JP6241213B2 - Binder resin composition for electrode, electrode mixture paste, and electrode - Google Patents
Binder resin composition for electrode, electrode mixture paste, and electrode Download PDFInfo
- Publication number
- JP6241213B2 JP6241213B2 JP2013231723A JP2013231723A JP6241213B2 JP 6241213 B2 JP6241213 B2 JP 6241213B2 JP 2013231723 A JP2013231723 A JP 2013231723A JP 2013231723 A JP2013231723 A JP 2013231723A JP 6241213 B2 JP6241213 B2 JP 6241213B2
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- electrode
- minutes
- binder resin
- resin composition
- paste
- Prior art date
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- 239000011230 binding agent Substances 0.000 title claims description 132
- 239000000203 mixture Substances 0.000 title claims description 107
- 239000011342 resin composition Substances 0.000 title claims description 90
- 238000010438 heat treatment Methods 0.000 claims description 54
- 229920001721 polyimide Polymers 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 43
- 239000009719 polyimide resin Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229920005575 poly(amic acid) Polymers 0.000 claims description 27
- 239000011863 silicon-based powder Substances 0.000 claims description 24
- -1 tetracarboxylic acid compound Chemical class 0.000 claims description 19
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 150000004984 aromatic diamines Chemical group 0.000 claims description 6
- 239000011883 electrode binding agent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 127
- 230000008961 swelling Effects 0.000 description 94
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 88
- 239000000243 solution Substances 0.000 description 77
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 75
- 239000000523 sample Substances 0.000 description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 62
- 239000011889 copper foil Substances 0.000 description 60
- 239000011521 glass Substances 0.000 description 58
- 239000011347 resin Substances 0.000 description 52
- 229920005989 resin Polymers 0.000 description 52
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 50
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- 239000011248 coating agent Substances 0.000 description 21
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
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- 150000001875 compounds Chemical class 0.000 description 7
- 238000006358 imidation reaction Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
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- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
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- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 4
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 4
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical group NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- 229940086681 4-aminobenzoate Drugs 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- JHAWWJQGHKGXHA-UHFFFAOYSA-N 6-tert-butylquinoline Chemical compound N1=CC=CC2=CC(C(C)(C)C)=CC=C21 JHAWWJQGHKGXHA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011530 conductive current collector Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000005187 foaming Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
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- VXGYRCVTBHVXMZ-UHFFFAOYSA-N quinoline-6-carboxylic acid Chemical compound N1=CC=CC2=CC(C(=O)O)=CC=C21 VXGYRCVTBHVXMZ-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- SFVSTECQIQQHHL-UHFFFAOYSA-N 1,2-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C1=C(N)C=C2S(=O)(=O)C3=CC(N)=C(C)C(C)=C3C2=C1 SFVSTECQIQQHHL-UHFFFAOYSA-N 0.000 description 1
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- JEFLTMZOOWERRP-UHFFFAOYSA-N 2,3,5,6-tetrachlorobenzene-1,4-diamine Chemical compound NC1=C(Cl)C(Cl)=C(N)C(Cl)=C1Cl JEFLTMZOOWERRP-UHFFFAOYSA-N 0.000 description 1
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- BHPCMPVIMAJIQS-UHFFFAOYSA-N 2,3,5,6-tetrakis(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=C(C(F)(F)F)C(C(F)(F)F)=C(N)C(C(F)(F)F)=C1C(F)(F)F BHPCMPVIMAJIQS-UHFFFAOYSA-N 0.000 description 1
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- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
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- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- OMIOAPDWNQGXED-UHFFFAOYSA-N 3-amino-n-(3-aminophenyl)benzamide Chemical compound NC1=CC=CC(NC(=O)C=2C=C(N)C=CC=2)=C1 OMIOAPDWNQGXED-UHFFFAOYSA-N 0.000 description 1
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical group C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- VFBWINMDCKEILI-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrachlorophenyl)-2,3,5,6-tetrachloroaniline Chemical compound ClC1=C(Cl)C(N)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(N)C(Cl)=C1Cl VFBWINMDCKEILI-UHFFFAOYSA-N 0.000 description 1
- SKQMJTLFJLUFHC-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenoxy)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1OC1=C(F)C(F)=C(N)C(F)=C1F SKQMJTLFJLUFHC-UHFFFAOYSA-N 0.000 description 1
- VSCWVWFFQWMDGE-UHFFFAOYSA-N 4-(4-amino-2,5-difluorophenyl)-2,5-difluoroaniline Chemical compound C1=C(F)C(N)=CC(F)=C1C1=CC(F)=C(N)C=C1F VSCWVWFFQWMDGE-UHFFFAOYSA-N 0.000 description 1
- PTQLPRQTQOOTRL-UHFFFAOYSA-N 4-(4-amino-2,6-dichlorophenyl)-3,5-dichloroaniline Chemical compound ClC1=CC(N)=CC(Cl)=C1C1=C(Cl)C=C(N)C=C1Cl PTQLPRQTQOOTRL-UHFFFAOYSA-N 0.000 description 1
- JQVZQTDUPLLZLN-UHFFFAOYSA-N 4-(4-amino-2,6-difluorophenyl)-3,5-difluoroaniline Chemical compound FC1=CC(N)=CC(F)=C1C1=C(F)C=C(N)C=C1F JQVZQTDUPLLZLN-UHFFFAOYSA-N 0.000 description 1
- XKXPBJBODVHDAW-UHFFFAOYSA-N 4-(4-amino-2-chlorophenyl)-3-chloroaniline Chemical compound ClC1=CC(N)=CC=C1C1=CC=C(N)C=C1Cl XKXPBJBODVHDAW-UHFFFAOYSA-N 0.000 description 1
- LSJAPRRUOIMQSN-UHFFFAOYSA-N 4-(4-amino-2-fluorophenyl)-3-fluoroaniline Chemical compound FC1=CC(N)=CC=C1C1=CC=C(N)C=C1F LSJAPRRUOIMQSN-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- LVNPGQZSPDFZNC-UHFFFAOYSA-N 4-(4-amino-3-fluorophenyl)-2-fluoroaniline Chemical compound C1=C(F)C(N)=CC=C1C1=CC=C(N)C(F)=C1 LVNPGQZSPDFZNC-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- YFKPQCYLWJULME-UHFFFAOYSA-N 4-[(4-amino-2-methylphenyl)methyl]-3-methylaniline Chemical compound CC1=CC(N)=CC=C1CC1=CC=C(N)C=C1C YFKPQCYLWJULME-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- QBSMHWVGUPQNJJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(C=2C=CC(N)=CC=2)C=C1 QBSMHWVGUPQNJJ-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- QMEPPSJSNJRUEV-UHFFFAOYSA-N 4-[4-amino-2,5-bis(trifluoromethyl)phenyl]-2,5-bis(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC(C(F)(F)F)=C1C1=CC(C(F)(F)F)=C(N)C=C1C(F)(F)F QMEPPSJSNJRUEV-UHFFFAOYSA-N 0.000 description 1
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 1
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- QNDFYLBDUWCFJO-UHFFFAOYSA-N 4-fluorobenzene-1,3-diamine Chemical compound NC1=CC=C(F)C(N)=C1 QNDFYLBDUWCFJO-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QQPYIXJPRJQUDC-UHFFFAOYSA-N 5-(3-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1C(O)=O QQPYIXJPRJQUDC-UHFFFAOYSA-N 0.000 description 1
- JJJDAERKXDTMPH-UHFFFAOYSA-N 5-(4-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=C1C(O)=O JJJDAERKXDTMPH-UHFFFAOYSA-N 0.000 description 1
- ZMPPXANJPWZRRK-UHFFFAOYSA-N CN1C(N(CC1)C)=O.CN1C(CCCCC1)=O Chemical compound CN1C(N(CC1)C)=O.CN1C(CCCCC1)=O ZMPPXANJPWZRRK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- PAHDBSAHHYDWFA-UHFFFAOYSA-N FC(C1=C(C(=C(C(=C1C(F)(F)F)N)C(F)(F)F)C(F)(F)F)C1=C(C(=C(N)C(=C1C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)(F)F Chemical compound FC(C1=C(C(=C(C(=C1C(F)(F)F)N)C(F)(F)F)C(F)(F)F)C1=C(C(=C(N)C(=C1C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)(F)F PAHDBSAHHYDWFA-UHFFFAOYSA-N 0.000 description 1
- URVMUAJVLNDZPM-UHFFFAOYSA-N O(C=1C=C(N)C=CC=1C(F)(F)F)C=1C=C(N)C=CC=1C(F)(F)F Chemical compound O(C=1C=C(N)C=CC=1C(F)(F)F)C=1C=C(N)C=CC=1C(F)(F)F URVMUAJVLNDZPM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- CTLVQCQPPLNJQW-UHFFFAOYSA-N S(=O)(=O)=NC1=CC=CC=C1.C12=CC=C(C=C1)S2 Chemical compound S(=O)(=O)=NC1=CC=CC=C1.C12=CC=C(C=C1)S2 CTLVQCQPPLNJQW-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- 239000000654 additive Substances 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
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Description
本発明は、リチウムイオン二次電池、電気二重層キャパシタなどの電気化学素子の電極用のバインダー樹脂組成物に関する。 The present invention relates to a binder resin composition for electrodes of electrochemical devices such as lithium ion secondary batteries and electric double layer capacitors.
リチウムイオン二次電池は、高いエネルギー密度を有し、高容量であるため、移動情報端末の駆動電源などとして広く利用されている。近年は、大容量を必要とする電気・ハイブリッド自動車への搭載など産業用途での使用も広まりつつあり、更なる高容量化や高性能化のための検討がなされている。その試みの一つは、例えば負極活物質として単位体積あたりのリチウム吸蔵量の多いケイ素やスズ、或いはこれらを含む合金を用いて、充放電容量を増大させようとするものである。 Lithium ion secondary batteries have high energy density and high capacity, and are therefore widely used as driving power sources for mobile information terminals. In recent years, use in industrial applications such as mounting on electric / hybrid vehicles that require large capacity is becoming widespread, and studies are being conducted for further increase in capacity and performance. One of the attempts is to increase the charge / discharge capacity by using, for example, silicon or tin having a large amount of lithium occlusion per unit volume or an alloy containing these as a negative electrode active material.
