CN117242634A - Coating material raw material for secondary battery separator, coating material for secondary battery separator, method for producing secondary battery separator, and secondary battery - Google Patents
Coating material raw material for secondary battery separator, coating material for secondary battery separator, method for producing secondary battery separator, and secondary battery Download PDFInfo
- Publication number
- CN117242634A CN117242634A CN202280029862.XA CN202280029862A CN117242634A CN 117242634 A CN117242634 A CN 117242634A CN 202280029862 A CN202280029862 A CN 202280029862A CN 117242634 A CN117242634 A CN 117242634A
- Authority
- CN
- China
- Prior art keywords
- water
- secondary battery
- battery separator
- reactive functional
- mass
- 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
- 239000002994 raw material Substances 0.000 title claims abstract description 124
- 238000000576 coating method Methods 0.000 title claims abstract description 122
- 239000011248 coating agent Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 157
- 125000000524 functional group Chemical group 0.000 claims abstract description 140
- 229920003176 water-insoluble polymer Polymers 0.000 claims abstract description 119
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims description 169
- 229920002554 vinyl polymer Polymers 0.000 claims description 73
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 36
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 25
- 230000009477 glass transition Effects 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 description 30
- 230000008859 change Effects 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 25
- 230000035699 permeability Effects 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- 239000002346 layers by function Substances 0.000 description 13
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000005484 gravity Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002861 polymer material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 230000000379 polymerizing effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000004815 dispersion polymer Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 125000001302 tertiary amino group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Chemical group 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229920001223 polyethylene glycol Chemical group 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910001648 diaspore Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- NZQQFMVULBBDSP-FPLPWBNLSA-N bis(4-methylpentan-2-yl) (z)-but-2-enedioate Chemical compound CC(C)CC(C)OC(=O)\C=C/C(=O)OC(C)CC(C)C NZQQFMVULBBDSP-FPLPWBNLSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000006277 halobenzyl group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The coating material raw material for secondary battery separator contains a coating material having an SP value of 13.0 (cal/cm) 3 ) 1/2 The water-soluble polymer has a SP value of less than 13.0 (cal/cm 3 ) 1/2 Is a composite polymer of a water-insoluble polymer. The water-soluble polymer comprises the 1 st reactive functional group. The water insoluble polymer comprises a 2 nd reactive functional group capable of chemically bonding with the 1 st reactive functional group. In the composite polymer, at least a portion of the 1 st reactive functional group is chemically bonded to at least a portion of the 2 nd reactive functional group.
Description
Technical Field
The present invention relates to a coating material raw material for secondary battery separator, a coating material for secondary battery separator, a method for producing a secondary battery separator, and a secondary battery.
Background
Conventionally, a secondary battery is provided with a separator for separating a positive electrode from a negative electrode and passing ions in an electrolyte.
As such a separator, for example, a polyolefin porous film is known, and it is also known to provide various functional layers on the surface of the separator.
As a functional layer formed on a separator, for example, a functional layer obtained by coating a composition for a functional layer containing alumina and a resin on a polyethylene separator substrate and drying the same is known. As a composition for a functional layer, a mixture of a water-soluble polymer obtained by polymerizing acrylamide, methacrylic acid, and dimethylacrylamide, a particulate polymer obtained by polymerizing N-butyl acrylate, methacrylic acid, acrylonitrile, N-methylolacrylamide, and allyl glycidyl ether, alumina, a dispersant, and a surfactant has been proposed (for example, see patent document 1 (example 1)).
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/026095
Disclosure of Invention
Problems to be solved by the invention
On the other hand, if the shape of the separator changes due to shrinkage by heat, there is a possibility that a short circuit may occur between the positive electrode and the negative electrode. Therefore, heat resistance is required for the functional layer. However, the functional layer described above has a disadvantage that heat resistance is insufficient.
In addition, the separator of the secondary battery needs to pass ions in order to generate electricity. Therefore, breathability is required for the functional layer. However, the functional layer described above has a problem that the air permeability of the separator is reduced.
Further, improvement of adhesion to the separator is required for the functional layer. However, the functional layer described above has a problem that adhesion to the separator is insufficient.
In addition, the composition for a functional layer is required to have storage stability, uniform dispersibility, and low tackiness from the viewpoint of productivity of the functional layer.
The present invention provides a secondary battery separator which has excellent heat resistance, air permeability and adhesion, and further has excellent storage stability, uniform dispersibility and low viscosity, a secondary battery separator coating material comprising the secondary battery separator coating material, a secondary battery separator comprising the secondary battery separator coating film, a method for producing the secondary battery separator, and a secondary battery comprising the secondary battery separator.
Means for solving the problems
The invention [1 ]]Comprises a coating material raw material for secondary battery separator comprising a material having an SP value of 13.0 (cal/cm 3 ) 1/2 The water-soluble polymer has a SP value of less than 13.0 (cal/cm 3 ) 1/2 The water-insoluble polymer includes a 1 st reactive functional group, the water-insoluble polymer includes a 2 nd reactive functional group capable of chemically bonding to the 1 st reactive functional group, and at least a part of the 1 st reactive functional group and at least a part of the 2 nd reactive functional group are chemically bonded to each other in the composite polymer.
The invention [2] includes the coating material raw material for a secondary battery separator according to [1], wherein the 1 st reactive functional group of the water-soluble polymer contains a carboxyl group and the 2 nd reactive functional group of the water-insoluble polymer contains a glycidyl group.
The invention [3] includes the coating material raw material for a secondary battery separator according to [1] or [2], wherein the water-soluble polymer has a repeating unit derived from (meth) acrylamide and a repeating unit derived from a carboxyl group-containing vinyl monomer, and the water-insoluble polymer has a repeating unit derived from an alkyl (meth) acrylate and a repeating unit derived from a glycidyl group-containing vinyl monomer.
The invention [4] includes the coating material raw material for a secondary battery separator according to any one of [1] to [3], wherein the water-soluble polymer is 50 parts by mass to 99 parts by mass, and the water-insoluble polymer is 1 part by mass to 50 parts by mass, based on 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer.
The invention [5] includes the coating material raw material for a secondary battery separator according to any one of the above [1] to [4], wherein the weight average molecular weight of the water-soluble polymer is 1 to 20 tens of thousands.
The invention [6] includes the coating material raw material for a secondary battery separator according to any one of the above [1] to [5], wherein the water-soluble polymer has a glass transition temperature of 150 ℃ to 240 ℃.
The invention [7] includes the coating material raw material for a secondary battery separator according to any one of the above [1] to [6], wherein the glass transition temperature of the water-insoluble polymer is from-40 ℃ to 50 ℃.
The invention [8] includes a coating material for a secondary battery separator, which contains the coating material raw material for a secondary battery separator described in any one of the above [1] to [7 ].
The invention [9] includes the coating material for a secondary battery separator described in the above [8], which further contains an inorganic filler and a dispersant.
The invention [10] includes a secondary battery separator comprising a porous film and a coating film of the coating material for a secondary battery separator described in [8] or [9], wherein the coating film is disposed on at least one surface of the porous film.
The invention [11] includes a method for manufacturing a secondary battery separator, comprising the steps of: preparing a porous film; and a step of applying the coating material for a secondary battery separator according to [8] or [9] to at least one surface of the porous film.
The invention [12] includes a secondary battery comprising a positive electrode, a negative electrode, and the secondary battery separator described in the above [10] disposed between the positive electrode and the negative electrode.
Effects of the invention
The coating material raw material for a secondary battery separator of the present invention comprises a composite polymer of a water-soluble polymer and a non-water-soluble polymer, the water-soluble polymer comprising a 1 st reactive functional group, the non-water-soluble polymer comprising a 2 nd reactive functional group capable of chemically bonding to the 1 st reactive functional group, at least a part of the 1 st reactive functional group being chemically bonded to at least a part of the 2 nd reactive functional group in the composite polymer.
Therefore, the coating material raw material for a secondary battery separator of the present invention is excellent in storage stability, uniform dispersibility, and low viscosity. Further, according to the coating material raw material for a secondary battery separator of the present invention, a secondary battery separator excellent in heat resistance, air permeability and adhesion can be obtained.
The coating material for a secondary battery separator of the present invention contains the above-described coating material raw material for a secondary battery separator, and thus can achieve an improvement in productivity of a secondary battery separator. The coating material for a secondary battery separator of the present invention can provide a secondary battery separator excellent in heat resistance, air permeability and adhesion.
The secondary battery separator of the present invention has the coating film of the coating material for a secondary battery separator described above, and therefore is excellent in productivity, heat resistance, air permeability, and adhesion.
According to the method for producing a secondary battery separator of the present invention, a secondary battery separator excellent in heat resistance, air permeability, and adhesion can be produced efficiently.
The secondary battery of the present invention is excellent in productivity, heat resistance, air permeability and adhesion because the secondary battery separator is provided with the secondary battery separator. As a result, the secondary battery of the present invention is excellent in productivity, heat resistance, air permeability, and adhesion.
Detailed Description
The coating material raw material for a secondary battery separator of the present invention contains a composite polymer of a water-soluble polymer and a non-water-soluble polymer. The composite polymer comprises a water-soluble polymer and a water-insoluble polymer, the water-soluble polymer being chemically bonded to the water-insoluble polymer. That is, the composite polymer is formed by chemically bonding the water-soluble polymer and the non-water-soluble polymer.
