potassium persulfate.
6. The negative electrode binder for a lithium ion battery according to claim 2, characterized in that: the acrylate monomer is at least one of acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate and isobutyl acrylate.
7. The negative electrode binder for a lithium ion battery according to claim 2, characterized in that: the carboxylic acid monomer 1 and the carboxylic acid monomer 2 are both selected from at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
8. A method for preparing the negative electrode binder for a lithium ion battery according to any one of claims 2 to 7,
the method is characterized by comprising the following steps:
step one, adding deionized water, emulsifier 1, emulsifier 2, initiator 1 and seed emulsion after vacuumizing a polymerization kettle, starting stirring and heating to 70-90 ℃;
step two: dropwise adding a mixture solution of halogenated styrene, 1, 3-butadiene, carboxylic acid monomer 1 and molecular weight regulator 1 into the heated mixed solution for free radical emulsion polymerization, wherein the reaction time is 3-6h, and keeping the temperature for 2h after heating to 90 ℃;
step three: and cooling the mixed solution subjected to heat preservation in the step two, adjusting the pH value to be 5-9 by using an alkaline substance after cooling, and filtering to obtain the negative electrode binder for the lithium ion battery.
9. The preparation method of the negative electrode binder for the lithium ion battery as claimed in claim 8, wherein the preparation method of the seed emulsion comprises the following steps:
vacuumizing a polymerization kettle, adding deionized water, an emulsifier 3, an emulsifier 4 and an initiator 2, stirring, heating to 70-90 ℃, dropwise adding a mixture solution of halogenated styrene, an acrylate monomer, a carboxylic acid monomer 2 and a molecular weight regulator 2 for free radical emulsion polymerization, reacting for 3-6 hours, heating to 90 ℃, preserving heat for 0.5 hour, cooling, and filtering to obtain the seed emulsion.
10. A lithium ion battery comprising the negative electrode binder for a lithium ion battery according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011022988.3A CN112151802A (en) | 2020-09-25 | 2020-09-25 | Negative electrode binder for lithium ion battery, preparation method of negative electrode binder and lithium ion battery containing negative electrode binder |
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| CN113736002A (en) * | 2021-09-13 | 2021-12-03 | 江西迪比科股份有限公司 | Modified polyhalogenated styrene-1, 3-butadiene emulsion binder, preparation and application thereof |
| CN113913130A (en) * | 2021-10-14 | 2022-01-11 | 惠州亿纬锂能股份有限公司 | Negative electrode emulsion binder and preparation method and application thereof |
| CN114957534A (en) * | 2021-08-12 | 2022-08-30 | 广州荣东新材料有限公司 | Heat-resistant battery negative electrode binder and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114957534A (en) * | 2021-08-12 | 2022-08-30 | 广州荣东新材料有限公司 | Heat-resistant battery negative electrode binder and preparation method thereof |
| CN114957534B (en) * | 2021-08-12 | 2024-03-26 | 广州荣东新材料有限公司 | Heat-resistant battery negative electrode binder and preparation method thereof |
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| CN113913130A (en) * | 2021-10-14 | 2022-01-11 | 惠州亿纬锂能股份有限公司 | Negative electrode emulsion binder and preparation method and application thereof |
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