しかし、ケイ素やスズ、或いはこれらを含む合金のような充放電容量の大きな活物質を用いると、充放電に伴って活物質が非常に大きな体積変化を起こすため、これまでの炭素を活物質として用いた電極で広く用いられていたポリフッ化ビニリデンやゴム系の樹脂をバインダー樹脂として用いたのでは、活物質層が破壊され易くなったり、集電体と活物質層との界面で剥離が発生し易くなったりするために、電極内の集電構造が破壊され、電極の電子伝導性が低下して電池のサイクル特性が容易に低下するという問題があった。
このため、非常に大きな体積変化に対しても電極の破壊や剥離を起こしにくい、電池環境下での靭性が高いバインダー樹脂組成物が望まれていた。
However, if an active material with a large charge / discharge capacity such as silicon, tin, or an alloy containing these is used, the active material undergoes a very large volume change along with charge / discharge. If polyvinylidene fluoride or rubber-based resin widely used for the electrode used is used as the binder resin, the active material layer is likely to be broken or peeling occurs at the interface between the current collector and the active material layer Therefore, there is a problem in that the current collecting structure in the electrode is broken, the electron conductivity of the electrode is lowered, and the cycle characteristics of the battery are easily lowered.
For this reason, there has been a demand for a binder resin composition that has high toughness in a battery environment and that does not easily break or peel off an electrode even with a very large volume change.
特許文献１に記載されているとおり、リチウムイオン二次電池の電極用の結着剤にポリイミド樹脂を用いることは公知ある。
特許文献２、特許文献３には、ケイ素合金やスズを含む合金からなる活物質に対して、それぞれ特定の機械的特性を有するバインダー樹脂を用いることが提案されている。しかしながら、ここでは樹脂の具体的な化学構造について開示されていない。
特許文献４には、ケイ素、及びケイ素系合金からなる活物質と、特定の化学構造を有するポリイミド樹脂をバインダーに用いたリチウム二次電池が提案されている。このポリイミド樹脂は、３，３’，４，４’−ベンゾフェノンテトラカルボン酸残基を有するポリイミドであった。
As described in Patent Document 1, it is known to use a polyimide resin as a binder for an electrode of a lithium ion secondary battery.
Patent Documents 2 and 3 propose using binder resins having specific mechanical properties for an active material made of an alloy containing a silicon alloy or tin. However, the specific chemical structure of the resin is not disclosed here.
Patent Document 4 proposes a lithium secondary battery using, as a binder, an active material composed of silicon and a silicon-based alloy and a polyimide resin having a specific chemical structure. This polyimide resin was a polyimide having 3,3 ′, 4,4′-benzophenone tetracarboxylic acid residues.
一方、非特許文献１には、電解液に対する電極用のバインダー樹脂の膨潤度が小さいほど充放電サイクルに伴う放電容量保持率が高くなるので好ましいことが示されている。 On the other hand, Non-Patent Document 1 shows that the smaller the degree of swelling of the binder resin for electrodes with respect to the electrolytic solution, the higher the discharge capacity retention rate associated with the charge / discharge cycle, which is preferable.
本発明の目的は、電池環境下でも膨潤度が小さく高い靱性を保つことができるバインダー樹脂を得ることができる、新たな化学構造からなる電極用バインダー樹脂組成物を提案することである。 An object of the present invention is to propose a binder resin composition for electrodes having a new chemical structure, which can obtain a binder resin having a small degree of swelling and high toughness even in a battery environment.
本発明願発明者らは、種々検討した結果、特定の化学構造からなる樹脂組成物を用いると、電池環境下でも膨潤度が小さく、高い靱性（大きな破断伸度及び破断エネルギー）を有する、新たな電極用バインダー樹脂組成物を得ることを見出して、本発明に至った。 As a result of various investigations, the inventors of the present invention have found that when a resin composition having a specific chemical structure is used, the degree of swelling is small even in a battery environment, and the toughness (large breaking elongation and breaking energy) is high. The present inventors have found that a binder resin composition for an electrode can be obtained, and have reached the present invention.
すなわち、本発明は以下の項に関する。
１． テトラカルボン酸成分とジアミン成分とからなるモノマー成分を反応して得られるポリアミック酸、および／または、ポリイミド樹脂を溶媒に溶解してなる電極用バインダー樹脂組成物であって、前記ポリアミック酸およびポリイミド樹脂が、テトラカルボン酸成分として分子内にアミド結合を１つまたは２つ有するテトラカルボン酸化合物を、および／または、ジアミン成分として分子内にアミド結合を１つまたは２つ有するジアミン化合物を含有するモノマー成分を重合して得られるものであることを特徴とする電極用バインダー樹脂組成物。
２． 分子内にアミド結合を１つまたは２つ有するテトラカルボン酸化合物が、下記一般式（１）および（２）からなる群から選択されることを特徴とする、前記項１に記載の電極用バインダー樹脂組成物。
３． 分子内にアミド結合を１つまたは２つ有するジアミン化合物が、ジアミノベンズアニリド類であることを特徴とする前記項１〜２のいずれかに記載の電極用バインダー樹脂組成物。
４． 分子内にアミド結合を有する化合物の含有量が、全モノマー成分の２０〜８０モル％の範囲であることを特徴とする前記項１〜３のいずれかに記載の電極用バインダー樹脂組成物。
５． 加熱処理して得られるバインダー樹脂が、２５℃で２４時間ジメチルカーボネートに浸漬したときの質量増加が２．０質量％以下であることを特徴とする前記項１〜４のいずれかに記載の電極用バインダー樹脂組成物。
That is, the present invention relates to the following items.
1. A polyamic acid obtained by reacting a monomer component composed of a tetracarboxylic acid component and a diamine component, and / or a binder resin composition for an electrode obtained by dissolving a polyimide resin in a solvent, the polyamic acid and the polyimide resin Contains a tetracarboxylic acid compound having one or two amide bonds in the molecule as a tetracarboxylic acid component and / or a diamine compound having one or two amide bonds in the molecule as a diamine component A binder resin composition for electrodes, which is obtained by polymerizing components.
2. 2. The electrode binder according to item 1, wherein the tetracarboxylic acid compound having one or two amide bonds in the molecule is selected from the group consisting of the following general formulas (1) and (2): Resin composition.
3. Item 3. The binder resin composition for electrodes according to any one of Items 1 to 2, wherein the diamine compound having one or two amide bonds in the molecule is diaminobenzanilide.
4). Item 4. The binder resin composition for an electrode according to any one of Items 1 to 3, wherein the content of the compound having an amide bond in the molecule is in the range of 20 to 80 mol% of the total monomer components.
5. Item 5. The electrode according to any one of Items 1 to 4, wherein the binder resin obtained by the heat treatment has a mass increase of 2.0% by mass or less when immersed in dimethyl carbonate at 25 ° C. for 24 hours. Binder resin composition.
６． 電極活物質と前記項１〜５のいずれかに記載の電極用バインダー樹脂組成物とを含む電極合剤ペースト。
７． 電極活物質が炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末であることを特徴とする前記項６に記載の電極合剤ペースト。
８． 前記項６〜７のいずれかに記載の電極合剤ペーストを集電体上に塗布し、加熱処理して溶媒を除去するとともにイミド化反応することにより得られることを特徴とする電極。
９． 加熱処理温度が２５０℃以下であることを特徴とする前記項８に記載の電極。
１０． リチウムイオン二次電池用負極であることを特徴とする前記項８〜９のいずれかに記載の電極。
6). The electrode mixture paste containing an electrode active material and the binder resin composition for electrodes according to any one of Items 1 to 5.
7). Item 7. The electrode mixture paste according to Item 6, wherein the electrode active material is carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin.
8). 8. An electrode obtained by applying the electrode mixture paste according to any one of Items 6 to 7 on a current collector, heating to remove the solvent, and imidizing reaction.
9. 9. The electrode according to item 8, wherein the heat treatment temperature is 250 ° C. or lower.
10. Item 10. The electrode according to any one of Items 8 to 9, which is a negative electrode for a lithium ion secondary battery.
本発明によれば、電池環境下でも膨潤度が小さく、高い靱性（大きな破断伸度及び破断エネルギー）を有するバインダー樹脂を得ることが可能な、新たな化学構造からなる電極用バインダー樹脂組成物を得ることができる。 According to the present invention, there is provided a binder resin composition for an electrode having a new chemical structure, which is capable of obtaining a binder resin having a low degree of swelling even under a battery environment and having high toughness (large breaking elongation and breaking energy). Can be obtained.
本発明の電極用バインダー樹脂組成物に用いるポリアミック酸およびポリイミド樹脂は、テトラカルボン酸成分として分子内にアミド結合を１つまたは２つ有するテトラカルボン酸化合物を、および／または、ジアミン成分として分子内にアミド結合を１つまたは２つ有するジアミン化合物を含有するモノマー成分を重合して得られるものであることを特徴とする。 The polyamic acid and the polyimide resin used for the binder resin composition for electrodes of the present invention include a tetracarboxylic acid compound having one or two amide bonds in the molecule as a tetracarboxylic acid component and / or an intramolecular as a diamine component. It is obtained by polymerizing a monomer component containing a diamine compound having one or two amide bonds.
本発明で用いる分子内にアミド結合を１つまたは２つ有するテトラカルボン酸化合物としては、下記一般式（１）および（２）で表されるアミド基含有テトラカルボン酸二無水物を挙げることができる。
Examples of the tetracarboxylic acid compound having one or two amide bonds in the molecule used in the present invention include amide group-containing tetracarboxylic dianhydrides represented by the following general formulas (1) and (2). it can.
上記一般式（１）および（２）におけるＲは、ベンゼン環を１から４個含む芳香族ジアミン残基であればよく、特に制限はないが、より具体的な芳香族ジアミンとして、ベンゼン環が１個の場合は、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，４−ジアミノキシレン、２，５−ジアミノキシレン、２，５−ジアミノデュレン、２−フルオロ−１，４−フェニレンジアミン、２−フルオロ−１，３−フェニレンジアミン、４−フルオロ−１，３−フェニレンジアミン、２，５−ジフルオロ−１，４−フェニレンジアミン、２，３，５，６−テトラフルオロ−１，４−フェニレンジアミン、２，４，５，６−テトラフルオロ−１，３−フェニレンジアミン、２−クロロ−１，４−フェニレンジアミン、２−クロロ−１，３−フェニレンジアミン、４−クロロ−１，３−フェニレンジアミン、２，５−ジクロロ−１，４−フェニレンジアミン、２，３，５，６−テトラクロロ−１，４−フェニレンジアミン、２，４，５，６−テトラクロロ−１，３−フェニレンジアミン、２−トリフルオロメチル−１，４−フェニレンジアミン、２−トリフルオロメチル−１，３−フェニレンジアミン、４−トリフルオロメチル−１，３−フェニレンジアミン、２，５−ビストリフルオロメチル−１，４−フェニレンジアミン、２，３，５，６−テトラキストリフルオロメチル−１，４−フェニレンジアミン、２，４，５，６−テトラキストリフルオロメチル−１，３−フェニレンジアミン等が挙げられる。 R in the general formulas (1) and (2) is not particularly limited as long as it is an aromatic diamine residue containing 1 to 4 benzene rings, but as a more specific aromatic diamine, In the case of one, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,5-diaminoxylene, 2,5-diaminodurene 2-fluoro-1,4-phenylenediamine, 2-fluoro-1,3-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,3 , 5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2-chloro-1, -Phenylenediamine, 2-chloro-1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2,3,5,6-tetrachloro- 1,4-phenylenediamine, 2,4,5,6-tetrachloro-1,3-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-trifluoromethyl-1,3-phenylenediamine 4-trifluoromethyl-1,3-phenylenediamine, 2,5-bistrifluoromethyl-1,4-phenylenediamine, 2,3,5,6-tetrakistrifluoromethyl-1,4-phenylenediamine, 2, 4,5,6-tetrakistrifluoromethyl-1,3-phenylenediamine and the like.