The water-soluble polymer is a polymer that improves the solubility of the coating material raw material for secondary battery separator in water. The water-soluble polymer was relatively hydrophilic, and the SP value (solubility parameter) of the water-soluble polymer was 13.0 (cal/cm 3 ) 1/2 The above.
The SP value may be calculated by using the calculation software choops (version 4.0) of the company Million Zillion Software. The calculation method used in the calculation software is described in chapter XII of Polymer computing materials science (Computational Materials Scienc e of Polymers) (A.A. Askadskii, cambridge Intl Science Pub (2005/12/30)), supra.
More specifically, the SP value (solubility parameter) of the water-soluble polymer is 13.0 (cal/cm 3 ) 1/2 Above, it is preferably 13.2 (cal/cm 3 ) 1/2 As described above, it is more preferably 13.4 (cal/cm 3 ) 1/2 The above. In addition, the SP value (solubility parameter) of the water-soluble polymer is, for example, 20.0 (cal/cm 3 ) 1/2 Hereinafter, it is preferably 18.0 (cal/cm 3 ) 1/2 Hereinafter, it is more preferably 16.0 (cal/cm 3 ) 1/2 The following is given.
The water-soluble polymer comprises the 1 st reactive functional group. The 1 st reactive functional group is a functional group for chemical bonding with a 2 nd reactive functional group (described below) of a water-insoluble polymer (described below). Examples of the 1 st reactive functional group include a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group, and a phosphate group. From the viewpoint of ease of production of the composite polymer, the 1 st reactive functional group is preferably a carboxyl group.
The water-soluble polymer can be obtained by polymerizing a water-soluble polymer raw material (monomer composition) by a known method. The water-soluble polymer raw material is suitably selected so that the SP value of the water-soluble polymer falls within the above range and the 1 st reactive functional group is contained in the water-soluble polymer.
More specifically, the water-soluble polymer raw material contains, for example, (meth) acrylamide, and a monomer containing the 1 st reactive functional group. The "(meth) propylene-" means "propylene-" and/or "meth-propylene-" (the same applies hereinafter).
If the water-soluble polymer raw material contains (meth) acrylamide, the water-soluble polymer has a repeating unit derived from (meth) acrylamide, and therefore the water solubility (SP value) can be adjusted to be good.
The (meth) acrylamide may be acrylamide or methacrylamide, and preferably methacrylamide.
The 1 st reactive functional group-containing monomer is a monomer containing the 1 st reactive functional group and an ethylenic double bond described above. Examples of the monomer having the 1 st reactive functional group include a carboxyl group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, a glycidyl group-containing vinyl monomer, an isocyanate group-containing vinyl monomer, and a phosphate group-containing vinyl monomer.
Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids, dicarboxylic acids, and salts thereof. Examples of the monocarboxylic acid include (meth) acrylic acid. Examples of the dicarboxylic acid include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride and fumaric anhydride. They may be used singly or in combination of 2 or more.
Examples of the hydroxyl group-containing vinyl monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether.
Examples of the isocyanate group-containing vinyl monomer include isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 1-methyl-2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, and 4-isocyanatobutyl (meth) acrylate.
Examples of the vinyl monomer having a phosphate group include acid phosphoryloxyethyl (meth) acrylate and mono (2-hydroxyethyl (meth) acrylate) phosphate.
These 1 st reactive functional group-containing monomers may be used alone or in combination of 2 or more. In the case where 2 or more kinds of the 1 st reactive functional group-containing monomers are used in combination, the kind of the 1 st reactive functional group-containing monomer is appropriately selected so that the 1 st reactive functional groups are not bonded to each other.
The 1 st reactive functional group-containing monomer is preferably a carboxyl group-containing vinyl monomer. If the water-soluble polymer raw material contains a carboxyl group-containing vinyl monomer, the water-soluble polymer has a repeating unit derived from the carboxyl group-containing vinyl monomer, and thus excellent water solubility can be obtained.
The water-soluble polymer raw material may contain a copolymerizable monomer (hereinafter referred to as a 1 st copolymerizable monomer) as an optional component. Examples of the 1 st copolymerizable monomer include monomers copolymerizable with (meth) acrylamide and/or a 1 st reactive functional group-containing monomer.
The 1 st copolymerizable monomer is, for example, an alkyl (meth) acrylate. Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl moiety having 1 to 20 carbon atoms. Examples of such alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate. They may be used singly or in combination of 2 or more.
Examples of the 1 st copolymerizable monomer include tertiary amino group-containing vinyl monomers, quaternary ammonium group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, and acetoacetoxy group-containing vinyl monomers.
Examples of the tertiary amino group-containing vinyl monomer include N, N-dialkylaminoalkyl (meth) acrylate and N, N-dialkylaminoalkyl (meth) acrylamide. Examples of the N, N-dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, N-di-t-butylaminoethyl (meth) acrylate, and N, N-dimethylaminobutyl (meth) acrylate. Examples of the N, N-dialkylaminoalkyl (meth) acrylamide include N, N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide.
Examples of the quaternary ammonium group-containing vinyl monomer include a quaternary ammonium compound obtained by allowing a quaternary ammonium agent to act on the tertiary amino group-containing monomer. Examples of the quaternizing agent include epihalohydrin, halobenzyl and haloalkyl.
Examples of the cyano group-containing vinyl monomer include (meth) acrylonitrile.
Examples of the sulfonic acid group-containing vinyl monomer include allylsulfonic acid, methacrylic sulfonic acid, and t-butyl acrylamide sulfonic acid. Further, as the sulfonic acid group-containing vinyl monomer, salts can be mentioned. Examples of the salt include sodium salt, potassium salt and ammonium salt. More specifically, examples of the salt of the sulfonic acid group-containing monomer include sodium allylsulfonate, sodium methallylsulfonate, and ammonium methallylsulfonate.
Examples of the acetoacetoxy-containing vinyl monomer include acetoacetoxyethyl (meth) acrylate.
Further, examples of the 1 st copolymerizable monomer include vinyl esters, aromatic vinyl monomers, unsaturated carboxylic acid amides (excluding (meth) acrylamides), heterocyclic vinyl compounds, vinylidene halide compounds, α -olefins, dienes, and crosslinkable vinyl monomers. Examples of vinyl esters include vinyl acetate and vinyl propionate. Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene. Examples of the unsaturated carboxylic acid amide include N-methylol (meth) acrylamide. Examples of the heterocyclic vinyl compound include vinyl pyrrolidone. Examples of the vinylidene halide compound include vinylidene chloride and vinylidene fluoride. Examples of the α -olefins include ethylene and propylene. Examples of the diene include butadiene. Examples of the crosslinkable vinyl monomer include methylenebis (meth) acrylamide, divinylbenzene, polyethylene glycol chain-containing di (meth) acrylate, trimethylolpropane tetraacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
These 1 st copolymerizable monomers may be used alone or in combination of 2 or more. The 1 st copolymerizable monomer is preferably a vinyl monomer containing a tertiary amino group from the viewpoints of heat resistance and air permeability.
In addition, according to the combination of the 1 st reactive functional group and the 2 nd reactive functional group, the 1 st reactive functional group-containing monomer containing the 1 st reactive functional group of a kind that cannot react with the 2 nd reactive functional group (or that can react but hardly react from the viewpoint of the reaction rate or the like) is classified as a 1 st copolymerizable monomer. From the viewpoint of adjusting the degree of water solubility (SP value), the 1 st copolymerizable monomer is preferably the hydroxyl group-containing vinyl monomer described above as the 1 st reactive group-containing monomer.
In addition, the 1 st copolymerizable monomer preferably does not contain an alkyl (meth) acrylate. That is, the water-soluble polymer raw material preferably does not contain an alkyl (meth) acrylate. More specifically, the monomer composition containing no alkyl (meth) acrylate is preferably a water-soluble polymer material, and is distinguished from a water-insoluble polymer material described later.
The ratio of the monomers in the water-soluble polymer raw material is suitably selected so that the SP value of the water-soluble polymer falls within the above range and the water-soluble polymer contains the 1 st reactive functional group.
For example, the water-soluble polymer raw material is composed of (meth) acrylamide and a monomer having a 1 st reactive functional group, or is composed of (meth) acrylamide, a monomer having a 1 st reactive functional group, and a 1 st copolymerizable monomer.
The water-soluble polymer material is preferably composed of (meth) acrylamide and a carboxyl group-containing vinyl monomer, or is preferably composed of (meth) acrylamide, a carboxyl group-containing vinyl monomer and a 1 st copolymerizable monomer.
From the viewpoint of obtaining excellent heat resistance, the content of (meth) acrylamide is, for example, 40 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, relative to 100 parts by mass of the total amount of the water-soluble polymer raw materials. In addition, from the viewpoint of obtaining excellent heat resistance, the content of (meth) acrylamide is, for example, 97 parts by mass or less, preferably 96 parts by mass or less, and more preferably 95 parts by mass or less, relative to 100 parts by mass of the total amount of the water-soluble polymer raw materials.
The content of the 1 st reactive functional group-containing monomer is, for example, 3 parts by mass or more, preferably 8 parts by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the water-soluble polymer raw materials. The content of the 1 st reactive functional group-containing monomer is, for example, 60 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the water-soluble polymer raw material.