ベンゼン環が２個の場合は、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、２，４’−ジアミノジフェニルエーテル、２，２’−ビス（トリフルオロメチル）ベンジジン、３，３’−ビス（トリフルオロメチル）ベンジジン、２，２’，５，５’−テトラキス（トリフルオロメチル）ベンジジン、２，２’，６，６’−テトラキス（トリフルオロメチル）ベンジジン、２，２’，３，３’，５，５’，６，６’−オクタキス（トリフルオロメチル）ベンジジン、２，２’−ジフルオロベンジジン、３，３’−ジフルオロベンジジン、２，２’，５，５’−テトラフルオロベンジジン、２，２’，６，６’−テトラフルオロベンジジン、２，２’，３，３’，５，５’，６，６’−オクタフルオロベンジジン、２，２’−ジクロロベンジジン、３，３’−ジクロロベンジジン、２，２’，５，５’−テトラクロロベンジジン、２，２’，６，６’−テトラクロロベンジジン、２，２’，３，３’，５，５’，６，６’−オクタクロロベンジジン、４，４’−ジアミノジフェニルスルフォン、３，３’−ジアミノジフェニルスルフォン、３，４’−ジアミノジフェニルスルフォン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、３，４’−ジアミノベンゾフェノン、４，４’−ジアミノビフェニル、３，３’−ジアミノビフェニル、ｏ−トリジン、ｍ−トリジン、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、２，２’−ビス（４−アミノフェニル）ヘキサフルオロプロパン、２，２’−ビス（３−アミノフェニル）ヘキサフルオロプロパン、２，２’−（３，４−ジアミノジフェニル）ヘキサフルオロプロパン、４，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルメタン、４，４’−メチレンビス（２−メチルアニリン）、４，４’−メチレンビス（３−メチルアニリン）、４，４’−メチレンビス（２−エチルアニリン）、４，４’−メチレンビス（３−エチルアニリン）、４，４’−メチレンビス（２，６−ジメチルアニリン）、４，４’−メチレンビス（２，６−ジエチルアニリン）、４，４’−オキシビス(３−トリフルオロメチルアニリン)、３，３’−オキシビス(４−トリフルオロメチルアニリン)、４，４’−オキシビス(２，３，５，６−テトラフルオロアニリン)、４，４’−チオビス(２，３，５，６−テトラフルオロアニリン)、４，４’−ジアミノベンズアニリド、３，７−ジアミノ−ジメチルジベンゾチオフェン−５，５−ジオキシド等が挙げられる。 When there are two benzene rings, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 2,2′-bis (trifluoro) Methyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) benzidine, 2,2 ′, 6,6′-tetrakis (trifluoromethyl) ) Benzidine, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octakis (trifluoromethyl) benzidine, 2,2′-difluorobenzidine, 3,3′-difluorobenzidine, 2,2 ', 5,5'-tetrafluorobenzidine, 2,2', 6,6'-tetrafluorobenzidine, 2,2 ', 3,3', 5, ', 6,6'-octafluorobenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2', 5,5'-tetrachlorobenzidine, 2,2 ', 6,6' -Tetrachlorobenzidine, 2,2 ', 3,3', 5,5 ', 6,6'-octachlorobenzidine, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, o-tolidine, m-tolidine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 2,2′-bis (4-aminophenyl) hexafluoro Lopan, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2 ′-(3,4-diaminodiphenyl) hexafluoropropane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane 4,4′-methylenebis (2-methylaniline), 4,4′-methylenebis (3-methylaniline), 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (3-ethyl) Aniline), 4,4′-methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2,6-diethylaniline), 4,4′-oxybis (3-trifluoromethylaniline), 3, 3′-oxybis (4-trifluoromethylaniline), 4,4′-oxybis (2,3,5,6-tetrafluoroaniline), 4,4 Examples include '-thiobis (2,3,5,6-tetrafluoroaniline), 4,4'-diaminobenzanilide, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide.
ベンゼン環が３個の場合は、ｐ−ターフェニレンジアミン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン等が挙げられ、ベンゼン環が４個の場合は、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（３−アミノフェノキシ）フェニル）スルフォン、ビス（４−（４−アミノフェノキシ）フェニル）スルフォン、２，２’−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、２，２’−ビス（４−（４−アミノフェノキシ）フェニル）ヘキサフルオロプロパン、２，２’−ビス（４−（３−アミノフェノキシ）フェニル）ヘキサフルオロプロパン、４，４’−スルフォニルビス（４−フェニレンサルファニルアニリン）、３，３’−スルフォニルビス（ｐ−フェニレンサルファニルアニリン）等が挙げられる。 When there are three benzene rings, p-terphenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino When there are four benzene rings, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- ( 4-aminophenoxy) phenyl) sulfone, 2,2′-bis (4- (4-aminophenoxy) phenyl) propane, 2,2′-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2 , 2′-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 4,4′-sulfonylbis (4-phenylenesulfanyl) Diphosphate), 3,3'-sulfonyl bis (p- phenylene sulfide sulfonyl aniline), and the like.
上記一般式（１）および（２）におけるＲは、ベンゼン環を１または２個含む芳香族ジアミン残基であるのが好ましく、特に、下記（ｉ）から（ｉｖ）の中から選ばれる芳香族ジアミン残基であるのが好ましい。
本発明で用いる分子内にアミド結合を１つまたは２つ有するジアミン化合物としては、ジアミノベンズアニリド類を挙げることができる。具体的には４，４’−ジアミノベンズアニリド、３，３’−ジアミノベンズアニリド、２’，４−ジアミノベンズアニリド等が挙げられる。 Examples of the diamine compound having one or two amide bonds in the molecule used in the present invention include diaminobenzanilides. Specific examples include 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 2 ', 4-diaminobenzanilide, and the like.
本発明で用いるポリアミック酸およびポリイミド樹脂においては、アミド結合を有する化合物を全モノマー成分のうち、２０〜８０モル％の範囲で用いることが好ましい。これにより、得られるポリイミド樹脂の電解液に対する樹脂の膨潤度が小さく、破断伸度及び破断エネルギーが大きくなるので電極用バインダー樹脂として極めて好適である。 In the polyamic acid and the polyimide resin used in the present invention, it is preferable to use a compound having an amide bond in the range of 20 to 80 mol% of all monomer components. Thereby, since the swelling degree of the resin with respect to the electrolyte solution of the polyimide resin obtained is small and the breaking elongation and breaking energy are large, it is extremely suitable as a binder resin for electrodes.
本発明において使用可能な分子内にアミド結合を有しないテトラカルボン酸成分としては、例えば、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、４，４’−オキシジフタル酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物、ｐ−ターフェニルテトラカルボン酸二無水物、ｍ−ターフェニルテトラカルボン酸二無水物などが挙げられる。これらのうち、特に、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物が好ましい。 Examples of the tetracarboxylic acid component having no amide bond in the molecule usable in the present invention include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′. -Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid Anhydride, diphenylsulfone tetracarboxylic dianhydride, p-terphenyl tetracarboxylic dianhydride, m-terphenyl tetracarboxylic dianhydride, etc. are mentioned. Of these, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is particularly preferable.
本発明において使用可能な分子内にアミド結合を有しないジアミン成分としては、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、２，４−トルエンジアミン、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、ビス（４−アミノ−３−カルボキシフェニル）メタン、２，４−ジアミノトルエンなどが挙げられる。これらのうち、特に、ｐ−フェニレンジアミンおよび４，４’−ジアミノジフェニルエーテルが好ましい。 Examples of the diamine component having no amide bond in the molecule that can be used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4. Examples include '-diaminodiphenylmethane, 2,4-toluenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, and 2,4-diaminotoluene. . Of these, p-phenylenediamine and 4,4'-diaminodiphenyl ether are particularly preferable.
本発明のポリアミック酸およびポリイミド樹脂を構成するテトラカルボン酸成分とジアミン成分とのモル比［テトラカルボン酸成分／ジアミン成分］は略等モル、具体的には０．９５〜１．０５好ましくは０．９７〜１．０３になるようにすることが重要である。このモル比の範囲外では、得られるポリイミド樹脂の靭性が低くなる恐れがある。 The molar ratio of the tetracarboxylic acid component and the diamine component constituting the polyamic acid and polyimide resin of the present invention [tetracarboxylic acid component / diamine component] is approximately equimolar, specifically 0.95 to 1.05, preferably 0. It is important to set it to 97 to 1.03. Outside the range of this molar ratio, the toughness of the resulting polyimide resin may be reduced.
本発明で用いるポリアミック酸は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させることで容易に調製することができる。限定するものではないが、好ましくはジアミン成分を溶剤に溶解した溶液にテトラカルボン酸成分を一度に、或いは多段階で添加し、攪拌することにより好適に行うことができる。反応温度は１０℃〜６０℃が好ましく、１５℃〜５５℃がさらに好ましく、１５℃〜５０℃が特に好ましい。反応温度が１０℃より低いと反応が遅くなることから好ましくなく、６０℃より高いと溶液の粘度が低くなることがあり好ましくない。反応時間は、０．５時間〜７２時間の範囲が好ましく、１時間〜６０時間がさらに好ましく、１．５時間〜４８時間が特に好ましい。反応時間が０．５時間より短いと反応が十分進行せず、合成されたポリアミック酸溶液の粘度が不安定になることがある。一方、７２時間以上の時間をかけるのは生産性の面から好ましくない。 The polyamic acid used in the present invention can be easily prepared by reacting a diamine component and a tetracarboxylic acid component in a solvent. Although it does not limit, Preferably, it can carry out suitably by adding the tetracarboxylic acid component to the solution which melt | dissolved the diamine component in the solvent at once or in multistep, and stirring. The reaction temperature is preferably 10 ° C to 60 ° C, more preferably 15 ° C to 55 ° C, and particularly preferably 15 ° C to 50 ° C. When the reaction temperature is lower than 10 ° C, the reaction is slow, which is not preferable. The reaction time is preferably in the range of 0.5 to 72 hours, more preferably 1 to 60 hours, and particularly preferably 1.5 to 48 hours. When the reaction time is shorter than 0.5 hours, the reaction does not proceed sufficiently, and the viscosity of the synthesized polyamic acid solution may become unstable. On the other hand, taking 72 hours or more is not preferable from the viewpoint of productivity.
本発明で用いるポリイミド樹脂は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させることで製造することができる。限定するものではないが、好ましくはジアミン成分を溶剤に溶解した溶液にテトラカルボン酸成分を一度に、或いは多段階で添加し、攪拌することにより好適に行うことができる。反応温度は１２０℃〜２２０℃が好ましく、１５０℃〜２００℃がさらに好ましく、１６０℃〜１８０℃が特に好ましい。反応温度が１２０℃より低いとイミド化反応が遅くなることから好ましくなく、２２０℃より高いと溶媒の沸点よりも高くなり好ましくない。反応時間は、０．５時間〜７２時間の範囲が好ましく、１時間〜６０時間がさらに好ましく、１．５時間〜４８時間が特に好ましい。反応時間が０．５時間より短いと反応が十分進行せず、合成されたポリアミック酸溶液の粘度が不安定になることがある。一方、７２時間以上の時間をかけるのは生産性の面から好ましくない。 The polyimide resin used in the present invention can be produced by reacting a diamine component and a tetracarboxylic acid component in a solvent. Although it does not limit, Preferably, it can carry out suitably by adding the tetracarboxylic acid component to the solution which melt | dissolved the diamine component in the solvent at once or in multistep, and stirring. The reaction temperature is preferably 120 ° C to 220 ° C, more preferably 150 ° C to 200 ° C, and particularly preferably 160 ° C to 180 ° C. When the reaction temperature is lower than 120 ° C., the imidization reaction is slow, which is not preferable. The reaction time is preferably in the range of 0.5 to 72 hours, more preferably 1 to 60 hours, and particularly preferably 1.5 to 48 hours. When the reaction time is shorter than 0.5 hours, the reaction does not proceed sufficiently, and the viscosity of the synthesized polyamic acid solution may become unstable. On the other hand, taking 72 hours or more is not preferable from the viewpoint of productivity.
ポリイミド樹脂の製造においては、さらにピリジン類化合物を用いることが、得られるポリイミド樹脂の電解液に対する膨潤度をより小さくし、破断伸度及び破断エネルギーをより大きくすることができ、さらにポリイミド樹脂を得るための反応温度を低く抑えることができるので、好適である。
ピリジン類化合物は、化学構造中にピリジン骨格を有する化合物のことであり、例えばピリジン、３−ピリジノール、キノリン、イソキノリン、キノキサリン、６−ｔｅｒｔ−ブチルキノリン、アクリジン、６−キノリンカルボン酸、３，４−ルチジン、ピリダジン、などを好適に挙げることができる。これらのピリジン類化合物は、単独または２種以上併用して使用しても差し支えない。
In the production of the polyimide resin, the use of a pyridine compound can further reduce the degree of swelling of the resulting polyimide resin with respect to the electrolyte solution, increase the breaking elongation and breaking energy, and obtain a polyimide resin. Therefore, the reaction temperature can be kept low.
The pyridine compound is a compound having a pyridine skeleton in the chemical structure. For example, pyridine, 3-pyridinol, quinoline, isoquinoline, quinoxaline, 6-tert-butylquinoline, acridine, 6-quinolinecarboxylic acid, 3,4 -Lutidine, pyridazine, etc. can be mentioned preferably. These pyridine compounds may be used alone or in combination of two or more.
上記においてピリジン類化合物の添加量は、限定するものではないが、ポリイミド樹脂のイミド構造に対して（イミド構造１モル当たり）、好ましくは０．０５〜２．０モル当量、より好ましくは０．１〜１．０モル当量である。添加量がこの範囲外では、電解液に対する樹脂の膨潤度をより小さくし、得られるポリイミド樹脂の破断伸度及び破断エネルギーをより大きくし、さらにポリイミド樹脂を得るための反応温度を低く抑えるというピリジン類化合物の添加効果を得ることが難しい場合があり好ましくない。 In the above, the addition amount of the pyridine compound is not limited, but is preferably 0.05 to 2.0 molar equivalents, more preferably 0.00 relative to the imide structure of the polyimide resin (per mole of the imide structure). 1 to 1.0 molar equivalent. If the addition amount is outside this range, the swelling degree of the resin with respect to the electrolytic solution is reduced, the breaking elongation and breaking energy of the resulting polyimide resin are further increased, and further the reaction temperature for obtaining the polyimide resin is kept low. It is difficult to obtain the effect of adding a compound, which is not preferable.
ポリアミック酸およびポリイミド樹脂の調製には公知の有機溶剤を使用することができる。例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２−（２−メトキシエトキシ）エチル］エーテル、１，４−ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、ｍ−クレゾール、フェノール、γ−ブチロラクトンが挙げられる。これらの溶剤は、単独または２種以上混合して使用しても差し支えない。これらのうち、ポリアミック酸の溶解性、および安全性から、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、γ−ブチロラクトンが好ましく、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、γ−ブチロラクトンが特に好ましい。 A well-known organic solvent can be used for preparation of a polyamic acid and a polyimide resin. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2- Methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethylsulfoxide, dimethylsulfone, diphenylether, sulfolane, diphenylsulfone, tetramethylurea, anisole, m-cresol, phenol, γ-butyrolactone. These solvents may be used alone or in combination of two or more. Of these, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl are considered because of the solubility and safety of polyamic acid. 2-Imidazolidinone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are particularly preferable.
本発明の電池用バインダー樹脂組成物は、前記ポリアミック酸、および／または、ポリイミド樹脂を溶媒に均一に溶解してなる。この組成物は、ポリアミック酸、および／または、ポリイミド樹脂に起因する固形分濃度が５質量％超〜４５質量％、好ましくは１０質量％超〜４０質量％、より好ましくは１５質量％超〜３０質量％の組成物として好適に用いることができる。固形分濃度が５質量％より低いと溶液の粘度が低くなりすぎ、４５質量％より高いと溶液の流動性がなくなることがある。また溶液粘度は、３０℃における溶液粘度が、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは０．５〜５００Ｐａ・ｓｅｃ、さらに好ましくは１〜３００Ｐａ・ｓｅｃ、特に好ましくは３〜２００Ｐａ・ｓｅｃである。
溶液粘度が１０００Ｐａ・ｓｅｃを超えると、電極活物質粉末の混合や集電体上への均一な塗布が困難となり、また、０．５Ｐａ・ｓｅｃよりも低いと、電極活物質粉末の混合や集電体上への塗布時にたれなどが生じ、加熱乾燥、イミド化後のポリイミド樹脂の靭性が低くなる恐れがある。
The battery binder resin composition of the present invention is obtained by uniformly dissolving the polyamic acid and / or polyimide resin in a solvent. In this composition, the solid content concentration resulting from the polyamic acid and / or the polyimide resin is more than 5 mass% to 45 mass%, preferably more than 10 mass% to 40 mass%, more preferably more than 15 mass% to 30 mass%. It can be suitably used as a composition of mass%. When the solid content concentration is lower than 5% by mass, the viscosity of the solution becomes too low, and when it is higher than 45% by mass, the fluidity of the solution may be lost. The solution viscosity at 30 ° C. is preferably 1000 Pa · sec or less, more preferably 0.5 to 500 Pa · sec, still more preferably 1 to 300 Pa · sec, and particularly preferably 3 to 200 Pa · sec.
When the solution viscosity exceeds 1000 Pa · sec, it becomes difficult to mix the electrode active material powder and uniformly apply it onto the current collector. When the solution viscosity is lower than 0.5 Pa · sec, the electrode active material powder is mixed and collected. There is a risk that dripping or the like occurs during coating on the electric body, and the toughness of the polyimide resin after heat drying and imidization is lowered.
本発明の電極用バインダー樹脂組成物を調製する際に用いるポリアミック酸は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させて得られたポリアミック酸溶液を、例えば貧溶媒に投入して析出させる方法などにより単離して（それを、所定の溶剤に再度溶解させることによって）使用しても良いし、得られたポリアミック酸溶液を単離することなく、調製したものをそのままで、或いは単に希釈するなどして使用してもよい。生産性、コストの点から、得られたポリアミック酸溶液を単離することなくそのまま使用することが好ましい。 The polyamic acid used in preparing the electrode binder resin composition of the present invention is deposited by pouring a polyamic acid solution obtained by reacting a diamine component and a tetracarboxylic acid component in a solvent, for example, into a poor solvent. May be used (by re-dissolving it in a predetermined solvent), and the prepared polyamic acid solution may be used as it is without isolation, or simply It may be used after being diluted. From the viewpoint of productivity and cost, it is preferable to use the obtained polyamic acid solution as it is without isolation.
同様に、本発明の電極用バインダー樹脂組成物を調製する際に用いるポリイミド樹脂は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させて得られたポリイミド樹脂溶液を、例えば貧溶媒に投入して析出させる方法などにより単離して（それを、所定の溶剤に再度溶解させることによって）使用しても良いし、得られたポリイミド樹脂溶液を単離することなく、調製したものをそのままで、或いは単に希釈するなどして使用してもよい。生産性、コストの点から、得られたポリイミド樹脂溶液を単離することなくそのまま使用することが好ましい。 Similarly, the polyimide resin used when preparing the binder resin composition for an electrode of the present invention is a polyimide resin solution obtained by reacting a diamine component and a tetracarboxylic acid component in a solvent, for example, in a poor solvent. It may be used after isolation by a method such as precipitation (by re-dissolving it in a predetermined solvent), or the prepared polyimide resin solution may be used as it is without isolation. Alternatively, it may be used by simply diluting it. From the viewpoint of productivity and cost, it is preferable to use the obtained polyimide resin solution as it is without isolation.
本発明の電極用バインダー樹脂組成物を調製する際には、ポリアミック酸またはポリイミド樹脂を単独で用いても良いし、これらを混合して用いても良い。 When preparing the binder resin composition for electrodes of the present invention, a polyamic acid or a polyimide resin may be used alone, or a mixture thereof may be used.