The content of the 1 st copolymerizable monomer in the water-soluble polymer raw material is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, for example, 0 part by mass or more, based on 100 parts by mass of the total amount of the water-soluble polymer raw material.
The water-soluble polymer can be obtained by polymerizing the above-mentioned water-soluble polymer raw material by a method described later. The content of the repeating unit derived from each monomer in the water-soluble polymer is the same as the content of each monomer in the water-soluble polymer raw material.
That is, from the viewpoint of obtaining excellent heat resistance, the content of the repeating unit derived from (meth) acrylamide is, for example, 40 mass% or more, preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more, relative to the total amount of the water-soluble polymer. In addition, from the viewpoint of obtaining excellent heat resistance, the content of the repeating unit derived from (meth) acrylamide is, for example, 97% by mass or less, preferably 96% by mass or less, and more preferably 95% by mass or less, relative to the total amount of the water-soluble polymer.
The content of the repeating unit derived from the monomer having the 1 st reactive functional group is, for example, 3% by mass or more, preferably 8% by mass or more, and more preferably 10% by mass or more, based on the total amount of the water-soluble polymer. The content of the repeating unit derived from the monomer having the 1 st reactive functional group is, for example, 60% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the total amount of the water-soluble polymer.
The content of the repeating unit derived from the 1 st copolymerizable monomer is, for example, 40 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, for example, 0 mass% or more, based on the total amount of the water-soluble polymer.
From the viewpoints of heat resistance and air permeability, the weight average molecular weight of the water-soluble polymer (weight average molecular weight in terms of polyethylene glycol/polyethylene oxide by GPC) is, for example, 5 thousands or more, preferably 1 ten thousand or more, more preferably 3 ten thousand or more, and even more preferably 5 ten thousand or more. In addition, from the viewpoint of low tackiness, the weight average molecular weight of the water-soluble polymer (weight average molecular weight in terms of polyethylene glycol/polyethylene oxide by GPC) is, for example, 50 ten thousand or less, preferably 20 ten thousand or less, more preferably 15 ten thousand or less, further preferably 10 ten thousand or less, and particularly preferably 8 ten thousand or less.
When the weight average molecular weight of the water-soluble polymer is within the above range, improvement in storage stability, uniform dispersibility and low tackiness can be achieved in particular. The method for measuring the weight average molecular weight is according to examples described below.
In addition, from the viewpoints of heat resistance and air permeability, the glass transition temperature of the water-soluble polymer is, for example, 100 ℃ or higher, preferably 150 ℃ or higher, more preferably 200 ℃ or higher, and still more preferably 210 ℃ or higher. In addition, from the viewpoint of flexibility of a coating layer obtained by coating a coating material for a secondary battery separator, the glass transition temperature of the water-soluble polymer is, for example, 300 ℃ or less, preferably 240 ℃ or less, more preferably 230 ℃ or less, and even more preferably 220 ℃ or less.
When the glass transition temperature of the water-soluble polymer is within the above range, a secondary battery separator having heat resistance, air permeability and adhesion can be obtained, and further, storage stability, uniform dispersibility and low tackiness can be improved. The glass transition temperature was calculated using the FOX equation (the same applies hereinafter).
The specific gravity of the water-soluble polymer is, for example, 1.02 or more, preferably 1.05 or more. The specific gravity of the water-soluble polymer is, for example, 1.20 or less, preferably 1.15 or less.
The water-insoluble polymer is a polymer that improves the adhesion of the raw material of the coating material for secondary battery separator. The water insoluble polymer is relatively hydrophobic, and the SP value (solubility parameter) of the water insoluble polymer is less than 13.0 (cal/cm) 3 ) 1/2 。
More specifically, the SP value (solubility parameter) of the water-insoluble polymer is less than 13.0 (cal/cm) 3 ) 1/2 Preferably 12.5 (cal/cm 3 ) 1/2 Hereinafter, it is more preferably 12.0 (cal/cm 3 ) 1/2 Hereinafter, it is more preferably 11.0 (cal/cm 3 ) 1/2 The following is given. In addition, the SP value (solubility parameter) of the water-insoluble polymer is, for example, 7.0 (cal/cm 3 ) 1/2 Above, it is preferably 8.0 (cal/cm 3 ) 1/2 The above is more preferably 9.0 (cal/cm 3 ) 1/2 The above.
The water insoluble polymer contains the 2 nd reactive functional group. The 2 nd reactive functional group is a functional group for chemical bonding with the 1 st reactive functional group of the above water-soluble polymer. Examples of the 2 nd reactive functional group include a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group, and a phosphate group. The 2 nd reactive functional group may be appropriately selected according to the kind of the 1 st reactive functional group.
More specifically, for example, when the 1 st reactive functional group contains a carboxyl group, a glycidyl group bonded to the carboxyl group, for example, is selected as the 2 nd reactive functional group.
In addition, for example, when the 1 st reactive functional group contains a hydroxyl group, an isocyanate group bonded to a hydroxyl group, for example, is selected as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains a glycidyl group, a carboxyl group and/or a phosphate group capable of bonding to the glycidyl group is selected as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains an isocyanate group, a hydroxyl group capable of bonding to the isocyanate group is selected as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains a phosphate group, a glycidyl group capable of bonding to the phosphate group is selected as the 2 nd reactive functional group. From the viewpoint of ease of production of the composite polymer, the 2 nd reactive functional group is preferably a glycidyl group.
The water-insoluble polymer can be obtained by polymerizing a water-insoluble polymer raw material (monomer composition) by a known method. The water-soluble polymer raw material is suitably selected so that the SP value of the water-insoluble polymer falls within the above range and the 2 nd reactive functional group is contained in the water-insoluble polymer.
More specifically, the water-insoluble polymer raw material (monomer composition) contains, for example, an alkyl (meth) acrylate, and a monomer containing the 2 nd reactive functional group.
If the water-insoluble polymer raw material contains an alkyl (meth) acrylate, the water-insoluble polymer has a repeating unit derived from the alkyl (meth) acrylate, and therefore the water-insoluble property (SP value) can be adjusted to be good.
The alkyl (meth) acrylate includes, for example, the above-mentioned alkyl (meth) acrylate, and more specifically, an alkyl (meth) acrylate having an alkyl moiety having 1 to 20 carbon atoms. They may be used singly or in combination of 2 or more. The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl moiety having 1 to 4 carbon atoms, and more preferably n-butyl (meth) acrylate.
The monomer having the 2 nd reactive functional group is a monomer having the 2 nd reactive functional group and an ethylenic double bond described above. Examples of the monomer having a 2 nd reactive functional group include the above-mentioned carboxyl group-containing vinyl monomer, the above-mentioned hydroxyl group-containing vinyl monomer, the above-mentioned glycidyl group-containing vinyl monomer, the above-mentioned isocyanate group-containing vinyl monomer, and the above-mentioned phosphate group-containing vinyl monomer.
These monomers having the 2 nd reactive functional group may be used alone or in combination of 2 or more. In the case where 2 or more types of monomers having 2 nd reactive functional groups are used in combination, the types of monomers having 2 nd reactive functional groups are appropriately selected so that the 2 nd reactive functional groups are not bonded to each other.
The 2 nd reactive functional group-containing monomer may be appropriately selected depending on the kind of the 1 st reactive functional group-containing monomer. That is, the 1 st reactive functional group and the 2 nd reactive functional group are appropriately selected so as to be a combination of the above.
More specifically, for example, in the case where the 1 st reactive functional group-containing monomer contains a carboxyl group-containing vinyl monomer, as the 2 nd reactive functional group, for example, a glycidyl group-containing vinyl monomer is selected. In addition, for example, in the case where the 1 st reactive functional group-containing monomer contains a hydroxyl group-containing vinyl monomer, as the 2 nd reactive functional group-containing monomer, for example, an isocyanate group-containing vinyl monomer is selected. In addition, for example, when the 1 st reactive functional group-containing monomer contains a glycidyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer and/or a phosphate group-containing vinyl monomer is selected as the 2 nd reactive functional group-containing monomer.
In addition, for example, in the case where the 1 st reactive functional group-containing monomer contains an isocyanate group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer is selected as the 2 nd reactive functional group-containing monomer. In addition, for example, in the case where the 1 st reactive functional group-containing monomer contains a phosphoric acid group-containing vinyl monomer, a glycidyl group-containing vinyl monomer is selected as the 2 nd reactive functional group-containing monomer.
The monomer having the 2 nd reactive functional group is preferably a glycidyl group-containing vinyl monomer. If the water-insoluble polymer raw material contains a glycidyl group-containing vinyl monomer, the water-insoluble polymer has a repeating unit derived from the glycidyl group-containing vinyl monomer, and thus a composite polymer can be obtained with good productivity.
The water-insoluble polymer material may contain a copolymerizable monomer (hereinafter referred to as a 2 nd copolymerizable monomer) as an optional component. Examples of the 2 nd copolymerizable monomer include monomers copolymerizable with the alkyl (meth) acrylate and/or the 2 nd reactive functional group-containing monomer.
Examples of the 2 nd copolymerizable monomer include the tertiary amino group-containing vinyl monomer, the quaternary ammonium group-containing vinyl monomer, the cyano group-containing vinyl monomer, the sulfonic acid group-containing vinyl monomer, the acetoacetoxy group-containing vinyl monomer, the vinyl esters, the aromatic vinyl monomers, the unsaturated carboxylic acid amides (including (meth) acrylamides), the heterocyclic vinyl compounds, the vinylidene halide compounds, the α -olefins, the dienes, and the crosslinkable vinyl monomers.
These 2 nd copolymerizable monomers may be used alone or in combination of 2 or more. The 2 nd copolymerizable monomer is preferably an aromatic vinyl monomer from the viewpoint of adhesion.
The 2 nd reactive functional group-containing monomer containing the 2 nd reactive functional group of a type that cannot react with the 1 st reactive functional group (or that can react but hardly react from the viewpoint of reaction rate or the like) is classified as a 2 nd copolymerizable monomer according to the combination of the 1 st reactive functional group and the 2 nd reactive functional group. From the viewpoint of adjusting the degree of non-water solubility (SP value), the 2 nd copolymerizable monomer is preferably exemplified by the carboxyl group-containing vinyl monomer and hydroxyl group-containing vinyl monomer described hereinabove as the 2 nd reactive group-containing monomer.
In addition, the water-insoluble polymer raw material preferably contains substantially no cyano group-containing vinyl monomer (specifically, (meth) acrylonitrile). The substantially non-cyano group-containing vinyl monomer means that: the cyano group-containing vinyl monomer is, for example, 2.0 mass% or less, preferably 1.0 mass% or less, relative to the water-insoluble polymer raw material.
When a cyano group-containing vinyl monomer is blended, the electrolyte resistance of a coating material for a secondary battery separator (described later) may be lowered. Thus, the water-insoluble polymer raw material preferably does not contain a cyano group-containing vinyl monomer.
In the water-insoluble polymer raw material, the ratio of the monomers is suitably selected so that the SP value of the water-insoluble polymer falls within the above range and the water-insoluble polymer contains the 2 nd reactive functional group.
For example, the water-insoluble polymer raw material is composed of an alkyl (meth) acrylate and a monomer having a 2 nd reactive functional group, or is composed of an alkyl (meth) acrylate, a monomer having a 2 nd reactive functional group, and a 2 nd copolymerizable monomer.
The water-insoluble polymer material is preferably composed of an alkyl (meth) acrylate and a glycidyl group-containing vinyl monomer, or is preferably composed of an alkyl (meth) acrylate, a glycidyl group-containing vinyl monomer, and a 2 nd copolymerizable monomer.
For example, from the viewpoint of obtaining excellent adhesion, the content of the alkyl (meth) acrylate is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, relative to 100 parts by mass of the water-insoluble polymer material. In addition, from the viewpoint of obtaining excellent adhesion, the content of the alkyl (meth) acrylate is, for example, 99 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less, relative to 100 parts by mass of the water-insoluble polymer raw material.
The content ratio (total amount) of the 2 nd reactive functional group-containing monomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more, relative to 100 parts by mass of the water-insoluble polymer material. The content ratio (total amount) of the 2 nd reactive functional group-containing monomer is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the water-insoluble polymer material.
The content of the 2 nd copolymerizable monomer in the water-insoluble polymer raw material is, for example, 0 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of the water-insoluble polymer raw material. The content of the 2 nd copolymerizable monomer in the water-insoluble polymer raw material is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, based on 100 parts by mass of the total amount of the water-insoluble polymer raw material.
The water-insoluble polymer can be obtained by polymerizing the water-insoluble polymer raw material by a method described later. The content of the repeating unit derived from each monomer in the water-insoluble polymer is the same as the content of each monomer in the water-insoluble polymer raw material.
That is, the content of the repeating unit derived from the alkyl (meth) acrylate is, for example, 20 mass% or more, preferably 40 mass% or more, with respect to the total amount of the water-insoluble polymer, from the viewpoint of obtaining excellent adhesion. The content of the repeating unit derived from the alkyl (meth) acrylate is, for example, 99 mass% or less, preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less, based on the total amount of the water-insoluble polymer.
The content of the repeating unit derived from the monomer having the 2 nd reactive functional group is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more, based on the total amount of the water-insoluble polymer. The content of the repeating unit derived from the monomer having the 2 nd reactive functional group is, for example, 30 mass% or less, preferably 20 mass% or less, and more preferably 10 mass parts or less, based on the total amount of the water-insoluble polymer.
The content of the repeating unit derived from the 1 st copolymerizable monomer is, for example, 0% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, for example, 70% by mass or less, based on the total amount of the water-insoluble polymer.
The content of the repeating unit derived from the 2 nd copolymerizable monomer is, for example, 0% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, based on the total amount of the water-insoluble polymer. The content of the repeating unit derived from the 2 nd copolymerizable monomer is, for example, 80 mass% or less, preferably 70 mass% or less, based on the total amount of the water-insoluble polymer.
From the viewpoints of air permeability and adhesion, the glass transition temperature of the water-insoluble polymer is, for example, at least-60 ℃, preferably at least-40 ℃, more preferably at least-20 ℃, and even more preferably at least 0 ℃. In addition, from the viewpoint of low tackiness and adhesiveness, the glass transition temperature of the water-insoluble polymer is, for example, 70 ℃ or lower, preferably 50 ℃ or lower, more preferably 30 ℃ or lower, and still more preferably 10 ℃ or lower.
When the glass transition temperature of the water-insoluble polymer is within the above range, a secondary battery separator having heat resistance, air permeability and adhesion can be obtained, and further, storage stability, uniform dispersibility and low tackiness can be improved.
The specific gravity of the water-insoluble polymer is, for example, 0.85 or more, preferably 0.89 or more. The specific gravity of the water-insoluble polymer is, for example, 0.98 or less, preferably 0.95 or less.
The difference between the specific gravity of the water-soluble polymer and the specific gravity of the non-water-soluble polymer is, for example, 0.04 or more, preferably 0.10 or more. The difference between the specific gravity of the water-soluble polymer and the specific gravity of the non-water-soluble polymer is, for example, 0.35 or less, preferably 0.25 or less.
Next, a method for producing a composite polymer and a coating material raw material for a secondary battery separator will be described.
Specifically, as a method for producing a composite polymer and a coating material raw material for a secondary battery separator, for example, the 1 st method and the 2 nd method are mentioned. In the method 1, for example, a water-soluble polymer raw material is polymerized to obtain a water-soluble polymer, and then a water-insoluble polymer raw material is polymerized in the presence of the water-soluble polymer. In the method 2, first, a water-insoluble polymer material is polymerized to obtain a water-insoluble polymer, and then the water-soluble polymer material is polymerized in the presence of the water-insoluble polymer. The method 1 is preferable.
The 1 st method comprises the following steps: a step (step 1) of obtaining a water-soluble polymer obtained by polymerizing a water-soluble polymer raw material; and a step (step 2) of obtaining a water-soluble polymer obtained by polymerizing a water-insoluble polymer raw material in the presence of the water-soluble polymer and chemically bonding at least a part of the 1 st reactive functional group and at least a part of the 2 nd reactive functional group.
More specifically, in step 1, first, a water-soluble polymer raw material is polymerized to obtain a water-soluble polymer. In the synthesis of a water-soluble polymer, a known polymerization initiator is blended into water, and a water-soluble polymer raw material is added dropwise to the water to polymerize the water-soluble polymer raw material. In addition, in the polymerization of the water-soluble polymer, a known emulsifier (surfactant) may be blended as needed from the viewpoint of achieving an improvement in production stability.
The polymerization conditions may be appropriately set depending on the kind of the water-soluble polymer raw material. For example, the polymerization temperature is, for example, 30℃or higher, preferably 50℃or higher, under normal pressure. The polymerization temperature is, for example, 95℃or lower, preferably 85℃or lower. The polymerization time is, for example, 1 hour or more, preferably 2 hours or more. The polymerization time is, for example, 30 hours or less, preferably 20 hours or less.
In addition, in the polymerization of the water-insoluble polymer, for example, known additives may be blended in an appropriate ratio from the viewpoint of achieving an improvement in production stability. Examples of the additive include a pH adjuster, a metal ion sealer, and a molecular weight adjuster (chain transfer agent).
Thus, the water-soluble polymer raw material is polymerized to obtain a water-soluble polymer. The water-soluble polymer has repeating units derived from a monomer containing the 1 st reactive functional group. That is, the water-soluble polymer contains the 1 st reactive functional group in the molecule.
In addition, the water-soluble polymer is obtained in the form of an aqueous solution dissolved in water. The concentration of the solid content of the water-soluble polymer in the aqueous solution can be appropriately set according to the purpose and use.
Next, in step 2, the water-insoluble polymer raw material is polymerized in the presence of the water-soluble polymer. More specifically, the water-insoluble polymer raw material is emulsified in water, and the emulsion is added to the aqueous solution of the water-soluble polymer to polymerize the water-insoluble polymer raw material.
The polymerization conditions may be appropriately set depending on the kind of the water-insoluble polymer raw material. For example, the polymerization temperature is, for example, 30℃or higher, preferably 50℃or higher, under normal pressure. The polymerization temperature is, for example, 95℃or lower, preferably 85℃or lower. The polymerization time is, for example, 0.5 hours or more, preferably 1.5 hours or more. The polymerization time is, for example, 20 hours or less, preferably 10 hours or less.