本発明の電極用バインダー樹脂組成物で用いられる溶媒は、従来公知の有機溶媒を好適に用いることができる。常圧での沸点が３００℃以下の有機極性溶媒が好ましく、ポリアミック酸およびポリイミド樹脂の調製の際に用いられる前記溶媒を好適に用いることができる。 A conventionally well-known organic solvent can be used suitably for the solvent used with the binder resin composition for electrodes of this invention. An organic polar solvent having a boiling point of 300 ° C. or less at normal pressure is preferable, and the solvent used in preparing the polyamic acid and the polyimide resin can be suitably used.
本発明の電極用バインダー樹脂組成物において、ポリアミック酸を用いる場合は、さらにピリジン類化合物を含有することが、得られるポリイミド樹脂の電解液に対する膨潤度をより小さくし、破断伸度及び破断エネルギーをより大きくすることができ、さらに電極を得るための加熱処理温度を低く抑えることができるので、好適である。
ピリジン類化合物は、化学構造中にピリジン骨格を有する化合物のことであり、例えばピリジン、３−ピリジノール、キノリン、イソキノリン、キノキサリン、６−ｔｅｒｔ−ブチルキノリン、アクリジン、６−キノリンカルボン酸、３，４−ルチジン、ピリダジン、などを好適に挙げることができる。これらのピリジン類化合物は、単独または２種以上併用して使用しても差し支えない。
In the binder resin composition for an electrode of the present invention, when a polyamic acid is used, further containing a pyridine compound further reduces the degree of swelling of the resulting polyimide resin with respect to the electrolytic solution, and increases the elongation at break and the energy at break. This is preferable because it can be made larger and the heat treatment temperature for obtaining the electrode can be kept low.
The pyridine compound is a compound having a pyridine skeleton in the chemical structure. For example, pyridine, 3-pyridinol, quinoline, isoquinoline, quinoxaline, 6-tert-butylquinoline, acridine, 6-quinolinecarboxylic acid, 3,4 -Lutidine, pyridazine, etc. can be mentioned preferably. These pyridine compounds may be used alone or in combination of two or more.
電極用バインダー樹脂組成物におけるピリジン類化合物の添加量は、限定するものではないが、ポリアミック酸のアミック酸構造に対して（アミック酸構造１モル当たり）、好ましくは０．０５〜２．０モル当量、より好ましくは０．１〜１．０モル当量である。添加量がこの範囲外では、電解液に対する樹脂の膨潤度をより小さくし、得られるポリイミド樹脂の破断伸度及び破断エネルギーをより大きくし、さらに電極を得るための加熱処理温度を低く抑えるというピリジン類化合物の添加効果を得ることが難しい場合があり好ましくない。 The addition amount of the pyridine compound in the binder resin composition for electrodes is not limited, but is preferably 0.05 to 2.0 mol with respect to the amic acid structure of the polyamic acid (per mol of the amic acid structure). Equivalent, more preferably 0.1 to 1.0 molar equivalent. If the addition amount is outside this range, the degree of swelling of the resin with respect to the electrolyte solution is further reduced, the breaking elongation and the breaking energy of the resulting polyimide resin are further increased, and further the heat treatment temperature for obtaining the electrode is kept low. It is difficult to obtain the effect of adding a compound, which is not preferable.
ポリアミック酸を用いた電極用バインダー樹脂組成物は、加熱処理或いはイミド化剤などの化学的処理によって、容易にポリイミド樹脂になる。例えば、電極用バインダー樹脂組成物を基材上に流延あるいは塗布して１２０℃〜１８０℃の範囲で加熱乾燥後、自己支持性となったフィルムを基材から剥離し、金属枠などに固定して、さらに２００℃〜４００℃で５分〜１０時間加熱してポリイミド樹脂フィルムを好適にあることができる。
本発明の電極用バインダー樹脂組成物は、前記のような加熱処理によって得られたポリイミド樹脂が、ジメチルカーボネートに２５℃で２４時間浸漬したときに、その質量増加が好ましくは３質量％以下、より好ましくは２質量％以下になるので、電池用バインダー樹脂組成物として好適に用いることができる。
また、本発明の電極用バインダー樹脂組成物は、前記のような加熱処理によって得られたポリイミド樹脂の引張破断エネルギーが１００ＭＪ／ｍ３以上、より好ましくは１１０ＭＪ／ｍ３以上、さらに好ましくは１２０ＭＪ／ｍ３以上であり、且つジメチルカーボネートに２５℃で２４時間浸漬した後の引張破断エネルギーの保持率が７０％以上、より好ましくは７５％以上、さらに好ましくは８０％以上であり、優れた靱性を有するので、電池用バインダー樹脂組成物として好適に用いることができる。
The binder resin composition for electrodes using polyamic acid easily becomes a polyimide resin by heat treatment or chemical treatment such as an imidizing agent. For example, a binder resin composition for electrodes is cast or coated on a base material, heat-dried in the range of 120 ° C to 180 ° C, and then the self-supporting film is peeled off from the base material and fixed to a metal frame or the like. Further, the polyimide resin film can be suitably obtained by heating at 200 ° C. to 400 ° C. for 5 minutes to 10 hours.
When the polyimide resin obtained by the heat treatment as described above is immersed in dimethyl carbonate at 25 ° C. for 24 hours, the increase in mass is preferably 3% by mass or less. Since it becomes 2 mass% or less preferably, it can be used suitably as a binder resin composition for batteries.
Further, electrode binder resin composition of the present invention has a tensile energy to break of the polyimide resin obtained by the heat treatment as described above is 100 MJ / m 3 or more, more preferably 110 mJ / m 3 or more, more preferably 120 MJ / m 3 or more, and the retention of tensile fracture energy after being immersed in dimethyl carbonate at 25 ° C. for 24 hours is 70% or more, more preferably 75% or more, and still more preferably 80% or more, and has excellent toughness. Therefore, it can be suitably used as a battery binder resin composition.
本発明の電極用バインダー樹脂組成物に、少なくとも電極活物質を、限定するものではないが、好ましくは１０℃〜６０℃の温度範囲で混合することにより、電極合剤ペーストを好適に調製することができる。電極活物質は公知のものを好適に用いることができるが、リチウム含有金属複合酸化物、炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末が好ましい。電極合剤ペースト中の電極活物質の量は、格別限定されないが、通常、ポリアミック酸、および／または、ポリイミド樹脂に起因する固形分質量に対して、質量基準で０．１〜１０００倍、好ましくは１〜１０００倍、より好ましくは５〜１０００倍、さらに好ましくは１０〜１０００倍である。活物質量が少なすぎると、集電体に形成された活物質層に不活性な部分が多くなり、電極としての機能が不十分になることがある。また、活物質量が多すぎると活物質が集電体に十分に結着されずに脱落しやくなる。なお、電極合剤ペースト中には、必要に応じて界面活性剤や粘度調整剤や導電補助剤などの添加剤を加えることができる。また、ポリアミック酸、および／または、ポリイミド樹脂がペーストの全固形分中の１〜１５質量％となるよう混合することが好ましい。この範囲外では電極の性能が低下することがある。 Although at least an electrode active material is not limited to the binder resin composition for electrodes of this invention, Preferably it mixes in the temperature range of 10 to 60 degreeC, and prepares an electrode mixture paste suitably. Can do. Known electrode active materials can be preferably used, but lithium-containing metal composite oxides, carbon powders, silicon powders, tin powders, or alloy powders containing silicon or tin are preferable. The amount of the electrode active material in the electrode mixture paste is not particularly limited, but is usually 0.1 to 1000 times, preferably 0.1 to 1000 times on a mass basis with respect to the solid content mass resulting from the polyamic acid and / or the polyimide resin. Is 1 to 1000 times, more preferably 5 to 1000 times, and still more preferably 10 to 1000 times. When the amount of the active material is too small, an inactive portion is increased in the active material layer formed on the current collector, and the function as an electrode may be insufficient. On the other hand, when the amount of the active material is too large, the active material is not sufficiently bound to the current collector and easily falls off. In the electrode mixture paste, additives such as a surfactant, a viscosity modifier and a conductive additive can be added as necessary. Moreover, it is preferable to mix so that a polyamic acid and / or a polyimide resin may be 1-15 mass% in the total solid of a paste. Outside this range, the electrode performance may deteriorate.
充放電により可逆的にリチウムイオンを挿入・放出できる例えばリチウム含有金属複合酸化物のような電極活物質を用いて得られる電極合剤ペーストを、アルミニウムなどの導電性の集電体上に流延あるいは塗布して、８０〜４００℃、より好ましくは１２０〜３８０℃、特に好ましくは１５０〜３５０℃の温度範囲で加熱処理して溶媒を除去し、ポリアミック酸を含有する場合には同時にイミド化反応することにより電極を得ることができる。
加熱処理温度が上記の範囲外の場合、溶媒の除去が十分でなかったり、イミド化反応が十分に進行しなかったり、電極成形体の物性が低下したりすることがある。加熱処理は発泡や粉末化を防ぐために多段で行ってもよい。また、加熱処理時間は３分〜４８時間の範囲が好ましい。４８時間以上は生産性の点から好ましくなく、３分より短いとイミド化反応や溶媒の除去が不十分となることがあり好ましくない。
得られる電極はリチウムイオン二次電池の正極として特に好適に用いることができる。
An electrode mixture paste obtained by using an electrode active material such as a lithium-containing metal composite oxide capable of reversibly inserting and releasing lithium ions by charging and discharging is cast on a conductive current collector such as aluminum. Alternatively, it is applied to remove the solvent by heat treatment in the temperature range of 80 to 400 ° C., more preferably 120 to 380 ° C., particularly preferably 150 to 350 ° C. By doing so, an electrode can be obtained.
When the heat treatment temperature is out of the above range, the solvent may not be sufficiently removed, the imidization reaction may not proceed sufficiently, or the physical properties of the electrode molded body may be deteriorated. The heat treatment may be performed in multiple stages to prevent foaming or powdering. The heat treatment time is preferably in the range of 3 minutes to 48 hours. 48 hours or longer is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction or solvent removal may be insufficient, which is not preferable.
The obtained electrode can be particularly suitably used as a positive electrode of a lithium ion secondary battery.
また、充放電により可逆的にリチウムイオンを挿入・放出できる例えば炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末のような電極活物質を用いて得られる電極合剤ペーストを、銅などの導電性の集電体上に流延あるいは塗布する場合、８０〜３００℃、より好ましくは１２０〜２８０℃、特に好ましくは１５０〜２５０℃の温度範囲で加熱処理して溶媒を除去し、ポリアミック酸を含有する場合には同時にイミド化反応することにより電極を得ることができる。加熱処理温度が８０℃よりも低い場合、溶媒の除去が十分でなかったり、イミド化反応が十分に進行せずに電極成形体の物性が低下することがある。３００℃よりも高い温度で熱処理すると銅が変形などをしてしまい、電極として使用できなくなることがある。この場合も加熱処理は発泡や粉末化を防ぐために多段で行ってもよい。また、加熱処理時間は３分〜４８時間の範囲が好ましい。４８時間以上は生産性の点から好ましくなく、３分より短いとイミド化反応や溶媒の除去が不十分となることがあり好ましくない。
得られる電極はリチウムイオン二次電池の負極として好適に用いることができる。
Further, an electrode mixture paste obtained by using an electrode active material such as carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin capable of reversibly inserting and releasing lithium ions by charging and discharging, When cast or coated on a conductive current collector such as copper, the solvent is removed by heat treatment at a temperature of 80 to 300 ° C, more preferably 120 to 280 ° C, and particularly preferably 150 to 250 ° C. When the polyamic acid is contained, an electrode can be obtained by simultaneously performing an imidization reaction. When the heat treatment temperature is lower than 80 ° C., the removal of the solvent may not be sufficient, or the imidization reaction may not sufficiently proceed and the physical properties of the electrode molded body may be deteriorated. If heat treatment is performed at a temperature higher than 300 ° C., copper may be deformed and cannot be used as an electrode. Also in this case, the heat treatment may be performed in multiple stages in order to prevent foaming and powdering. The heat treatment time is preferably in the range of 3 minutes to 48 hours. 48 hours or longer is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction or solvent removal may be insufficient, which is not preferable.
The obtained electrode can be suitably used as a negative electrode of a lithium ion secondary battery.
以下、本発明を実施例及び比較例により更に具体的に説明するが、本発明は、これら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
以下の例で用いた特性の測定方法を以下に示す。
＜固形分濃度＞
試料溶液（その質量をｗ１とする）を、熱風乾燥機中１２０℃で１０分間、２５０℃で１０分間、次いで３５０℃で３０分間加熱処理して、加熱処理後の質量（その質量をｗ２とする）を測定する。固形分濃度［質量％］は、次式によって算出した。
固形分濃度［質量％］＝（ｗ２／ｗ１）×１００
＜対数粘度＞
試料溶液を、固形分濃度に基づいて濃度が０．５ｇ／ｄｌ（溶媒はＮＭＰ）になるように希釈した。この希釈液を、３０℃にて、キャノンフェンスケＮｏ．１００を用いて流下時間（Ｔ１）を測定した。対数粘度は、ブランクのＮＭＰの流下時間（Ｔ０）を用いて、次式から算出した。
対数粘度＝｛ｌｎ（Ｔ１／Ｔ０）｝／０．５
＜溶液粘度（回転粘度）＞
トキメック社製Ｅ型粘度計を用いて３０℃で測定した。
＜イミド化率測定＞
試料溶液を重水素化ジメチルスルホキシドに溶解及びろ過した後、テトラメチルシランを基準物質として室温で1Ｈ−ＮＭＲをＢＲＵＫＥＲ社 ＡＶＡＮＣＥ ＩＩＩ ４００Ｎ型を用いて測定し、次式からイミド化率を算出した。
イミド化率（％）＝（α−Ａ１／Ａ２）／（α−β）×１００
Ａ１：ＮＨ基のプロトン由来のピーク面積（１０〜１１ｐｐｍ付近）
Ａ２：芳香族部位のプロトン由来のピーク面積（７〜９ｐｐｍ付近）
α：重合体の前駆体（ポリアミック酸）における、芳香族部位のプロトン１個に対するＮＨ基のプロトンの個数割合
β：重合体（ポリアミドイミド）における、芳香族部位のプロトン１個に対するＮＨ基のプロトンの個数割合
＜膨潤試験＞
電極用バインダー樹脂組成物から得られたポリイミドフィルムを５ｃｍ角（厚さ：５０μｍ）に切り出したものを試料として用いた。６０℃で２４時間真空乾燥後の質量を乾燥質量（Ｗｄ）とし、ジメチルカーボネート溶液、或いはメトキシリチウムの１０質量％メタノール溶液に、２５℃で２４時間浸漬後の質量を膨潤質量（Ｗｗ）とし、それぞれ次式により膨潤度Ｓを計算した。
Ｓ［質量％］＝（Ｗｗ−Ｗｄ）／Ｗｗ×１００
＜付着性試験（クロスカット法）＞
付着性試験は、ＪＩＳ Ｋ ５６００−５−６に準拠して行った。なお、評価は目視により、評価基準（３）に準拠した分類０〜分類５（数字が小さいほど強固に付着している）で示した。
なお、付着性試験は、ジメチルカーボネート溶液での膨潤試験前後の試料について、それぞれ行った。
＜９０°ピール強度測定＞
９０°ピール強度試験は、万能試験機（オリエンテック社製ＲＴＣ−１２２５Ａ）を用いて、ＩＰＣ−ＴＭ６５０に準拠して測定した。
＜９０°ピール強度保持率＞
ジメチルカーボネート溶液での膨潤試験前後の試料について、９０°ピール強度を測定し、次式により９０°ピール強度の保持率を算出した。
９０°ピール強度保持率[％]
＝浸漬後の９０°ピール強度／浸漬前の９０°ピール強度×１００
A method for measuring the characteristics used in the following examples is shown below.
<Concentration of solid content>
The sample solution (whose mass is designated as w 1 ) is heat-treated in a hot air dryer at 120 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 30 minutes. Measure). Solid content concentration [mass%] was computed by the following formula.
Solid content concentration [% by mass] = (w 2 / w 1 ) × 100
<Logarithmic viscosity>
The sample solution was diluted to a concentration of 0.5 g / dl (solvent is NMP) based on the solid content concentration. This diluted solution was added to Cannon Fenceke No. The flow-down time (T 1 ) was measured using 100. The logarithmic viscosity was calculated from the following equation using the flow time (T 0 ) of blank NMP.
Logarithmic viscosity = {ln (T 1 / T 0 )} / 0.5
<Solution viscosity (rotational viscosity)>
It measured at 30 degreeC using the Tokimec E-type viscosity meter.
<Imidation rate measurement>
After dissolving and filtering the sample solution in deuterated dimethyl sulfoxide, 1 H-NMR was measured at room temperature using tetramethylsilane as a reference substance using a BRUKER AVANCE III 400N type, and the imidization rate was calculated from the following formula: .
Imidization rate (%) = (α−A1 / A2) / (α−β) × 100
A1: Peak area derived from proton of NH group (around 10 to 11 ppm)
A2: Proton-derived peak area of the aromatic moiety (around 7-9 ppm)
α: Proportion of the number of NH group protons relative to one aromatic moiety proton in the polymer precursor (polyamic acid) β: NH group proton relative to one aromatic moiety proton in the polymer (polyamideimide) Number ratio <Swelling test>
A sample obtained by cutting out a polyimide film obtained from the binder resin composition for electrodes into a 5 cm square (thickness: 50 μm) was used as a sample. The mass after vacuum drying at 60 ° C. for 24 hours is defined as the dry mass (Wd), and the mass after being immersed in a dimethyl carbonate solution or a 10% by mass methanol solution of methoxy lithium at 25 ° C. for 24 hours is defined as the swelling mass (Ww). The degree of swelling S was calculated by the following formula.
S [mass%] = (Ww−Wd) / Ww × 100
<Adhesion test (cross-cut method)>
The adhesion test was performed according to JIS K 5600-5-6. In addition, evaluation was shown by the classification | category 0-the classification | category 5 based on evaluation criteria (3) by visual observation (it adheres so firmly that a number is small).
The adhesion test was performed on samples before and after the swelling test with a dimethyl carbonate solution.
<90 ° peel strength measurement>
The 90 ° peel strength test was measured according to IPC-TM650 using a universal testing machine (Orientec RTC-1225A).
<90 ° peel strength retention>
About the sample before and after the swelling test with a dimethyl carbonate solution, 90 ° peel strength was measured, and the retention rate of 90 ° peel strength was calculated by the following formula.