Thus, the water-insoluble polymer raw material is polymerized to obtain a water-insoluble polymer. The water insoluble polymer has repeat units from the monomer containing the 2 nd reactive functional group. That is, the water-insoluble polymer contains the 2 nd reactive functional group in the molecule.
In this method, at least a part of the 2 nd reactive functional groups in the water-insoluble polymer and at least a part of the 1 st reactive functional groups in the water-soluble polymer are chemically bonded to each other while the water-insoluble polymer is being produced.
More specifically, for example, in the case where the 1 st reactive functional group contains a carboxyl group, the carboxyl group thereof is chemically bonded to a glycidyl group as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains a hydroxyl group, the hydroxyl group thereof is chemically bonded to an isocyanate group as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains a glycidyl group, the glycidyl group is chemically bonded to a carboxyl group and/or a phosphate group as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains an isocyanate group, the isocyanate group thereof is chemically bonded to a hydroxyl group as the 2 nd reactive functional group. In addition, for example, when the 1 st reactive functional group contains a phosphate group, the phosphate group is chemically bonded to a glycidyl group as the 2 nd reactive functional group.
The reaction conditions may be appropriately set according to the type of the 1 st reactive functional group and the type of the 2 nd reactive functional group. The reaction of the 1 st reactive functional group and the 2 nd reactive functional group is usually performed simultaneously with the synthesis of the water-insoluble polymer in the 2 nd step.
As a result, the water-soluble polymer and the water-insoluble polymer can be chemically bonded to each other, thereby obtaining a composite polymer of the water-soluble polymer and the water-insoluble polymer. Thus, a dispersion liquid (coating material raw material for secondary battery separator) containing the composite polymer was obtained.
In this dispersion, the content of the coating material raw material for a secondary battery separator (solid content concentration of the dispersion) is, for example, 5 mass% or more, and further, 50 mass% or less.
In the raw material of the coating material for a secondary battery separator, the ratio of the mass of the water-soluble polymer to the mass of the water-insoluble polymer can be appropriately set according to the purpose and use. For example, the water-soluble polymer is, for example, 40 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more, relative to 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer, from the viewpoint of heat resistance. The water-soluble polymer is, for example, 99.9 parts by mass or less, preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and even more preferably 95 parts by mass or less, based on 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer, from the viewpoints of air permeability and adhesion.
The water-insoluble polymer is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, based on 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer, from the viewpoints of air permeability and adhesion.
The water-insoluble polymer is, for example, 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer, from the viewpoint of heat resistance.
The mass of the water-insoluble polymer and the mass of the water-soluble polymer can be calculated from the amounts of the water-insoluble polymer raw material and the water-soluble polymer raw material charged. That is, the mass of the water-soluble polymer means the mass of the water-soluble polymer raw material, and the mass of the water-insoluble polymer means the mass of the water-insoluble polymer raw material.
The coating material raw material for a secondary battery separator of the present invention contains a composite polymer of a water-soluble polymer and a non-water-soluble polymer, wherein the water-soluble polymer contains a 1 st reactive functional group, the non-water-soluble polymer contains a 2 nd reactive functional group capable of chemically bonding to the 1 st reactive functional group, and at least a part of the 1 st reactive functional group and at least a part of the 2 nd reactive functional group are chemically bonded to each other in the composite polymer.
Therefore, the coating material raw material for secondary battery separator described above is excellent in storage stability, uniform dispersibility, and low viscosity. Further, according to the coating material raw material for a secondary battery separator, a secondary battery separator excellent in heat resistance, air permeability and adhesion can be obtained.
Particularly in the case where the water-soluble polymer and the water-insoluble polymer are mixed without forming a composite polymer, separation occurs due to a difference in specific gravity between the water-soluble polymer and the water-insoluble polymer. In addition, in order to suppress separation, a method of separately preparing a water-soluble polymer and a water-insoluble polymer and mixing them at the time of use has been studied, but the operation is complicated and the uniform dispersibility of the mixture is poor.
In contrast, in the above-described coating material raw material for secondary battery separator, the water-soluble polymer and the non-water-soluble polymer are chemically bonded to form a composite polymer, and therefore separation due to a specific gravity difference can be suppressed, and excellent storage stability can be obtained. Further, since the water-soluble polymer and the water-insoluble polymer are chemically bonded to form a composite polymer, a mixing step at the time of use is not required, and workability and uniform dispersibility are excellent.
In addition, in the case where the water-soluble polymer and the non-water-soluble polymer are not chemically bonded to each other and a composite polymer is not formed, the interaction between the water-soluble polymers is large, and thus, a high viscosity is caused.
In contrast, in the above-described coating material raw material for a secondary battery separator, the water-soluble polymer is chemically bonded to the water-insoluble polymer to form a composite polymer, and therefore the water-soluble polymer is fixed to the water-insoluble polymer. Therefore, the interaction between the water-soluble polymers can be suppressed, and as a result, the increase in viscosity can be suppressed, and excellent low viscosity can be obtained.
The coating material for a secondary battery separator of the present invention contains the above-described coating material raw material for a secondary battery separator, and, if necessary, an inorganic filler and a dispersant.
The mixing ratio of the coating material raw material for secondary battery separator is, for example, 0.1 part by mass or more (solid content) and, for example, 10 parts by mass or less (solid content) with respect to 100 parts by mass (solid content) of the total amount of the coating material raw material for secondary battery separator, the inorganic filler and the dispersant (hereinafter, referred to as the coating material component for secondary battery separator).
Examples of the inorganic filler include oxides, nitrides, carbides, sulfuric acid, hydroxides, silicic acid, and minerals. Examples of the oxide include alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, and iron oxide. Examples of the nitride include silicon nitride, titanium nitride, and boron nitride. Examples of the carbide include silicon carbide and calcium carbonate. Examples of the sulfuric acid compound include magnesium sulfate and aluminum sulfate. Examples of the hydroxide include aluminum hydroxide and diaspore. Examples of the silicic acid include calcium silicate, magnesium silicate, diatomaceous earth, silica sand, and glass. Examples of the minerals include talc, kaolinite, dickite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, mica, magnesia, bentonite, asbestos, and zeolite. The inorganic filler is preferably an oxide or hydroxide, more preferably alumina or diaspore.
The inorganic filler is blended in an amount of, for example, 50 parts by mass or more (solid content) and 99.7 parts by mass or less (solid content) with respect to 100 parts by mass (solid content) of the coating material component for a secondary battery separator.
Examples of the dispersant include ammonium polycarboxylic acid and sodium polycarboxylic acid. When the dispersing agent is ammonium polycarboxylate, the coating material raw material for secondary battery separator and the inorganic filler can be uniformly dispersed, and a coating film (described below) having a uniform thickness can be obtained.
The mixing ratio of the dispersant is, for example, 0.1 part by mass or more (solid content) with respect to 100 parts by mass (solid content) of the coating material component for a secondary battery separator, and is, for example, 5 parts by mass or less (solid content).
To obtain a coating material for a secondary battery separator, an inorganic filler and a dispersant are mixed in the above-described ratio in water to prepare an inorganic filler dispersion.
Next, a coating material raw material for a secondary battery separator (or a dispersion containing a coating material raw material for a secondary battery separator) is blended into the inorganic filler dispersion in the above-described ratio, and stirred. Thus, a coating material for secondary battery separator was obtained.
The stirring method is not particularly limited, and a known stirring device can be used. Examples of the stirring device include a ball mill, a bead mill, a planetary ball mill, a vibration ball mill, a sand mill, a colloid mill, an attritor, a roll crusher, a high-speed impeller dispersing device, a homogenizer, a high-speed impact mill, and an ultrasonic dispersing device.
The coating material for secondary battery separator is obtained, for example, in the form of a dispersion liquid dispersed in water. In addition, a known additive may be contained in the coating material for a secondary battery separator as necessary. Examples of the additives include hydrophilic resins, thickeners, humectants, antifoaming agents, and pH adjusters. The additives may be used singly or in combination of 2 or more.
The coating material for a secondary battery separator described above contains the coating material raw material for a secondary battery separator described above, and thus can achieve an improvement in productivity of a secondary battery separator. The coating material for a secondary battery separator can provide a secondary battery separator excellent in heat resistance, air permeability and adhesion.
Further, the coating material for secondary battery separator can be suitably used as a coating material for secondary battery separator.
The secondary battery separator of the present invention can be manufactured by a known method.
In this method, first, a porous film is prepared. Examples of the porous membrane include a polyolefin porous membrane and an aromatic polyamide porous membrane, and preferred examples thereof include a polyolefin porous membrane. Examples of the polyolefin include polyethylene and polypropylene. The porous film may be subjected to surface treatment as needed. The surface treatment may be, for example, corona treatment or plasma treatment.
The thickness of the porous film is, for example, 1 μm or more, preferably 5 μm or more. The thickness of the porous film is, for example, 40 μm or less, preferably 20 μm or less.
Next, in this method, the separator coating material is coated on at least one surface of the porous film. Then, the coating material for separator is dried as needed, thereby obtaining a coating film.
The coating method is not particularly limited, and examples thereof include gravure coating, small-diameter gravure coating, reverse roll coating, transfer roll coating, kiss coating, dip coating, micro gravure coating, doctor blade coating, air knife coating, blade coating, bar coating, extrusion coating, casting coating, die coating, screen printing, and spray coating.