90 ° peel strength retention [%]
= 90 ° peel strength after immersion / 90 ° peel strength before immersion x 100
以下の例で使用した化合物の略号について説明する。
ｓ−ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物
ａ−ＢＰＤＡ：２，３，３’，４’−ビフェニルテトラカルボン酸二無水物
ＴＭＡ：無水トリメリット酸
ＴＡＣ：無水トリメリット酸クロライド
ＴＡＣ（ＰＰＤ）：ビス（ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸）１，４−フェニレンジアミド
ＴＡＣ（ＯＤＡ）：ビス（ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸）４，４'−オキシジアニリド
Ｈ−ＴＡＣ（ＯＤＡ）：ビス（オクタヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸）４，４'−オキシジアニリド
ＯＤＡ：４，４’−ジアミノジフェニルエーテル
２，４−ＴＤＡ：２，４−ジアミノトルエン
ＰＰＤ：ｐ−フェニレンジアミン
４，４’−ＤＡＢＡ：４，４’−ジアミノベンズアニリド
ＢＡＢＢ：１，４−ベンゼンジオール，１，４−ビス（４−アミノベンゾエイト）
１，３ｐ−ＢＡＢＢ：１，３−ベンゼンジオール，１，３−ビス（４−アミノベンゾエイト）
２，４−ＴＤＩ：２，４−トリレンジイソシアネート
４，４’−ＭＤＩ：４，４’−ジフェニルメタンジイソシアネート
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＤＭＣ：ジメチルカーボネート
The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride TMA: trimellitic anhydride TAC: Trimellitic anhydride chloride TAC (PPD): bis (dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid) 1,4-phenylenediamide TAC (ODA): bis (dihydro-1,3-dioxo-5- Isobenzofurancarboxylic acid) 4,4′-oxydianilide H-TAC (ODA): bis (octahydro-1,3-dioxo-5-isobenzofurancarboxylic acid) 4,4′-oxydianilide ODA: 4,4 '-Diaminodiphenyl ether 2,4-TDA: 2,4-diaminotoluene PPD: p-phenylenediamine 4,4'-DABA: 4,4' Diamino benzanilide BABB: 1,4 benzenediol, 1,4-bis (4-amino benzoate)
1,3p-BABB: 1,3-benzenediol, 1,3-bis (4-aminobenzoate)
2,4-TDI: 2,4-tolylene diisocyanate 4,4′-MDI: 4,4′-diphenylmethane diisocyanate NMP: N-methyl-2-pyrrolidone DMC: dimethyl carbonate
〔実施例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これに４，４’−ＤＡＢＡの３２．６９ｇ（０．１４４モル）と、ｓ−ＢＰＤＡの４２．３１ｇ（０．１４４モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．０質量％、溶液粘度８．５Ｐａ・ｓ、対数粘度１．０８の電極用バインダー樹脂組成物を得た。
[Example 1]
To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge pipe, 425 g of NMP was added as a solvent, and 32.69 g (0.144 mol) of 4,4′-DABA was added thereto. 42.31 g (0.144 mol) of s-BPDA was added and stirred at 50 ° C. for 12 hours to obtain an electrode having a solid content concentration of 14.0% by mass, a solution viscosity of 8.5 Pa · s, and a logarithmic viscosity of 1.08. A binder resin composition was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．７ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.7 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これに４，４’−ＤＡＢＡの２４．９３ｇ（０．１１０モル）と、ＴＡＣ（ＰＰＤ）の５０．０７ｇ（０．１１０モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．０質量％、溶液粘度１５．０Ｐａ・ｓ、対数粘度１．０７の電極用バインダー樹脂組成物を得た。
[Example 2]
To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 425 g of NMP was added as a solvent, and 24.93 g (0.110 mol) of 4,4′-DABA was added thereto. Add 50.07 g (0.110 mol) of TAC (PPD) and stir at 50 ° C. for 12 hours to obtain a solid content concentration of 14.0% by mass, a solution viscosity of 15.0 Pa · s, and a logarithmic viscosity of 1.07. An electrode binder resin composition was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．７ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.7 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの２２．８７ｇ（０．１１４モル）と、ＴＡＣ（ＰＰＤ）の５２．１３ｇ（０．１１４モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．３質量％、溶液粘度１０．０Ｐａ・ｓ、対数粘度０．６７の電極用バインダー樹脂組成物を得た。
Example 3
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 22.87 g (0.114 mol) of ODA and TAC (PPD) 52.13 g (0.114 mol) was added, and the mixture was stirred at 50 ° C. for 12 hours. The binder resin composition for an electrode having a solid content concentration of 14.3% by mass, a solution viscosity of 10.0 Pa · s, and a logarithmic viscosity of 0.67. I got a thing.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．６ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.6 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to obtain an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これに４，４’−ＤＡＢＡの２１．９７ｇ（０．０９７モル）と、ＴＡＣ（ＯＤＡ）の５３．０３ｇ（０．０９７モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．１質量％、溶液粘度３．５Ｐａ・ｓ、対数粘度０．９０の電極用バインダー樹脂組成物を得た。
Example 4
To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 425 g of NMP was added as a solvent, and 21.97 g (0.097 mol) of 4,4′-DABA was added thereto. Add 53.03 g (0.097 mol) of TAC (ODA) and stir at 50 ° C. for 12 hours to obtain a solid content concentration of 14.1% by mass, a solution viscosity of 3.5 Pa · s, and a logarithmic viscosity of 0.90. An electrode binder resin composition was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．７ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.7 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの２０．０６ｇ（０．１００モル）と、ＴＡＣ（ＯＤＡ）の５４．９４ｇ（０．１００モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．１質量％、溶液粘度１７．０Ｐａ・ｓ、対数粘度０．７７の電極用バインダー樹脂組成物を得た。
Example 5
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 20.06 g (0.100 mol) of ODA and TAC (ODA) 54.94 g (0.100 mol) was added, and the mixture was stirred at 50 ° C. for 12 hours. The binder resin composition for an electrode having a solid content of 14.1% by mass, a solution viscosity of 17.0 Pa · s, and a logarithmic viscosity of 0.77. I got a thing.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．７ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.7 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例６〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの１９．７４ｇ（０．０９９モル）と、Ｈ−ＴＡＣ（ＯＤＡ）の５５．２６ｇ（０．０９９モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１３．８質量％、溶液粘度２．５Ｐａ・ｓ、対数粘度０．１９の電極用バインダー樹脂組成物を得た。
Example 6
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 19.74 g (0.099 mol) of ODA and H-TAC (ODA ), And stirred at 50 ° C. for 12 hours to obtain a binder for an electrode having a solid content concentration of 13.8% by mass, a solution viscosity of 2.5 Pa · s, and a logarithmic viscosity of 0.19. A resin composition was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．８ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.8 g of the obtained binder resin composition (solid weight mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例７〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの１９．９４ｇ（０．１００モル）及び４，４’−ＤＡＢＡの７．５４ｇ（０．０３３モル）と、ｓ−ＢＰＤＡの２９．３０ｇ（０．１００モル）及びＴＡＣ（ＯＤＡ）の１８．２１ｇ（０．０３３モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．２質量％、溶液粘度４．８Ｐａ・ｓ、対数粘度０．５５の電極用バインダー樹脂組成物を得た。
Example 7
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 19.94 g (0.100 mol) of ODA and 4,4′-DABA were added thereto. 7.54 g (0.033 mol) of s-BPDA, and 18.21 g (0.033 mol) of TAC (ODA) were added and stirred at 50 ° C. for 12 hours. Thus, a binder resin composition for an electrode having a solid content concentration of 14.2% by mass, a solution viscosity of 4.8 Pa · s, and a logarithmic viscosity of 0.55 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．６ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.6 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to obtain an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例８〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの２４．１６ｇ（０．１２０モル）と、ｓ−ＢＰＤＡの１７．７５ｇ（０．０６０モル）及びＴＡＣ（ＯＤＡ）の３３．０９ｇ（０．０６０モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．０質量％、溶液粘度４．９Ｐａ・ｓ、対数粘度０．５２の電極用バインダー樹脂組成物を得た。
Example 8
425 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 24.16 g (0.120 mol) of ODA and 17 of s-BPDA were added thereto. .75 g (0.060 mol) and 33.09 g (0.060 mol) of TAC (ODA) were added and stirred at 50 ° C. for 12 hours to obtain a solid content concentration of 14.0% by mass and a solution viscosity of 4.9 Pa. -The binder resin composition for electrodes of s and logarithmic viscosity 0.52 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．７ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.7 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔実施例９〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＯＤＡの１４．７８ｇ（０．０７４モル）及び４，４’−ＤＡＢＡの１６．７８ｇ（０．０７４モル）と、ｓ−ＢＰＤＡの４３．４４ｇ（０．１４８モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１４．２質量％、溶液粘度５．２Ｐａ・ｓ、対数粘度０．６８の電極用バインダー樹脂組成物を得た。
Example 9
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 14.78 g (0.074 mol) of ODA and 4,4′-DABA were added thereto. 16.78 g (0.074 mol) of s-BPDA and 43.44 g (0.148 mol) of s-BPDA were added and stirred at 50 ° C. for 12 hours to obtain a solid content concentration of 14.2% by mass and a solution viscosity of 5 A binder resin composition for an electrode having a viscosity of 0.6 Pa and a viscosity of 0.68 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
これらの結果を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 1.
得られたバインダー樹脂組成物５．６ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表１に示した。
5.6 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to obtain an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 1.
〔比較例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これにＢＡＢＢの４０．６６ｇ（０．１１７モル）と、ｓ−ＢＰＤＡの３４．３４ｇ（０．１１７モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１３．９質量％、溶液粘度７．４Ｐａ・ｓ、対数粘度１．１５の電極用バインダー樹脂組成物を得た。
[Comparative Example 1]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 425 g of NMP was added as a solvent, and 40.66 g (0.117 mol) of BABB and 34 of s-BPDA were added thereto. .34 g (0.117 mol) was added and stirred at 50 ° C. for 12 hours to obtain a binder resin composition for an electrode having a solid content concentration of 13.9% by mass, a solution viscosity of 7.4 Pa · s, and a logarithmic viscosity of 1.15. Got.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test was performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 2.
得られたバインダー樹脂組成物５．８ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
5.8 g of the obtained binder resin composition (solid weight mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 2.
〔比較例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４２５ｇを加え、これに１，３ｐ−ＢＡＢＢの４０．６６ｇ（０．１１７モル）と、ｓ−ＢＰＤＡの３４．３４ｇ（０．１１７モル）とを加え、５０℃で１２時間撹拌して、固形分濃度１３．７質量％、溶液粘度１．２Ｐａ・ｓ、対数粘度０．６２の電極用バインダー樹脂組成物を得た。
[Comparative Example 2]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 425 g of NMP was added as a solvent, and 40.66 g (0.117 mol) of 1,3p-BABB was added thereto. -Add 34.34 g (0.117 mol) of BPDA and stir at 50 ° C. for 12 hours, for an electrode having a solid content concentration of 13.7% by mass, a solution viscosity of 1.2 Pa · s, and a logarithmic viscosity of 0.62. A binder resin composition was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test was performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 2.
得られたバインダー樹脂組成物５．８ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
5.8 g of the obtained binder resin composition (solid weight mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 2.
〔比較例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これに２，４−ＴＤＩの４７．５５ｇ（０．２７３モル）と、ＴＭＡの５２．４５ｇ（０．２７３モル）とを加え、１００℃で３時間撹拌後、１２０℃に昇温して６時間反応を行い、固形分濃度１３．１質量％、溶液粘度０．５Ｐａ・ｓ、対数粘度１．１０の電極用バインダー樹脂組成物を得た。
[Comparative Example 3]
To a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet / outlet pipe, 400 g of NMP was added as a solvent, and 47.55 g (0.273 mol) of 2,4-TDI was added to the TMA. After stirring at 100 ° C. for 3 hours, the mixture was heated to 120 ° C. and reacted for 6 hours to obtain a solid concentration of 13.1% by mass and a solution viscosity of 0.5 Pa ·. s and the binder resin composition for electrodes of logarithmic viscosity 1.10 were obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test was performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 2.
得られたバインダー樹脂組成物６．１ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
6.1 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 2.
〔比較例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これに４，４’−ＭＤＩの５６．５７ｇ（０．２２６モル）と、ＴＭＡの４３．４３ｇ（０．２２６モル）とを加え、１００℃で３時間撹拌後、１２０℃に昇温して６時間反応を行い、固形分濃度１３．２質量％、溶液粘度０．３Ｐａ・ｓ、対数粘度１．１８の電極用バインダー樹脂組成物を得た。
[Comparative Example 4]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, and 56.57 g (0.226 mol) of 4,4′-MDI was added thereto. 43.43 g (0.226 mol) of TMA was added, stirred at 100 ° C. for 3 hours, heated to 120 ° C. and reacted for 6 hours, solid content concentration 13.2% by mass, solution viscosity 0.3 Pa. -The binder resin composition for electrodes of s and logarithmic viscosity 1.18 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness of 25 μm The binder resin film was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test was performed on the samples before and after the swelling test with the DMC solution.
These results are shown in Table 2.
得られたバインダー樹脂組成物６．１ｇ（イミド化後の固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表２に示した。
6.1 g of the obtained binder resin composition (solid content mass after imidization 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 2.
〔比較例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＰＰＤの３３．９３ｇ（０．３１４モル）と、ＴＡＣの６６．０７ｇ（０．３１４モル）を加え、２５℃で６時間撹拌したが、均一に溶解することがなく、ポリイミド前駆体水溶液組成物を得ることができなかった。
結果を表２に示した。
[Comparative Example 5]
To a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet / outlet pipe, 400 g of NMP was added as a solvent, and 33.93 g (0.314 mol) of PPD and 66.07 g of TAC were added thereto. (0.314 mol) was added, and the mixture was stirred at 25 ° C. for 6 hours. However, it was not uniformly dissolved, and a polyimide precursor aqueous solution composition could not be obtained.
The results are shown in Table 2.
〔実施例１０〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４４０ｇを加え、これにＯＤＡの１６．０５ｇ（０．０８０モル）と、ＴＡＣ（ＯＤＡ）の４３．９５ｇ（０．０８０モル）とを加え、７０℃で４時間撹拌した後、１８０℃で１６時間撹拌し、固形分濃度１０．３質量％、溶液粘度２３．１Ｐａ・ｓ、対数粘度１．８１の電極用バインダー樹脂組成物を得た。この組成物に含まれるポリイミド樹脂のイミド化率は１００％であった。
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
Example 10
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 440 g of NMP was added as a solvent, and 16.05 g (0.080 mol) of ODA and TAC (ODA) 43.95 g (0.080 mol) was added, and the mixture was stirred at 70 ° C. for 4 hours and then stirred at 180 ° C. for 16 hours. .81 binder resin composition for electrodes was obtained. The imidation ratio of the polyimide resin contained in this composition was 100%.
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. It put into the hot air dryer under gas atmosphere, and heat-processed at 120 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
得られたバインダー樹脂組成物７．８ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表３に示した。
7.8 g of the resulting binder resin composition (solid content: 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode mixture paste) Was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 120 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 3.
〔実施例１１〕
実施例１０で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１５０℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
Example 11
After applying the binder resin composition for an electrode obtained in Example 10 onto a glass plate of a substrate by a bar coater, and defoaming and predrying the coating film at 25 ° C. for 30 minutes under reduced pressure, It put into the hot-air dryer under normal pressure and nitrogen gas atmosphere, and heat-processed at 150 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
実施例１０と同様に、得られたバインダー樹脂組成物７．８ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１５０℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表３に示した。
In the same manner as in Example 10, 7.8 g (solid content: 0.8 g) of the obtained binder resin composition and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to form an electrode mixture composition. A product (electrode mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 150 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 3.
〔実施例１２〕
実施例１０で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
Example 12
After applying the binder resin composition for an electrode obtained in Example 10 onto a glass plate of a substrate by a bar coater, and defoaming and predrying the coating film at 25 ° C. for 30 minutes under reduced pressure, It put into the hot-air dryer under normal pressure and nitrogen gas atmosphere, and heat-processed at 200 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
実施例１０と同様に、得られたバインダー樹脂組成物７．８ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表３に示した。
In the same manner as in Example 10, 7.8 g (solid content: 0.8 g) of the obtained binder resin composition and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to form an electrode mixture composition. A product (electrode mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil to which the paste was applied was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 200 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 3.
〔実施例１３〕
実施例１０で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
Example 13
After applying the binder resin composition for an electrode obtained in Example 10 onto a glass plate of a substrate by a bar coater, and defoaming and predrying the coating film at 25 ° C. for 30 minutes under reduced pressure, Put in a hot air drier under normal pressure and nitrogen gas atmosphere, heat treatment at 120 ° C for 30 minutes, 150 ° C for 10 minutes, 200 ° C for 10 minutes, 250 ° C for 10 minutes, then 350 ° C for 10 minutes, A binder resin film having a thickness of 25 μm was formed.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
実施例１０と同様に、得られたバインダー樹脂組成物７．８ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表３に示した。
In the same manner as in Example 10, 7.8 g (solid content: 0.8 g) of the obtained binder resin composition and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar to form an electrode mixture composition. A product (electrode mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil coated with the paste is fixed on the substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 30 minutes at 120 ° C. Then, heat treatment was performed at 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to prepare an electrode having an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 3.
〔比較例６〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４４０ｇを加え、これに２，４−ＴＤＡの１７．６０ｇ（０．１４４モル）と、ｓ−ＢＰＤＡの４２．４０ｇ（０．１４４モル）とを加え、７０℃で４時間撹拌した後、１８０℃で１６時間撹拌し、固形分濃度１１．６質量％、溶液粘度７２．５Ｐａ・ｓ、対数粘度１．０８の電極用バインダー樹脂組成物を得た。この組成物に含まれるポリイミド樹脂のイミド化率は１００％であった。
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
[Comparative Example 6]
440 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 17.60 g (0.144 mol) of 2,4-TDA was added to this, and s -42.40 g (0.144 mol) of BPDA was added and stirred at 70 ° C. for 4 hours, and then stirred at 180 ° C. for 16 hours. The solid content concentration was 11.6% by mass, the solution viscosity was 72.5 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 1.08 was obtained. The imidation ratio of the polyimide resin contained in this composition was 100%.
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. It put into the hot air dryer under gas atmosphere, and heat-processed at 200 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
得られたバインダー樹脂組成物６．９ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表４に示した。
The obtained binder resin composition 6.9 g (solid content weight 0.8 g) and 325 mesh pass silicon powder 9.2 g were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode mixture paste) Was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil to which the paste was applied was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 200 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 4.
〔比較例７〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４４０ｇを加え、これにＴＰＥ−Ｒの２９．９０ｇ（０．１０２モル）と、ａ−ＢＰＤＡの３０．１０ｇ（０．１０２モル）とを加え、７０℃で４時間撹拌した後、１８０℃で１６時間撹拌し、固形分濃度１１．３質量％、溶液粘度１３．７Ｐａ・ｓ、対数粘度０．８８の電極用バインダー樹脂組成物を得た。この組成物に含まれるポリイミド樹脂のイミド化率は１００％であった。
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
[Comparative Example 7]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 440 g of NMP was added as a solvent, and 29.90 g (0.102 mol) of TPE-R and a-BPDA were added thereto. 30.10 g (0.102 mol) of the mixture was added and stirred at 70 ° C. for 4 hours and then at 180 ° C. for 16 hours. The solid content concentration was 11.3 mass%, the solution viscosity was 13.7 Pa · s, and the logarithmic viscosity. 0.88 binder resin composition for electrodes was obtained. The imidation ratio of the polyimide resin contained in this composition was 100%.
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. It put into the hot air dryer under gas atmosphere, and heat-processed at 200 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
得られたバインダー樹脂組成物７．１ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表４に示した。
The obtained binder resin composition (7.1 g, solid content mass: 0.8 g) and 325 mesh pass silicon powder (9.2 g) were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode mixture paste) Was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil to which the paste was applied was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 200 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 4.
〔比較例８〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４４０ｇを加え、これにＢＡＰＰの３４．９５ｇ（０．０８５モル）と、ａ−ＢＰＤＡの２５．０５ｇ（０．０８５モル）とを加え、７０℃で４時間撹拌した後、１８０℃で１６時間撹拌し、固形分濃度１１．５質量％、溶液粘度９．８Ｐａ・ｓ、対数粘度０．６５の電極用バインダー樹脂組成物を得た。この組成物に含まれるポリイミド樹脂のイミド化率は１００％であった。
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、厚さが２５μｍのバインダー樹脂フィルムを形成した。
銅箔上に形成したバインダー樹脂フィルムを試料としてＤＭＣ膨潤試験を行った。またＤＭＣ溶液での膨潤試験前後の試料について付着性試験及び９０°ピール強度測定を行った。
[Comparative Example 8]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 440 g of NMP was added as a solvent, and 34.95 g (0.085 mol) of BAPP and 25 of a-BPDA were added thereto. 0.05 g (0.085 mol) was added, and the mixture was stirred at 70 ° C. for 4 hours and then stirred at 180 ° C. for 16 hours. The solid content concentration was 11.5% by mass, the solution viscosity was 9.8 Pa · s, and the logarithmic viscosity was 0.00. 65 binder resin compositions for electrodes were obtained. The imidation ratio of the polyimide resin contained in this composition was 100%.
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. It put into the hot air dryer under gas atmosphere, and heat-processed at 200 degreeC for 2 hours, and formed the 25-micrometer-thick binder resin film.
A DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. In addition, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with the DMC solution.
得られたバインダー樹脂組成物７．０ｇ（固形分質量０．８ｇ）と３２５メッシュパスのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤組成物（電極合剤ペースト）を調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。
ペーストを塗布した銅箔を基板上に固定し、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、２００℃で２時間加熱処理して、電極合剤層の厚みが１００μｍの電極を作製した。
得られた電極を試料としてＤＭＣ膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表４に示した。
7.0 g of the obtained binder resin composition (solid mass: 0.8 g) and 9.2 g of 325 mesh pass silicon powder were kneaded so as to be ground in a mortar, and an electrode mixture composition (electrode mixture paste) Was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
The copper foil to which the paste was applied was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 2 hours at 200 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 μm.
A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
These results are shown in Table 4.
Claims (7)
（式中、Ｒはベンゼン環を１から４個有する芳香族ジアミン残基を表す。）
A polyamic acid obtained by reacting a monomer component composed of a tetracarboxylic acid component and a diamine component, and / or a binder resin composition for an electrode obtained by dissolving a polyimide resin in a solvent, the polyamic acid and the polyimide resin Is obtained by polymerizing a monomer component containing a tetracarboxylic acid compound having an amide bond in the molecule selected from the group consisting of the following general formulas (1) and (2) as a tetracarboxylic acid component An electrode binder resin composition characterized by the above.
(In the formula, R represents an aromatic diamine residue having 1 to 4 benzene rings.)
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| JP6806068B2 (en) * | 2015-09-17 | 2021-01-06 | 日本電気株式会社 | Resin composition |
| KR102430152B1 (en) * | 2017-12-08 | 2022-08-08 | 주식회사 두산 | Polyamic acid solution, transparent polyimide film and transparent substrate using the same |
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| CN103238241B (en) * | 2010-11-30 | 2015-04-01 | 东丽株式会社 | Binder for electrodes of lithium ion batteries, paste for negative electrodes of lithium ion batteries, and method for producing negative electrode of lithium ion battery |
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| CN112399980B (en) * | 2018-05-24 | 2022-01-14 | 宇部兴产株式会社 | Binder resin composition for electrode, electrode mixture paste, and electrode |
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