The drying conditions are, for example, 40℃or higher and, for example, 80℃or lower. The thickness of the dried coating film is, for example, 1 μm or more, preferably 2 μm or more. The thickness of the dried coating film is, for example, 10 μm or less, preferably 8 μm or less.
Thus, a secondary battery separator is produced which comprises a porous film and a coating film of the coating material for a secondary battery separator disposed on at least one surface of the porous film.
In the above description, the coating film of the coating material for a secondary battery separator is disposed on at least one surface of the porous film, but the coating film may be disposed on both surfaces of the porous film.
The secondary battery separator is excellent in productivity, heat resistance, air permeability and adhesion because it is provided with the coating film of the coating material for a secondary battery separator.
In addition, according to the above-described method for manufacturing a secondary battery separator, a secondary battery separator excellent in heat resistance, air permeability, and adhesion can be manufactured efficiently.
The secondary battery separator can be suitably used as a separator for a secondary battery.
The secondary battery of the present invention comprises a positive electrode, a negative electrode, the secondary battery separator disposed between the positive electrode and the negative electrode, and an electrolyte impregnated into the positive electrode, the negative electrode, and the secondary battery separator.
As the positive electrode, for example, a known electrode including a current collector for a positive electrode and a positive electrode active material laminated on the current collector for a positive electrode can be used.
As the current collector for the positive electrode, a known conductive material is exemplified. Examples of the conductive material include aluminum, titanium, stainless steel, nickel, fired carbon, conductive polymer, and conductive glass. They may be used singly or in combination of 2 or more.
The positive electrode active material is not particularly limited, and examples thereof include lithium-containing transition metal oxides, lithium-containing phosphates, and lithium-containing sulfates. They may be used singly or in combination of 2 or more.
As the negative electrode, for example, a known electrode including a current collector for a negative electrode and a negative electrode active material laminated on the current collector for a negative electrode can be used.
Examples of the negative electrode current collector include copper and nickel. They may be used singly or in combination of 2 or more.
Examples of the negative electrode active material include graphite, soft carbon, and hard carbon. They may be used singly or in combination of 2 or more.
In the case where the secondary battery is a lithium ion battery, examples of the electrolyte include a solution obtained by dissolving a lithium salt in a carbonate compound. Examples of the carbonate compound include Ethylene Carbonate (EC), propylene Carbonate (PC) and ethylmethyl carbonate (EMC).
In order to manufacture a secondary battery, for example, a separator of the secondary battery is sandwiched between a positive electrode and a negative electrode, and these are housed in a battery case (cell), and an electrolyte is injected into the battery case.
Thereby, a secondary battery can be obtained.
The secondary battery described above is excellent in productivity, heat resistance, air permeability, and adhesion because the secondary battery separator described above is provided. As a result, the secondary battery described above is excellent in productivity, heat resistance, air permeability, and adhesion.
Examples
Specific numerical values such as the blending ratio (content ratio), physical property value, and parameter used in the following description may be replaced with the upper limit value (numerical value defined in the form of "below", "less than", or the lower limit value (numerical value defined in the form of "above", "greater than") described in the above "specific embodiment" and described in correspondence with the blending ratio (content ratio), physical property value, and parameter. In the following description, unless otherwise specified, "parts" and "%" are based on mass.
1. Preparation of coating material raw material for secondary battery separator
Examples 1 to 23 and comparative examples 1 to 6
600 parts of distilled water and 1 part of sodium lauryl sulfate (surfactant) were charged into a detachable flask equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ℃. Next, potassium persulfate (KPS, polymerization initiator) was added to the separable flask as described in tables 1 to 4.
100 parts of a water-soluble polymer raw material prepared as described in tables 1 to 4 was dissolved in 300 parts of distilled water. Next, this solution was continuously added to the above-mentioned detachable flask, which was replaced with nitrogen gas, at 75 ℃ for 180 minutes. Then, the water-soluble polymer raw material was stirred at 75℃for 4 hours to complete the polymerization. Thus, an aqueous solution of a water-soluble polymer having a carboxyl group (1 st reactive functional group) was obtained.
Next, the water-insoluble polymer raw materials prepared as described in tables 1 to 4 were emulsified with soap water. Next, the emulsion was added to the aqueous solution of the water-soluble polymer at one time. These mixtures were stirred and at 75 ℃ for 4 hours to complete the polymerization. Thus, a water-insoluble polymer having glycidyl groups (2 nd reactive functional groups) was obtained. In addition, at the same time, the carboxyl group of the water-soluble polymer is reacted with the glycidyl group of the water-insoluble polymer to obtain a composite polymer in which the water-soluble polymer and the water-insoluble polymer are chemically bonded. The water-insoluble polymers of comparative examples 1 to 6 did not have a glycidyl group (2 nd reactive functional group), and the water-soluble polymer did not react with the water-insoluble polymer. Therefore, in comparative examples 1 to 6, a composite polymer was not obtained, and a mixed polymer of a water-soluble polymer and a non-water-soluble polymer was obtained.
Thus, a coating material raw material for a separator is obtained in the form of a dispersion of a composite polymer or a dispersion of a mixed polymer (hereinafter referred to as a polymer dispersion). The solid content concentration of the dispersion was 10.0 mass%.
The glass transition temperatures (Tg, units:. Degree. C.) of the water-insoluble polymer and the water-soluble polymer were calculated by using the following FOX equation.
1/Tg＝W 1 /Tg 1 +W 2 /Tg 2 +···+W n /Tg n (1)
[ wherein Tg represents the glass transition temperature (unit: K) of the copolymer, tg i (i=1, 2 the expression of the glass transition temperature (unit: K), W i (i=1, 2 the term n) represents the mass fraction of the monomers i in the total monomers.]
Further, the solubility parameters (SP value, unit (cal/cm)) of the water-insoluble polymer and the water-soluble polymer were calculated by using the computer software CHEOPS (version 4.0) of Million Zillion Software company 3 ) 1/2 ). The calculation method uses the method described in chapter XII of polymer calculation materials science (A.A.Askadskii, cambridge Intl Science Pub (2005/12/30)).
The weight average molecular weight of the water-soluble polymer was measured by the following method and conditions. That is, the water-soluble polymer is sampled at the point in time when the polymerization of the water-soluble polymer is completed. Next, the weight average molecular weight (Mw) of the sample was determined using a GPC apparatus (apparatus name: P KP-22, FLOM Co.). The measurement conditions are described below. The weight average molecular weight is a molecular weight in terms of standard polyethylene glycol/polyethylene oxide.
Sample concentration: 0.1 (w/v)%
Sample injection amount: 100 mu L
Eluent: 0.2M NaNO 3 Acrylonitrile (AN) =90/10
Flow rate: 1.0ml/min
Measurement temperature: 40 DEG C
Column: shodexohPAK SB-806 MHQ×2
Comparative example 7
According to example 1 of International publication WO2017/026095, a dispersion as a raw material of a coating material for a separator was obtained.
Specifically, according to the descriptions in tables 1 to 4, a water-soluble polymer raw material was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and oxygen in the reaction system was removed by nitrogen gas. Then, 7 parts of a 5% ammonium persulfate aqueous solution and 3 parts of a 5% sodium hydrogensulfite aqueous solution as polymerization initiators were charged into a flask with stirring, and then the temperature was raised from room temperature to 80℃and kept for 3 hours to polymerize the water-soluble polymer raw material. Then, 162 parts of ion-exchanged water was added to obtain an aqueous solution of a water-soluble polymer.
Separately, 70 parts of ion exchange water, 0.15 parts of sodium lauryl sulfate as an emulsifier, and 0.5 parts of ammonium peroxodisulfate as a polymerization initiator were supplied to a reactor equipped with a stirrer, and the gas phase was replaced with nitrogen gas, and the temperature was raised to 60 ℃. Then, as shown in tables 1 to 4, the water-insoluble polymer raw materials were continuously added to the reactor, polymerization was performed at 60℃during the addition, and after the addition was completed, the reaction was completed after stirring at 70℃for 3 hours. Thus, a dispersion of the water-insoluble polymer was obtained.
Then, the obtained dispersion of the water-soluble polymer and the dispersion of the water-insoluble polymer are mixed to obtain a dispersion of the mixed polymer (polymer dispersion) as a coating material raw material for a separator. The mixing ratio was set to a ratio of 2 parts by mass of the particulate polymer relative to 1 part by mass of the water-soluble polymer.
Comparative example 8
600 parts of distilled water and 1 part of sodium lauryl sulfate (surfactant) were charged into a detachable flask equipped with a stirrer and a reflux condenser, and the temperature was raised to 70 ℃. Next, potassium persulfate (KPS, polymerization initiator) was added to the separable flask as described in table 5.
100 parts of a high SP value polymer raw material prepared as described in Table 5 was dissolved in 300 parts of distilled water. As the emulsifier, 2 parts of sodium lauryl sulfate (surfactant) was added. Next, this emulsion was continuously added to the above-mentioned detachable flask, which was replaced with nitrogen gas, at 75 ℃ for 180 minutes. The emulsion was then stirred at 75℃for 2 hours to complete the polymerization. Thus, an aqueous dispersion of a polymer having a carboxyl group (1 st reactive functional group) and having a high SP value was obtained.
Next, a low SP value polymer raw material prepared as described in Table 5 was emulsified with 1 part of sodium lauryl sulfate (surfactant). Next, the emulsion was added to the aqueous dispersion of the high SP value polymer at a time. These mixtures were stirred and at 75 ℃ for 4 hours to complete the polymerization. Thus, a low SP value polymer having glycidyl groups (2 nd reactive functional groups) was obtained. At the same time, a core-shell aqueous dispersion in which a high SP value polymer and a low SP value polymer are bonded via a glycidyl group and a carboxyl group is obtained.
Comparative example 9
According to example 1 of International publication WO2010/134501, a dispersion liquid was obtained as a raw material of a coating material for a separator.
That is, 230 parts of toluene, 50 parts of n-butyl acrylate, 50 parts of styrene oligomer, and 1 part of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) were charged into an autoclave equipped with a stirrer, and stirred sufficiently. The styrene oligomer was a single-terminal methacryloylated polystyrene oligomer (trade name AS-6, manufactured by Toyama Synthesis chemical industry Co., ltd., SP value 9.9 (cal/cm) 3 ) 1/2 )。
Then, the autoclave was heated to 90℃to polymerize the above-mentioned components. Thus, a solution of a polymer (hereinafter referred to as a graft polymer) was obtained. The main chain of the graft polymer is composed of n-butyl acrylate (a component exhibiting swelling properties in an electrolyte). The side chains of the graft polymer are composed of styrene (a component that does not exhibit swelling in the electrolyte).
The polymerization conversion was calculated from the solid content concentration of the solution. The polymerization addition rate was about 98%. The weight average molecular weight of the graft polymer was about 5 ten thousand. The glass transition temperature of the graft polymer was 25 ℃.
2. Coating material for secondary battery separator and production of secondary battery separator
Using the coating material raw materials for secondary battery separators of each example and each comparative example, a coating material for secondary battery separators was prepared, and secondary battery separators were obtained.
Specifically, 100 parts by mass of diasporite (Boehmite GradeC06, manufactured by Damine chemical Co., ltd., particle diameter: 0.7 μm) as a pigment and 3.0 parts by mass (in terms of solid content) of an aqueous solution of ammonium polycarboxylate (SAN NOPCO Co., ltd., SN dispersont 5468) as a Dispersant were uniformly dispersed in 110 parts by mass of water to obtain a pigment dispersion. Next, a polymer dispersion (a coating material raw material for a secondary battery separator) was added to the pigment dispersion so that the solid content was converted to 5 parts by mass, and water was further added so that the solid content was 40% by mass, and the mixture was stirred for 15 minutes to prepare a coating material for a secondary battery separator.
On the other hand, the surface of the polyolefin resin porous film is subjected to corona treatment. More specifically, as a polyolefin resin porous film, product No. SW509C+ (film thickness 9.6 μm, porosity 40.6%, air permeability 158g/100ml, areal density 5.5 g/m) was prepared 2 Changzhou Star New energy materials Co., ltd.). Then, the surface of the porous polyolefin resin film was cut into A4 size, and then corona-treated with a steering automatic corona surface treatment device (manufactured by WEDGE corporation) under conditions of an output of 0.15KW, a transport speed of 3.0m/s×2 times, and a corona discharge distance of 9 mm.
Next, the coating material for secondary battery separator described above was coated on the surface of the corona-treated polyolefin resin porous film using a wire bar. After the coating, drying was performed at 50℃to thereby form a 5 μm coating film on the surface of the polyolefin resin porous film.
Thereby, a secondary battery separator was manufactured.
3. Evaluation
(1) Heat resistance
The secondary battery separator was cut into 5cm×5cm pieces, which were used as test pieces. The test piece was placed in an oven at 150℃for 1 hour, and then the length of each side was measured to calculate the heat shrinkage.
In addition, regarding heat resistance, the quality was evaluated according to the following criteria.
And (3) the following materials: the heat shrinkage is less than 15%.
O: the heat shrinkage is 15% or more and less than 25%.
Delta: the heat shrinkage is 25% or more and less than 65%.
Delta delta: the heat shrinkage is 65% or more and less than 80%.
X: the heat shrinkage rate is more than 80%.
(2) Air permeability
The air resistance of the secondary battery separator was measured in accordance with JIS-P-8117 by using a Wang Yan air permeability smoothness tester manufactured by Asahi Seiko corporation. The smaller the air resistance, the more excellent the ion permeability was evaluated. The ion permeability was evaluated according to the following criteria.
And (3) the following materials: the air resistance is less than 180s/100mL.
O: the air resistance is more than 180s/100mL and less than 220s/100mL.
Delta: the air resistance is 220s/100mL or more and less than 300s/100mL.
X: the air resistance is more than 300s/100mL.
(3) Adhesion of
The secondary battery separator was cut into 5cm×10cm pieces, which were used as test pieces. The 180 ° peel test was performed by attaching a cellophane adhesive tape to a coating film of a coating material for secondary battery separator according to the method of JIS Z1522. At this time, the stretching speed of the cellophane adhesive tape was set to 10 mm/min. The measurement was performed 3 times, and the average value was calculated. In addition, regarding the adhesion, the quality was evaluated according to the following criteria.
And (3) the following materials: the average value of the bonding strength is 70N/m or more.
O: the average value of the adhesive strength is 50N/m or more and less than 70N/m.
Delta: the average value of the adhesive strength is 20N/m or more and less than 50N/m.
Delta delta: the average value of the adhesive strength is 1N/m or more and less than 20N/m.
X: the average value of the bonding strength is less than 1N/m.
(4) Storage stability
The storage stability of the coating material raw material for secondary battery separator was evaluated by the following method. That is, 1L of the polymer dispersion (coating material raw material for secondary battery separator) was stored in a constant temperature bath at 40 ℃. After half a year, the viscosity change and pH change of the dispersion of the composite polymer were measured. Further, the appearance change (layer separation and hue) of the dispersion of the composite polymer was visually observed. Then, the viscosity change, pH change and appearance change were evaluated at 1 to 4 points, respectively, and the storage stability was evaluated based on the lowest point. Evaluation criteria are described below.
Viscosity Change
4, the following steps: 0% to 5%
3, the method comprises the following steps: more than 5% and less than 10%
2, the method comprises the following steps: more than 10% and less than 30%
1, the method comprises the following steps: more than 30%
pH Change
4, the following steps: 0 to 0.5
3, the method comprises the following steps: more than 0.5 and less than 1.0
2, the method comprises the following steps: greater than 1.0 and less than 2.0
1, the method comprises the following steps: greater than 2.0
Appearance change
4, the following steps: no change in appearance.
3, the method comprises the following steps: there is a slight change in appearance.
2, the method comprises the following steps: there is a change in appearance.
1, the method comprises the following steps: there is a significant change in appearance.
Comprehensive evaluation (storage stability)
And (3) the following materials: the minimum score in the evaluation of the viscosity change, pH change and appearance change was 4 minutes.
O: the minimum score in the evaluation of the viscosity change, pH change and appearance change was 3 minutes.
Delta: the minimum score in the evaluation of the viscosity change, pH change and appearance change was 2.
X: the minimum score in the evaluation of the viscosity change, pH change and appearance change was 1 minute.
(5) Uniform dispersion
The uniform dispersibility of the raw material of the coating material for secondary battery separator was evaluated by the following method. Specifically, the Zeta potential of the coating material for a secondary battery separator was measured 10 times by using a Zeta potential measuring device (ELSZ-2000, manufactured by Otsuka electronics Co., ltd.) as a thick battery cell. Then, the uniform dispersibility was evaluated based on the following criteria.
And (3) the following materials: the difference between the maximum and minimum of 10 measurements of Zeta potential is less than 5% relative to the average of 10 measurements.
O: the difference between the maximum value and the minimum value in 10 measurements of Zeta potential is 5% or more and less than 10% relative to the average value of 10 measurements.
Delta: the difference between the maximum value and the minimum value in 10 measurements of Zeta potential is 10% or more and less than 15% relative to the average value of 10 measurements.
X: the difference between the maximum value and the minimum value in 10 measurements of Zeta potential is 15% or more relative to the average value of 10 measurements.
(6) Low viscosity
The low viscosity of the coating material raw material for secondary battery separator was evaluated by the following method. That is, the solid content concentration of the polymer dispersion was adjusted to 10 mass%, and the viscosity of the dispersion at 25℃was measured by a BM type viscometer. Evaluation criteria are described below.
And (3) the following materials: less than 1000 mPas
O: 1000 mPas or more and less than 2000 mPas
Delta: 2000 mPas or more and less than 6000 mPas
X: 6000 mPas or more
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 5
The formulation (parts by mass) of the water-soluble polymer raw materials in the table indicates the blending amount of the raw material components (monomers) with respect to 100 parts by mass of the water-soluble polymer. The formulation (parts by mass) of the water-insoluble polymer raw material represents the amount of the raw material component (monomer) blended per 100 parts by mass of the water-insoluble polymer. In addition, the ratio of the water-soluble polymer to the water-insoluble polymer is in accordance with "water-insoluble polymer/water-soluble polymer (mass ratio)" in the table.
The blending formula (parts by mass) of the high SP value polymer raw materials in the table indicates the blending amount of the raw material components (monomers) with respect to 100 parts by mass of the high SP value polymer. The compounding formula (parts by mass) of the low SP value polymer raw material indicates the compounding amount of the raw material component (monomer) with respect to 100 parts by mass of the low SP value polymer. In addition, the ratio of the high SP value polymer to the low SP value polymer is in accordance with "high SP value polymer/low SP value polymer (mass ratio)" in the table.
In addition, details of abbreviations in the tables are described below.
Mam: methacrylamide
AM: acrylamide
Mac: methacrylic acid
Ac: acrylic acid
HEMA: methacrylic acid 2-hydroxy ethyl ester
DMAEMA: n, N-dimethylaminoethyl methacrylate
DMAM: dimethylacrylamide
St: styrene
MMA: methyl methacrylate
BA: acrylic acid n-butyl ester
2EHA: 2-ethylhexyl acrylate
GMA: glycidyl methacrylate
AN: acrylonitrile (Acrylonitrile)
N-MAM: n-methylolacrylamide
AGE: allyl glycidyl ether
KPS: potassium persulfate
Tg: glass transition temperature, unit: DEG C
SP value: solubility parameter, unit: (cal/cm) 3 ) 1/2
The present invention is provided as an example embodiment of the present invention, and is merely illustrative and not limitative. Variations of the present invention that are apparent to those skilled in the art are also encompassed by the appended claims.
Industrial applicability
The coating material raw material for secondary battery separator, the coating material for secondary battery separator, the method for producing the secondary battery separator, and the secondary battery of the present invention can be suitably used in the field of secondary batteries.
Claims (12)
1. A coating material raw material for a secondary battery separator,it contains a SP value of 13.0 (cal/cm 3 ) 1/2 The water-soluble polymer has a SP value of less than 13.0 (cal/cm 3 ) 1/2 A composite polymer of the water-insoluble polymer of (a),
the water-soluble polymer comprises a 1 st reactive functional group,
the water insoluble polymer comprises a 2 nd reactive functional group capable of chemically bonding with the 1 st reactive functional group,
in the composite polymer, at least a portion of the 1 st reactive functional group is chemically bonded to at least a portion of the 2 nd reactive functional group.
2. The coating material raw material for a secondary battery separator according to claim 1, wherein the 1 st reactive functional group of the water-soluble polymer contains a carboxyl group,
the 2 nd reactive functional group of the water insoluble polymer comprises a glycidyl group.
3. The coating material raw material for a secondary battery separator according to claim 1, wherein the water-soluble polymer has a repeating unit derived from (meth) acrylamide and a repeating unit derived from a carboxyl group-containing vinyl monomer,
the water-insoluble polymer has a repeating unit derived from an alkyl (meth) acrylate and a repeating unit derived from a glycidyl group-containing vinyl monomer.
4. The coating material raw material for a secondary battery separator according to claim 1, wherein, with respect to 100 parts by mass of the total amount of the water-soluble polymer and the water-insoluble polymer,
the water-soluble polymer is 50 to 99 parts by mass,
the water-insoluble polymer is 1 to 50 parts by mass.
5. The coating material raw material for a secondary battery separator according to claim 1, wherein the water-soluble polymer has a weight average molecular weight of 1 to 20 ten thousand.
6. The coating material raw material for a secondary battery separator according to claim 1, wherein the water-soluble polymer has a glass transition temperature of 150 ℃ to 240 ℃.
7. The coating material raw material for a secondary battery separator according to claim 1, wherein the water-insoluble polymer has a glass transition temperature of-40 ℃ to 50 ℃.
8. A coating material for a secondary battery separator, comprising the coating material raw material for a secondary battery separator according to claim 1.
9. The coating material for a secondary battery separator according to claim 8, further comprising an inorganic filler and a dispersant.
10. A secondary battery separator is characterized by comprising:
A porous membrane; and
the coating film of the coating material for a secondary battery separator according to claim 8, which is disposed on at least one surface of the porous film.
11. A method for manufacturing a secondary battery separator, characterized by comprising the following steps:
preparing a porous film; the method comprises the steps of,
a step of applying the coating material for secondary battery separator according to claim 8 to at least one surface of the porous film.
12. A secondary battery comprising a positive electrode, a negative electrode, and the secondary battery separator according to claim 10 disposed between the positive electrode and the negative electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021108376 | 2021-06-30 | ||
| JP2021-108376 | 2021-06-30 | ||
| PCT/JP2022/025239 WO2023276867A1 (en) | 2021-06-30 | 2022-06-24 | Coating starting material for secondary battery separator, coating material for secondary battery separator, secondary battery separator, method for producing secondary battery separator, and secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117242634A true CN117242634A (en) | 2023-12-15 |
Family
ID=84691282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280029862.XA Pending CN117242634A (en) | 2021-06-30 | 2022-06-24 | Coating material raw material for secondary battery separator, coating material for secondary battery separator, method for producing secondary battery separator, and secondary battery |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2023276867A1 (en) |
| KR (1) | KR20230162050A (en) |
| CN (1) | CN117242634A (en) |
| WO (1) | WO2023276867A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9450223B2 (en) * | 2012-02-06 | 2016-09-20 | Samsung Sdi Co., Ltd. | Lithium secondary battery |
| JP6552921B2 (en) | 2015-08-31 | 2019-07-31 | 住友重機械工業株式会社 | Injection device |
| WO2018173717A1 (en) * | 2017-03-24 | 2018-09-27 | 日本ゼオン株式会社 | Binder composition for nonaqueous secondary batteries and slurry composition for nonaqueous secondary batteries |
| JP2019192339A (en) * | 2018-04-18 | 2019-10-31 | 三井化学株式会社 | Secondary battery separator, secondary battery laminate and wound body including the same, and non-aqueous secondary battery |
-
2022
- 2022-06-24 CN CN202280029862.XA patent/CN117242634A/en active Pending
- 2022-06-24 KR KR1020237036846A patent/KR20230162050A/en unknown
- 2022-06-24 WO PCT/JP2022/025239 patent/WO2023276867A1/en active Application Filing
- 2022-06-24 JP JP2023531892A patent/JPWO2023276867A1/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023276867A1 (en) | 2023-01-05 |
| JPWO2023276867A1 (en) | 2023-01-05 |
| KR20230162050A (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7185504B2 (en) | Raw material for coating material for secondary battery separator, method for producing raw material for coating material for secondary battery separator, coating material for secondary battery separator, secondary battery separator, method for producing secondary battery separator, and secondary battery | |
| CN109266266B (en) | Water-based polyacrylate/polyurethane/SiO2Preparation method of nano composite adhesive | |
| JP2014175055A (en) | Porous film for secondary battery, slurry for secondary battery porous film, method of manufacturing porous film for secondary battery, electrode for secondary battery, separator for secondary battery, and secondary battery | |
| WO2015093765A1 (en) | Method for preparing aqueous binder for positive electrode active material of secondary battery | |
| CN108117855B (en) | Binder composition for electricity storage device, slurry for porous layer, separator, and lithium ion secondary battery | |
| Li et al. | Acrylic emulsion pressure-sensitive adhesives (PSAS) reinforced with layered silicate | |
| CN117242634A (en) | Coating material raw material for secondary battery separator, coating material for secondary battery separator, method for producing secondary battery separator, and secondary battery | |
| WO2021210499A1 (en) | Coating material feedstock for secondary battery separator, coating material for secondary battery separator, secondary battery separator, secondary battery separator production method, and secondary battery | |
| JP7311587B2 (en) | Coating material for secondary battery separator | |
| JP5881496B2 (en) | Undercoat for release substrate | |
| WO2022241068A1 (en) | Binder composition for negative electrode | |
| JP7220216B2 (en) | Composition for power storage device, slurry for power storage device electrode, power storage device electrode, and power storage device | |
| CN115461922B (en) | Coating material raw material for secondary battery separator, coating material for secondary battery separator, method for producing secondary battery separator, and secondary battery | |
| WO2021141119A1 (en) | Aqueous dispersion, adhesive for lithium ion secondary batteries, slurry for lithium ion secondary battery porous layers, lithium ion secondary battery porous layer, separator for lithium ion secondary batteries, and lithium ion secondary battery | |
| WO2023136319A1 (en) | Coating material for secondary battery separator, secondary battery separator, and secondary battery | |
| WO2015119085A1 (en) | Method for estimating binding properties between fine particles and binder resin in coating film, and method for improving binding properties between fine particles and binder resin in coating film | |
| WO2023228877A1 (en) | Starting material of coating material for secondary battery separators, coating material for secondary battery separators, secondary battery separator and secondary battery | |
| JP2024007496A (en) | Coat material raw material for secondary battery separator, coat material for secondary battery separator, secondary battery separator, and second battery | |
| WO2024116997A1 (en) | Starting material for coating material for secondary battery separator, coating material for secondary battery separator, secondary battery separator, and secondary battery | |
| TW202244223A (en) | Adhesive composition and method of making same | |
| JP2024007380A (en) | Binder for nonaqueous secondary battery, slurry for lithium ion secondary battery porous layer, lithium ion secondary battery porous layer, lithium ion secondary battery separator, and lithium ion secondary battery | |
| CN115651581A (en) | Preparation method of acrylate polymer modified heat-conducting structural adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |