JP2015230884A - Resin for power storage device - Google Patents
Resin for power storage device Download PDFInfo
- Publication number
- JP2015230884A JP2015230884A JP2014117993A JP2014117993A JP2015230884A JP 2015230884 A JP2015230884 A JP 2015230884A JP 2014117993 A JP2014117993 A JP 2014117993A JP 2014117993 A JP2014117993 A JP 2014117993A JP 2015230884 A JP2015230884 A JP 2015230884A
- Authority
- JP
- Japan
- Prior art keywords
- storage device
- electricity storage
- resin
- electrode
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000003860 storage Methods 0.000 title claims abstract description 103
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 239000004020 conductor Substances 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 6
- 230000005611 electricity Effects 0.000 claims description 82
- 239000010410 layer Substances 0.000 claims description 66
- 239000012528 membrane Substances 0.000 claims description 41
- 238000000926 separation method Methods 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
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- 239000002245 particle Substances 0.000 claims description 23
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- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 11
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- 239000000463 material Substances 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 3
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- 238000000576 coating method Methods 0.000 abstract description 33
- 239000011248 coating agent Substances 0.000 abstract description 28
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 239000004641 Diallyl-phthalate Substances 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N ethylene glycol dimethyl ether Natural products COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium erythorbate Chemical compound [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
- 239000011755 sodium-L-ascorbate Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Cell Separators (AREA)
Abstract
Description
本発明は、蓄電デバイスの内部の被膜に使用する樹脂および樹脂組成物に関する。 The present invention relates to a resin and a resin composition used for a film inside an electricity storage device.
近年、デジタルカメラや携帯電話のような小型携帯型電子機器が広く用いられるようになってきた。これらの電子機器には、大きさが小さく、かつ重量を軽くすることが常に求められてきており、搭載される電池においても、小型、軽量かつ大容量の電池の実現が求められている。また、自動車等に搭載する大型二次電池においても、従来の鉛蓄電池に代えて、軽量で高出力性能を有する大型電池の実現が望まれている。さらに、高出力かつ高エネルギー密度な蓄電デバイスとしては、電気二重層キャパシター、リチウムイオンキャパシターなどのキャパシターも注目されている。 In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices are always required to be small in size and light in weight, and the batteries to be mounted are also required to be small, light and large capacity. In addition, in a large-sized secondary battery mounted on an automobile or the like, it is desired to realize a large-sized battery that is lightweight and has high output performance, instead of a conventional lead storage battery. In addition, capacitors such as electric double layer capacitors and lithium ion capacitors are also attracting attention as power storage devices with high output and high energy density.
上記環境下、リチウムイオン二次電池およびアルカリ二次電池等の二次電池、ならびにキャパシター等の蓄電デバイスの開発が行なわれている。この蓄電デバイスに使用する電極は、金属箔に下地層および合材層を備えているが、これらの層に使用する導電材料や活物質を被膜として固定するためには、バインダー樹脂が必要である。また蓄電デバイスの分離膜も生成したデンドライドによる分離膜の損傷を防止するため保護層が形成されているが、その保護層に使用する無機粒子を被膜として固定するバインダー樹脂も必要である。このバインダー樹脂には、活物質や導電材料等を分散させる分散性、保護層や集電体等との密着性、電解液耐性、繰り返される充放電サイクルへの耐久性、および電池特性を低下させない等の性能が必要であった。 Under such circumstances, secondary batteries such as lithium ion secondary batteries and alkaline secondary batteries, and power storage devices such as capacitors have been developed. The electrode used for this electricity storage device is provided with a base layer and a composite layer on a metal foil, but a binder resin is required to fix the conductive material and active material used for these layers as a film. . In addition, a protective layer is formed to prevent damage to the separation membrane due to the dendrites that have also formed the separation membrane of the electricity storage device. However, a binder resin for fixing the inorganic particles used in the protective layer as a coating is also necessary. This binder resin does not deteriorate the dispersibility of dispersing active materials, conductive materials, etc., adhesion to protective layers, current collectors, etc., electrolyte resistance, durability to repeated charge / discharge cycles, and battery characteristics. Etc. were required.
そこで特許文献１には、所定のモノマーを使用した重量平均分子量が５０万以上の水溶性高分子のバインダー樹脂が開示されている。
また、特許文献２には、アクリロニトリルを使用したゴム状高分子のバインダー樹脂が開示されている。
Therefore, Patent Document 1 discloses a water-soluble polymer binder resin using a predetermined monomer and having a weight average molecular weight of 500,000 or more.
Patent Document 2 discloses a rubbery polymer binder resin using acrylonitrile.
しかし、水溶性高分子を配合したバインダー樹脂は、溶液の粘度が高いため、合材層等の被膜形成の際の塗工性が悪く、平滑で緻密な被膜の形成が難しく被膜に欠陥が生じやすい。この被膜欠陥により電極の均一性が低下し、充放電サイクル性能が低下しやすい等の問題があった。
また、ゴム状高分子を使用した場合、集電体との密着性が低く、導電材料の分散性が不足し、塗工性が低く被膜欠陥が生じやすい等の問題があった。
However, binder resins formulated with water-soluble polymers have a high viscosity of the solution, so that the coating property when forming a film such as a composite layer is poor, and it is difficult to form a smooth and dense film, resulting in defects in the film. Cheap. Due to this coating defect, there is a problem that the uniformity of the electrode is lowered and the charge / discharge cycle performance is likely to be lowered.
In addition, when a rubbery polymer is used, there are problems such as poor adhesion to the current collector, insufficient dispersibility of the conductive material, low coatability, and film defects.
本発明は、密着性、塗工性、および活物質や導電材料の分散性が優れ、さらに電解液耐性が優れる被膜を形成できる蓄電デバイス用樹脂の提供を目的とする。 An object of the present invention is to provide a resin for an electricity storage device capable of forming a film having excellent adhesion, coating properties, dispersibility of an active material and a conductive material, and excellent electrolyte solution resistance.
本発明の蓄電デバイス用樹脂は、カルボキシル基含有モノマー（ｂ１）：５〜５０重量％、架橋性モノマー（ｂ２）：０．１〜５重量％、その他のモノマー（ｂ３）：４５〜９４．９重量％（但し、前記（ｂ１）〜（ｂ３）の合計を１００重量％とする）を重合してなり、
前記架橋性モノマー（ｂ２）が、二重結合を２つ以上有するモノマーおよびアルコキシシリル基含有モノマーの少なくとも何れかである。
Resin for electrical storage devices of the present invention comprises carboxyl group-containing monomer (b1): 5 to 50% by weight, crosslinkable monomer (b2): 0.1 to 5% by weight, other monomer (b3): 45 to 94.9. % By weight (provided that the total of (b1) to (b3) is 100% by weight),
The crosslinkable monomer (b2) is at least one of a monomer having two or more double bonds and an alkoxysilyl group-containing monomer.
上記の本発明によれば、分散性および密着性向上のためにカルボキシル基含有モノマーを多量に使用すると、樹脂の粘度が上昇するところ、架橋性モノマーを併用したことで樹脂内に３次元ポリマーネットワークが形成する。この３次元ポリマーネットワークにより樹脂のモビリティが下がることで、樹脂の水溶性が低下し、エマルションを形成することで粘度が下がり流動性が向上することで塗工性が向上した。この塗工性の向上により、均一で欠陥が少ない被膜が形成できた上、被膜の電解液耐性が向上する効果も得られた。 According to the present invention, when a large amount of a carboxyl group-containing monomer is used to improve dispersibility and adhesion, the viscosity of the resin increases. By using a crosslinkable monomer in combination, a three-dimensional polymer network is formed in the resin. Form. By reducing the mobility of the resin by this three-dimensional polymer network, the water solubility of the resin is lowered, and by forming an emulsion, the viscosity is lowered and the fluidity is improved, thereby improving the coating property. By improving the coatability, it was possible to form a uniform film with few defects and to improve the resistance of the film to electrolyte.
本発明により密着性、塗工性、および活物質や導電材料の分散性が優れ、さらに電解液耐性が優れる被膜を形成できる蓄電デバイス用樹脂を提供できる。 According to the present invention, it is possible to provide a resin for an electricity storage device that can form a film having excellent adhesion, coating property, dispersibility of an active material and a conductive material, and excellent electrolyte solution resistance.
本発明を説明する前に用語を定義する。まず蓄電デバイスとは、二次電池およびキャパシタ等、電気の蓄積および放出を繰り返すことができる装置を言う。被膜とは、下地層、合材層、保護層およびその他の蓄電デバイス内の部材に形成できる層の総称である。また、その他のモノマー（ｂ３）とは、カルボキシル基含有モノマー（ｂ１）および架橋性モノマー（ｂ２）以外のモノマーである。また、モノマーとは、エチレン性不飽和二重結合含有単量体である。また、（メタ）アクリレートとは、アクリレートおよびメタクリレートを含む。 Before describing the present invention, terms will be defined. First, an electricity storage device refers to a device that can repeatedly store and discharge electricity, such as a secondary battery and a capacitor. A coating is a general term for layers that can be formed on a base layer, a composite layer, a protective layer, and other members in an electricity storage device. The other monomer (b3) is a monomer other than the carboxyl group-containing monomer (b1) and the crosslinkable monomer (b2). Moreover, a monomer is an ethylenically unsaturated double bond containing monomer. The (meth) acrylate includes acrylate and methacrylate.
本発明の蓄電デバイス用樹脂は、カルボキシル基含有モノマー（ｂ１）：５〜５０重量％、架橋性モノマー（ｂ２）：０．１〜５重量％、その他のモノマー（ｂ３）：４５〜９４．９重量％（但し、前記（ｂ１）〜（ｂ３）の合計を１００重量％とする）を含むモノマー混合物を重合してなり、
前記架橋性モノマー（ｂ２）が、二重結合を２つ以上有するモノマーおよびアルコキシシリル基含有モノマーの少なくとも何れかである。
Resin for electrical storage devices of the present invention comprises carboxyl group-containing monomer (b1): 5 to 50% by weight, crosslinkable monomer (b2): 0.1 to 5% by weight, other monomer (b3): 45 to 94.9. By polymerizing a monomer mixture containing wt% (provided that the sum of (b1) to (b3) is 100 wt%),
The crosslinkable monomer (b2) is at least one of a monomer having two or more double bonds and an alkoxysilyl group-containing monomer.
本発明の蓄電デバイス用樹脂は、電極の集電体上に形成する下地層のバインダー樹脂、同集電体上ないし下地層上に形成する合材層のバインダー樹脂、分離膜（セパレータともいう）上に形成する保護層のバインダー樹脂、ならび合材層を保護するために形成する樹脂層として使用することが好ましい。すなわち、本発明の蓄電デバイス用樹脂は、蓄電デバイス内の様々な部材の被膜形成用樹脂として使用することが好ましい。 The resin for an electricity storage device of the present invention includes a binder resin for a base layer formed on a current collector of an electrode, a binder resin for a composite layer formed on the current collector or on the base layer, and a separation membrane (also referred to as a separator). It is preferable to use it as a resin layer formed to protect the binder resin and the composite material layer of the protective layer formed above. That is, the resin for an electricity storage device of the present invention is preferably used as a film forming resin for various members in the electricity storage device.
本発明の蓄電デバイス用樹脂（以下、単に「樹脂」ということがある）は、カルボキシル基含有モノマー（ｂ１）、架橋性モノマー（ｂ２）、その他のモノマー（ｂ３）を乳化重合して得る。 The resin for an electricity storage device of the present invention (hereinafter sometimes simply referred to as “resin”) is obtained by emulsion polymerization of a carboxyl group-containing monomer (b1), a crosslinkable monomer (b2), and another monomer (b3).
カルボキシル基含有モノマー（ｂ１）は、被膜と、集電体ないし分離膜等との密着性を向上させるために使用する。カルボキシル基含有モノマー（ｂ１）は、例えば、マレイン酸、フマル酸、イタコン酸、およびシトラコン酸、ならびにこれらのアルキルモノエステルないしアルケニルモノエステル；
フタル酸β−（メタ）アクリロキシエチルモノエステル、イソフタル酸β−（メタ）アクリロキシエチルモノエステル、テレフタル酸β−（メタ）アクリロキシエチルモノエステル、コハク酸β−（メタ）アクリロキシエチルモノエステル、アクリル酸、メタクリル酸、クロトン酸、けい皮酸等が挙げられる。
カルボキシル基含有モノマー（ｂ１）は、単独または複数を併用できる。
The carboxyl group-containing monomer (b1) is used for improving the adhesion between the coating and the current collector or separation membrane. The carboxyl group-containing monomer (b1) is, for example, maleic acid, fumaric acid, itaconic acid, and citraconic acid, and alkyl monoesters or alkenyl monoesters thereof;
Phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester Examples include esters, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.
The carboxyl group-containing monomer (b1) can be used alone or in combination.
カルボキシル基含有モノマー（ｂ１）は、モノマー混合物中、５〜５０重量％を配合することが好ましく、１０〜４８重量％がより好ましく、１５〜４６重量％がさらに好ましい。配合量が５重量％以上になるとより高い密着性が得られる。また、配合量が５０重量％以下になると重合安定性がより向上する。 The carboxyl group-containing monomer (b1) is preferably added in an amount of 5 to 50% by weight in the monomer mixture, more preferably 10 to 48% by weight, and still more preferably 15 to 46% by weight. When the blending amount is 5% by weight or more, higher adhesion can be obtained. Further, when the blending amount is 50% by weight or less, the polymerization stability is further improved.
架橋性モノマー（ｂ２）は、自己架橋型反応性官能基を有しており、主に重合中において前記官能基が自己架橋することでポリマー同士が３次元ポリマーネットワークを形成する。この３次元ポリマーネットワークにより架橋密度が高い樹脂が得られるため、その後、樹脂は、塩基性化合物で中和した後も水に対して溶解せず、エマルションを形成するため電解液耐性が向上する。
架橋性モノマー（ｂ２）は、二重結合を２つ以上有するモノマー、およびアルコキシシリル基含有モノマーのうち少なくとも何れかを使用する。なお、二重結合とは、エチレン性不飽和二重結合である。
The crosslinkable monomer (b2) has a self-crosslinking type reactive functional group, and the polymer forms a three-dimensional polymer network mainly by self-crosslinking of the functional group during polymerization. Since a resin having a high crosslinking density is obtained by this three-dimensional polymer network, the resin does not dissolve in water even after neutralization with a basic compound and forms an emulsion, so that the resistance to the electrolyte is improved.
As the crosslinkable monomer (b2), at least one of a monomer having two or more double bonds and an alkoxysilyl group-containing monomer is used. The double bond is an ethylenically unsaturated double bond.
二重結合を２つ以上有するモノマーは、例えばジビニルベンゼン、およびアジピン酸ジビニル等のジビニル；イソフタル酸ジアリル、フタル酸ジアリル、およびマレイン酸ジアリル等のジアリル；等が挙げられる。 Examples of the monomer having two or more double bonds include divinylbenzene and divinyl such as divinyl adipate; diallyl such as diallyl isophthalate, diallyl phthalate, and diallyl maleate;
アルコキシシリル基含有モノマーは、例えばγ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリブトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシメチルトリメトキシシラン、γ−アクリロキシメチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、およびビニルメチルジメトキシシラン等が挙げられる。 Examples of the alkoxysilyl group-containing monomer include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropylmethyl. Diethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyl Examples include trimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinylmethyldimethoxysilane.
架橋性モノマー（ｂ２）は、モノマー混合物中、０．１〜５重量％を配合することが好ましく、０．２〜４．５重量％がより好ましく、０．３〜４重量％がさらに好ましい。配合量が０．１重量％以上になると樹脂の架橋がより向上し、電解液耐性がより向上する。また、配合量が５重量％以下になると重合安定性がより向上し、樹脂の保存安定性がより向上する。 The crosslinkable monomer (b2) is preferably added in an amount of 0.1 to 5% by weight, more preferably 0.2 to 4.5% by weight, and still more preferably 0.3 to 4% by weight in the monomer mixture. When the blending amount is 0.1% by weight or more, the crosslinking of the resin is further improved, and the resistance to the electrolytic solution is further improved. Further, when the blending amount is 5% by weight or less, the polymerization stability is further improved, and the storage stability of the resin is further improved.
その他のモノマー（ｂ３）は、その使用により樹脂の水に対する溶解度、親水性およびガラス転移温度を調整できる。その他のモノマー（ｂ３）は、アルキル基含有モノマー、ポリエーテル鎖含有モノマー、エポキシ基含有モノマー、アミド基含有モノマー、水酸基含有モノマー、および芳香環含有モノマー等が好ましい。 The other monomer (b3) can adjust the solubility of the resin in water, hydrophilicity and glass transition temperature. The other monomer (b3) is preferably an alkyl group-containing monomer, a polyether chain-containing monomer, an epoxy group-containing monomer, an amide group-containing monomer, a hydroxyl group-containing monomer, an aromatic ring-containing monomer, or the like.
アルキル基含有モノマーは、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、およびラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。
ポリエーテル鎖含有モノマーは、例えばポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、およびエトキシポリエチレングリコール（メタ）アクリレート等が挙げられる。
エポキシ基含有モノマーは、例えばグリシジル（メタ）アクリレート、および３，４−エポキシシクロヘキシル（メタ）アクリレート水酸基含有モノマー
アミド基含有モノマーは、例えば（メタ）アクリルアミド等が挙げられる。
水酸基含有モノマーは、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、および４−ヒドロキシブチル（メタ）アクリレート等が挙げられる。
芳香環含有モノマーは、例えばスチレン、α−メチルスチレン、およびベンジルメタクリレート等が挙げられる。
その他のモノマー（ｂ３）は、単独または複数を使用できる。
Examples of the alkyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( And (meth) acrylate.
Examples of the polyether chain-containing monomer include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meth) acrylate.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate hydroxyl group-containing monomer. Examples of the amide group-containing monomer include (meth) acrylamide.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the aromatic ring-containing monomer include styrene, α-methylstyrene, and benzyl methacrylate.
The other monomer (b3) can be used alone or in combination.
その他のモノマー（ｂ３）は、モノマー混合物中、４５〜９４．９重量％を配合することが好ましく、５０〜９０重量％がより好ましく、５５〜８５重量％がさらに好ましい。カルボキシル基含有モノマー（ｂ１）、架橋性モノマー（ｂ２）は比較的ガラス転移点が高いため、その他のモノマー（ｂ３）を４５重量％以上配合した方が樹脂の柔軟性がより高くなる。一方、９４．９重量％以下にすることで、樹脂の被膜強度がより高くなる。 The other monomer (b3) is preferably added in an amount of 45 to 94.9% by weight, more preferably 50 to 90% by weight, and still more preferably 55 to 85% by weight in the monomer mixture. Since the carboxyl group-containing monomer (b1) and the crosslinkable monomer (b2) have a relatively high glass transition point, the resin becomes more flexible when blended with 45% by weight or more of the other monomer (b3). On the other hand, when the content is 94.9% by weight or less, the coating strength of the resin is further increased.
本発明の蓄電デバイス用樹脂は、乳化重合で合成することが好ましい。乳化重合で合成した蓄電デバイス用樹脂は、粘度が低いため塗工性が優れており緻密で平滑な被膜が形成できる。この乳化重合には、一般的に乳化剤を使用できる。乳化剤は、アニオン性乳化剤およびノニオン性乳化剤を単独若しくは併用できる。また、乳化剤は、ラジカル重合性の官能基を有する乳化剤（以下、反応性乳化剤という）およびラジカル重合性の官能基を有さない乳化剤（以下、非反応性乳化剤という）を使用できる。両者は併用できる。 The resin for an electricity storage device of the present invention is preferably synthesized by emulsion polymerization. A resin for an electricity storage device synthesized by emulsion polymerization has a low viscosity and thus has excellent coating properties, and can form a dense and smooth film. In this emulsion polymerization, an emulsifier can generally be used. As the emulsifier, an anionic emulsifier and a nonionic emulsifier can be used alone or in combination. As the emulsifier, an emulsifier having a radical polymerizable functional group (hereinafter referred to as a reactive emulsifier) and an emulsifier having no radical polymerizable functional group (hereinafter referred to as a non-reactive emulsifier) can be used. Both can be used together.
反応性乳化剤は、例えば、スルホコハク酸エステル系乳化剤、アルキルフェノールエーテル系乳化剤等が挙げられる。 Examples of reactive emulsifiers include sulfosuccinic acid ester emulsifiers and alkylphenol ether emulsifiers.
非反応性乳化剤は、例えばポリオキシエチレンアルキルフェニルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩等のアニオン系非反応性乳化剤；ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンジスチレン化フェニルエーテル等のポリオキシ多環フェニルエーテル類；ポリオキシエチレンソルビタン脂肪酸エステル等のノニオン系非反応性乳化剤等が挙げられる。 Non-reactive emulsifiers are, for example, anionic non-reactive emulsifiers such as polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene alkyl ether sulfate; Polyoxyethylene alkyl phenyl ethers such as oxyethylene octyl phenyl ether; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether And nonionic non-reactive emulsifiers such as polyoxyethylene sorbitan fatty acid esters.
乳化剤は、モノマー混合物１００重量部に対して、０．１〜５重量部程度を使用するのが好ましく、１〜３重量部程度がより好ましい。乳化剤を０．１重量部以上使用すると重合安定性がより向上する。また、乳化剤を５重量部以下使用すると電解液耐性がより向上する。 As for an emulsifier, it is preferable to use about 0.1-5 weight part with respect to 100 weight part of monomer mixtures, and about 1-3 weight part is more preferable. When 0.1 weight part or more of an emulsifier is used, the polymerization stability is further improved. Moreover, when 5 weight part or less of emulsifiers are used, electrolyte solution tolerance will improve more.
前記乳化重合に使用する重合開始剤は、過硫酸塩、過酸化物、およびアゾ化合物等が好ましく、過硫酸塩がより好ましい。
過硫酸塩は、例えば過硫酸カリウム、過硫酸アンモニウム、および過硫酸ナトリウム等が挙げられる。
過酸化物は、例えばターシャリーブチルハイドロパーオキサイド、ターシャリーブチルペルオキシ−２−エチルヘキサノエート、キュメンハイドロパーオキサイド、およびｐ−メンタンハイドロパーオキサイド等が挙げられる。
また乳化重合には、重合開始剤と還元剤を併用した開始剤（以下、レドックス開始剤という）を使用することも好ましい。レドックス開始剤は、過酸化物と還元剤とを組合せて使用できる。
還元剤は、例えばイソアスコルビン酸ナトリウム、Ｌ−アスコルビン酸ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、ピロ亜硫酸ナトリウム、および次亜硫酸ナトリウム等が挙げられる。
The polymerization initiator used for the emulsion polymerization is preferably a persulfate, a peroxide, an azo compound or the like, and more preferably a persulfate.
Examples of the persulfate include potassium persulfate, ammonium persulfate, and sodium persulfate.
Examples of the peroxide include tertiary butyl hydroperoxide, tertiary butyl peroxy-2-ethylhexanoate, cumene hydroperoxide, and p-menthane hydroperoxide.
For emulsion polymerization, it is also preferable to use an initiator (hereinafter referred to as a redox initiator) in which a polymerization initiator and a reducing agent are used in combination. The redox initiator can be used in combination with a peroxide and a reducing agent.
Examples of the reducing agent include sodium isoascorbate, sodium L-ascorbate, sodium sulfite, sodium hydrogen sulfite, sodium pyrosulfite, and sodium hyposulfite.
重合開始剤は、モノマー混合物１００重量部に対して、０．１〜１重量部を使用するのが好ましく、０．２〜０．８重量部がより好ましい。配合量が０．１重量％以上になると、重合安定性がより向上する。また、配合量が１重量％以下になると、耐水性がより向上する。 The polymerization initiator is preferably used in an amount of 0.1 to 1 part by weight, more preferably 0.2 to 0.8 part by weight, based on 100 parts by weight of the monomer mixture. When the blending amount is 0.1% by weight or more, the polymerization stability is further improved. Further, when the blending amount is 1% by weight or less, the water resistance is further improved.
本発明の蓄電デバイス用樹脂のガラス転移温度（以下、Ｔｇともいう）は、−５０〜７０℃が好ましく、−３０〜３０℃がより好ましい。Ｔｇが−５０℃以上になると電池特性がより向上する。また、Ｔｇが７０℃以下になると密着性および塗工性がより向上する。なお、ガラス転移温度は、ＤＳＣ（示差走査熱量計）を用いて求めた実測値である。 The glass transition temperature (hereinafter also referred to as Tg) of the resin for an electricity storage device of the present invention is preferably −50 to 70 ° C., more preferably −30 to 30 ° C. When Tg is −50 ° C. or higher, battery characteristics are further improved. Further, when the Tg is 70 ° C. or lower, the adhesion and coating properties are further improved. The glass transition temperature is an actual measurement value obtained using a DSC (differential scanning calorimeter).
ＤＳＣ（示差走査熱量計）によるＴｇの測定は、例えば蓄電デバイス用樹脂を乾固し約２ｍｇをアルミニウムパン上で秤量し、前記アルミニウムパンをＤＳＣ測定ホルダーにセットし、１０℃／分の昇温条件にて得られるチャートの吸熱ピークを読み取る。このときのピーク温度を本発明のＴｇとする Measurement of Tg by DSC (differential scanning calorimeter) is, for example, to dry the resin for the electricity storage device, weigh about 2 mg on an aluminum pan, set the aluminum pan on the DSC measurement holder, and increase the temperature by 10 ° C./min. Read the endothermic peak of the chart obtained under the conditions. The peak temperature at this time is defined as Tg of the present invention.
蓄電デバイス用樹脂は、重合前ないし重合後に塩基性化合物で中和することができる。塩基性化合物は、アンモニア；トリメチルアミン、トリエチルアミン、ブチルアミン等のアルキルアミン；２−ジメチルアミノエタノール、ジエタノールアミン、トリエタノールアミン、アミノメチルプロパノール等のアルコールアミン；モルホリン等が挙げられる。蓄電デバイス用樹脂を塩基性化合物で中和すると密着性がより向上する。 The resin for an electricity storage device can be neutralized with a basic compound before polymerization or after polymerization. Examples of the basic compound include ammonia; alkylamines such as trimethylamine, triethylamine, and butylamine; alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, and aminomethylpropanol; morpholine. Adhesion is further improved by neutralizing the resin for an electricity storage device with a basic compound.
本発明の蓄電デバイス用樹脂は、蓄電デバイス内に設置する部材の被膜として使用することが好ましい。具体的には、電極の集電体上に形成する下地層、電極の合材層、電極表面ないし分離膜のプラスチック膜上に形成する保護層、ならびに合材層を保護する樹脂層等に使用する被膜として使用することが好ましい。 The resin for an electricity storage device of the present invention is preferably used as a film for a member installed in the electricity storage device. Specifically, it is used for the base layer formed on the current collector of the electrode, the electrode mixture layer, the protective layer formed on the electrode surface or the plastic film of the separation membrane, and the resin layer for protecting the mixture layer It is preferable to use it as a coating film.
本発明の蓄電デバイス電極用樹脂組成物は、集電体上に形成する下地層、ないし合材層等として使用できる。
本発明の蓄電デバイス電極用樹脂組成物は、蓄電デバイス用樹脂と、導電材料とを含む。前記導電材料は、導電性が良好でコストを抑制できる、カーボンブラックおよび黒鉛粒子の少なくともいずれかを含むことが好ましい。
The resin composition for an electricity storage device electrode of the present invention can be used as an underlayer or a composite material layer formed on a current collector.
The resin composition for an electricity storage device electrode of the present invention includes a resin for an electricity storage device and a conductive material. The conductive material preferably contains at least one of carbon black and graphite particles that have good conductivity and can reduce costs.
カーボンブラックは、気体もしくは液体の原料を反応炉中で連続的に熱分解し製造するファーネスブラック、特にエチレン重油を原料としたケッチェンブラック、原料ガスを燃焼させて、その炎をチャンネル鋼底面にあて急冷し析出させたチャンネルブラック、ガスを原料とし燃焼と熱分解を周期的に繰り返すことにより得られるサーマルブラック、特にアセチレンガスを原料とするアセチレンブラック等が好ましい。なお、カーボンブラックは、酸化処理をされたカーボンブラック、および中空カーボンブラック等も好ましい。
これらは単独または２種類以上併用できる。
Carbon black is a furnace black that is produced by continuously pyrolyzing a gas or liquid raw material in a reaction furnace, especially ketjen black using ethylene heavy oil as a raw material. Preference is given to channel black that has been rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using a gas as a raw material, and particularly acetylene black using an acetylene gas as a raw material. The carbon black is preferably oxidized carbon black, hollow carbon black, or the like.
These can be used alone or in combination of two or more.
カーボンの酸化処理は、カーボンを空気中で高温処理する方法、または硝酸、二酸化窒素、あるいはオゾン等で二次的に処理する方法により、例えばフェノール基、キノン基、カルボキシル基、カルボニル基等の酸素含有極性官能基をカーボン表面に直接導入（共有結合）する処理であり、カーボンの分散性を向上させるために一般的な方法である。しかし、前記官能基の導入量に比例してカーボンの導電性が低下するため酸化処理をされたカーボンブラックの使用量は、出来だけ少量が好ましい。 The oxidation treatment of carbon is performed by a method of treating carbon at a high temperature in air or a method of secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, oxygen such as phenol group, quinone group, carboxyl group, carbonyl group, etc. This is a treatment for directly introducing (covalently bonding) the contained polar functional group to the carbon surface, and is a general method for improving the dispersibility of carbon. However, since the conductivity of carbon decreases in proportion to the amount of functional group introduced, the amount of carbon black subjected to oxidation treatment is preferably as small as possible.
カーボンブラックの比表面積は、数値の増加に比例して、カーボンブラック粒子どうしの接触点が増えるため、電極の内部抵抗を下げるのに有利となる。そのためカーボンブラックの比表面積は、窒素の吸着量から求められる比表面積（ＢＥＴ）で、２０〜１５００ｍ2／ｇが好ましく、５０〜１５００ｍ2／ｇがより好ましく、１００〜１５００ｍ2／ｇがさらに好ましい。比表面積が２０ｍ2／ｇ以上になるとカーボンブラックの導電性がより向上する。また、比表面積が１５００ｍ2／ｇ以下のカーボンブラックでないと現在の技術水準では市場で入手できない。 The specific surface area of carbon black is advantageous in reducing the internal resistance of the electrode because the number of contact points between the carbon black particles increases in proportion to the increase in the numerical value. Therefore the specific surface area of the carbon black, a specific surface area determined from the adsorption of nitrogen (BET), preferably from 20~1500m 2 / g, more preferably 50~1500m 2 / g, more preferably 100~1500m 2 / g . When the specific surface area is 20 m 2 / g or more, the conductivity of the carbon black is further improved. In addition, carbon black having a specific surface area of 1500 m 2 / g or less cannot be obtained on the market with the current technical level.
カーボンブラックの平均粒子径は、平均一次粒子径で０．００５〜１μｍが好ましく、、０．０１〜０．２μｍがより好ましい。なお、平均一次粒子径とは、走査型電子顕微鏡の拡大画像（千倍〜１万倍程度）から１０〜２０個程度の一次粒子を平均した数値である。また、粒子の平均アスペクト比１．５以上である場合、長軸長さと短軸長さのうち長軸長さを平均する。 The average particle size of carbon black is preferably 0.005 to 1 μm, more preferably 0.01 to 0.2 μm, in terms of average primary particle size. In addition, an average primary particle diameter is the numerical value which averaged about 10-20 primary particles from the enlarged image (about 1000 times-10,000 times) of the scanning electron microscope. When the average aspect ratio of the particles is 1.5 or more, the major axis length is averaged out of the major axis length and minor axis length.
黒鉛は、葉状、球状、および土状等の形状の粒子であり、導電性の面で葉状黒鉛粒子が好ましい。 Graphite is a particle having a leaf-like shape, a spherical shape, and a soil-like shape, and the leaf-like graphite particle is preferable in terms of conductivity.
黒鉛粒子の平均粒子径は、平均一次粒子径であり１〜５０μｍが好ましく、３〜４０μｍがより好ましい。なお、葉状黒鉛粒子を使用する場合、表面が平滑で導電性が良好な被膜が得られることからその厚みは、０．０１〜２μｍが好ましい。 The average particle diameter of the graphite particles is an average primary particle diameter, preferably 1 to 50 μm, and more preferably 3 to 40 μm. In addition, when using foliar graphite particle | grains, since the surface is smooth and the film | membrane with favorable electroconductivity is obtained, the thickness has preferable 0.01-2 micrometers.
葉状黒鉛粒子は、例えば、塊状の天然黒鉛を粉砕する方法、または天然黒鉛の層間化合物のへき開面に沿って、層間剥離を行なう方法で得ることができる。前記粉砕の場合、例えば、ボールミルなどを用いた乾式粉砕法が好ましい。 The foliar graphite particles can be obtained, for example, by a method of pulverizing massive natural graphite or a method of performing delamination along a cleavage plane of an intercalation compound of natural graphite. In the case of the pulverization, for example, a dry pulverization method using a ball mill or the like is preferable.
導電材料は、蓄電デバイス用樹脂および導電材料の合計１００重量％中、１０〜７０重量％含むことが好ましく、１５〜６５重量％がより好ましい。導電材料が１０重量％以上になると導電性がより向上する。また、導電材料が７０重量％以下になると被膜の密着性がより向上する。 The conductive material is preferably contained in an amount of 10 to 70% by weight, more preferably 15 to 65% by weight, in a total of 100% by weight of the resin for an electricity storage device and the conductive material. When the conductive material is 10% by weight or more, the conductivity is further improved. Further, when the conductive material is 70% by weight or less, the adhesion of the coating is further improved.
本発明の蓄電デバイス電極用樹脂組成物を製造する際、導電材料と蓄電デバイス用樹脂との混合は、導電材料を予備分散してから蓄電デバイス用樹脂と混合すると、導電材料を被膜中により微細に、より均一に、分散できる。予備分散には、水および水溶性の分散樹脂を使用することが好ましい。水溶性の分散樹脂は、例えばセルロース樹脂、アクリル樹脂、スチレン・アクリル樹脂、ポリエステル樹脂、およびウレタン樹脂等が好ましい。 When the resin composition for an electricity storage device electrode according to the present invention is produced, the conductive material and the resin for the electricity storage device are mixed with each other by pre-dispersing the conductive material and then mixing with the resin for the electricity storage device. More uniformly. For the preliminary dispersion, it is preferable to use water and a water-soluble dispersion resin. The water-soluble dispersion resin is preferably a cellulose resin, an acrylic resin, a styrene / acrylic resin, a polyester resin, a urethane resin, or the like.
本発明の蓄電デバイス電極用樹脂組成物は、さらに溶剤、成膜助剤、消泡剤、レベリング剤、防腐剤、ｐＨ調整剤、粘性調整剤等を含むことができる。 The resin composition for an electricity storage device electrode of the present invention can further contain a solvent, a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjusting agent, a viscosity adjusting agent and the like.
本発明の蓄電デバイス電極用樹脂組成物は、そのまま集電体上に塗工すると下地層を形成できる。または、蓄電デバイス電極用樹脂組成物と活物質とを配合し合材インキを得た後、集電体上ないし下地層上に塗工することで合材層を形成できる。 When the resin composition for an electricity storage device electrode of the present invention is applied as it is onto a current collector, a base layer can be formed. Alternatively, the composite material layer can be formed by coating a resin composition for an electricity storage device electrode and an active material to obtain a composite ink, and then coating on the current collector or the base layer.
本発明の蓄電デバイス電極は、少なくとも、集電体と、蓄電デバイス電極用樹脂組成物から形成されてなる下地層とを備えている。本発明の蓄電デバイス電極を備えた蓄電デバイスは、導電性が良好な下地層の存在により電池性能が向上する。 The electricity storage device electrode of the present invention includes at least a current collector and a base layer formed from the resin composition for an electricity storage device electrode. The power storage device provided with the power storage device electrode of the present invention has improved battery performance due to the presence of a base layer having good conductivity.
集電体は、蓄電デバイスの電極で一般的に使用されている集電体である。集電体の素材は、例えば、アルミニウム、銅、ニッケル、チタン、およびステンレス等の金属ならびにこれらの合金が挙げられる。蓄電デバイスが例えばリチウムイオン電池の場合、特に正極用集電体は、アルミニウムが好ましく、負極用集電体は、銅が好ましい。集電体の形状は、蓄電デバイスの形状に応じた形状で使用できる。一般的には平板上の箔が用いられているが、表面を粗面化した集電体、小穴を形成した集電体、メッシュ状の集電体等が挙げられる。 The current collector is a current collector generally used for an electrode of an electricity storage device. Examples of the material of the current collector include metals such as aluminum, copper, nickel, titanium, and stainless steel, and alloys thereof. When the power storage device is a lithium ion battery, for example, the positive electrode current collector is preferably aluminum, and the negative electrode current collector is preferably copper. The shape of the current collector can be used in a shape corresponding to the shape of the electricity storage device. In general, a foil on a flat plate is used, and examples thereof include a current collector having a roughened surface, a current collector having a small hole, and a mesh current collector.
集電体の厚みは、一般的には１〜１００μｍ程度であり、５〜５０μｍ程度がより好ましい。 The thickness of the current collector is generally about 1 to 100 μm, and more preferably about 5 to 50 μm.
前記下地層の形成は、集電体上に蓄電デバイス電極用樹脂組成物を塗工して形成する。下地層の厚みは、一般的には０．１〜５μｍ程度であり、０．１〜２μｍがより好ましい。
前記塗工は、例えばダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法および静電塗装法等の公知の塗工方法が可能である。また、塗工の際、乾燥工程を行うことが好ましい。乾燥工程は、例えば送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機等の公知の乾燥装置を使用できる。また、平版プレスやカレンダーロール等による圧延処理を行い下地層の表面を平滑することができる。
The underlayer is formed by applying a resin composition for an electricity storage device electrode on a current collector. The thickness of the underlayer is generally about 0.1 to 5 μm, and more preferably 0.1 to 2 μm.
Examples of the coating include known coating methods such as a die coating method, a dip coating method, a roll coating method, a doctor coating method, a knife coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Is possible. Moreover, it is preferable to perform a drying process in the case of coating. For the drying step, for example, a known drying device such as a blower dryer, a hot air dryer, an infrared heater, or a far infrared heater can be used. Further, the surface of the underlayer can be smoothed by performing a rolling process using a lithographic press or a calender roll.
蓄電デバイス電極用樹脂組成物を合材層の形成に使用する場合、さらに活物質を配合した合材インキを作製してから使用できる。活物質は、蓄電デバイスの種類により化合物が異なる。
まず、リチウムイオン二次電池の正極用活物質は、例えばリチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物、および導電性高分子等が挙げられる。金属酸化物は、例えば、Ｆｅ、Ｃｏ、Ｎｉ、およびＭｎ等の遷移金属の酸化物、ならびにリチウムとの複合酸化物等が好ましい。
金属硫化物は、遷移金属硫化物等が好ましい。具体的には、ＭｎＯ、Ｖ2Ｏ5、Ｖ6Ｏ13、ＴｉＯ2等の遷移金属酸化物粉末；、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウム等のリチウムと遷移金属との複合酸化物；、オリビン構造のリン酸化合物であるリン酸鉄リチウム；、ＴｉＳ2、ＦｅＳ等の遷移金属硫化物等が挙げられる。
When the resin composition for an electricity storage device electrode is used for forming a composite layer, it can be used after preparing a composite ink containing an active material. The active material has different compounds depending on the type of power storage device.
First, examples of the positive electrode active material of the lithium ion secondary battery include metal oxides, metal sulfides, and conductive polymers that can be doped or intercalated with lithium ions. As the metal oxide, for example, oxides of transition metals such as Fe, Co, Ni, and Mn, and composite oxides with lithium are preferable.
The metal sulfide is preferably a transition metal sulfide. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , and TiO 2 ; lithium nickelate having a layered structure, lithium cobaltate, lithium manganate, lithium manganate having a spinel structure, etc. A composite oxide of lithium and a transition metal; lithium iron phosphate which is a phosphate compound having an olivine structure; and transition metal sulfides such as TiS 2 and FeS.
前記正極用活物質の平均一次粒子径は、０．０５〜１００μｍ程度が好ましく、０．１〜５０μｍ程度がより好ましい。
The average primary particle diameter of the positive electrode active material is preferably about 0.05 to 100 μm, and more preferably about 0.1 to 50 μm.
なお、合材インキ中に分散された状態（溶液）の活物質の平均粒子径（以下、分散粒子径ともいう）は、０．５〜２０μｍが好ましい。なお分散粒子径とは、体積粒度分布におけるＤ５０平均粒子径であり、一般的な粒度分布計、例えば、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）等で測定できる。 The average particle size (hereinafter also referred to as dispersed particle size) of the active material (solution) dispersed in the composite ink is preferably 0.5 to 20 μm. The dispersed particle size is the D50 average particle size in the volume particle size distribution, and can be measured with a general particle size distribution meter, for example, a dynamic light scattering type particle size distribution meter (“Microtrac UPA” manufactured by Nikkiso Co., Ltd.). .
リチウムイオン二次電池の負極用活物質は、例えば金属リチウム、ならびにその錫、シリコンおよび鉛等との合金、ＬｉXＦｅ2Ｏ3、ＬｉXＦｅ3Ｏ4、ＬｉXＷＯ2、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物：、ポリアセチレン、ポリ−ｐ−フェニレン等の導電性高分子、ソフトカーボンおよびハードカーボン等のアモルファスカーボン；。人造黒鉛および天然黒鉛等の黒鉛粒子、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維等が挙げられる。 Examples of the active material for the negative electrode of the lithium ion secondary battery include metallic lithium and alloys thereof such as tin, silicon and lead, Li x Fe 2 O 3 , Li x Fe 3 O 4 , Li x WO 2 and lithium titanate. Metal oxides such as lithium vanadate and lithium siliconate, conductive polymers such as polyacetylene and poly-p-phenylene, and amorphous carbon such as soft carbon and hard carbon; Examples thereof include graphite particles such as artificial graphite and natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, air-growth carbon fiber, and carbon fiber.
前記負極用活物質の平均一次粒子径は、０．０５〜１００μｍ程度が好ましく、０．１〜５０程度μｍが好ましい。 The average primary particle size of the negative electrode active material is preferably about 0.05 to 100 μm, and preferably about 0.1 to 50 μm.
次に、キャパシターは、例えば電気二重層キャパシターおよびリチウムイオンキャパシター等が挙げられる。
電気二重層キャパシターの活物質は、例えば活性炭、ポリアセン、カーボンウィスカおよびグラファイトが好ましい。電気二重層キャパシターの活物質は、同じ重量でもより広い面積の界面を形成することが可能な、比表面積の大きい活物質が好ましい。具体的には、比表面積が３０ｍ2／ｇ〜１００００ｍ2／ｇが好ましく、５００〜５０００ｍ2／ｇがより好ましく、１０００〜 ３０００ｍ2／ｇがさらに好ましい。
Next, examples of the capacitor include an electric double layer capacitor and a lithium ion capacitor.
As the active material of the electric double layer capacitor, for example, activated carbon, polyacene, carbon whisker and graphite are preferable. The active material of the electric double layer capacitor is preferably an active material having a large specific surface area that can form an interface having a larger area even with the same weight. Specifically, the ratio is preferably 30m 2 / g~10000m 2 / g surface area, more preferably 500~5000m 2 / g, more preferably 1000~ 3000m 2 / g.
リチウムイオンキャパシターの活物質は、リチウムイオン二次電池の正極用活物質を用いることができる。 As the active material of the lithium ion capacitor, an active material for a positive electrode of a lithium ion secondary battery can be used.
活物質は、導電性を高めるために合材インキ中にできるだけ多く配合することが好ましいので合材インキの不揮発分１００重量％のうち、８０〜９９重量％を含むことが好ましい。 Since it is preferable to mix the active material as much as possible in the composite ink in order to increase the conductivity, it is preferable that 80 to 99% by weight is included in 100% by weight of the non-volatile content of the composite ink.
蓄電デバイス電極用樹脂組成物を合材層として使用する場合（合材インキ）、活物質の他に、さらに添加剤として成膜助剤、消泡剤、レベリング剤、防腐剤、ｐＨ調整剤、粘性調整剤等を配合できる。前記添加剤は、二次電池ないしキャパシターの種類に応じて適宜調整できる。 When using the resin composition for an electricity storage device electrode as a composite layer (composite ink), in addition to the active material, as additives, film forming aids, antifoaming agents, leveling agents, preservatives, pH adjusters, Viscosity modifiers can be blended. The additive can be appropriately adjusted according to the type of secondary battery or capacitor.
前記合材インキの製造は、攪拌混合に顔料分散等で使用されている分散機ないし混合機を用いることが好ましい。ここから
分散機ないし混合機は、例えば、ディスパー、ホモミキサー、およびプラネタリーミキサー等のミキサー；ボールミル、サンドミル、アトライター、パールミル、およびコボールミル等のメディア型分散機；湿式ジェットミル等のメディアレス分散機；その他ロールミル等が挙げられるが、これらに限定されるものではない。また、分散機としては、分散機からの金属混入防止処理を施した装置を用いることが好ましい。
In the production of the composite ink, it is preferable to use a disperser or a mixer that is used for stirring and mixing by pigment dispersion or the like. From here, dispersers or mixers include, for example, mixers such as dispersers, homomixers, and planetary mixers; media type dispersers such as ball mills, sand mills, attritors, pearl mills, and coball mills; medialess dispersions such as wet jet mills Machine; other roll mills and the like, but not limited thereto. Further, as the disperser, it is preferable to use an apparatus that has been subjected to a metal contamination prevention process from the disperser.
合材層は、合材インキを集電体上に塗工して形成できる。または合材インキを集電体上に形成した下地層上に塗工して形成できる。または、合材インキを剥離性シート上に塗工して合材層を形成し、前記合材層を集電体上ないし下地層上に転写することでも形成できる。
合材インキの塗工は、下地層の形成で説明した塗工方法を使用できる。
The composite material layer can be formed by applying a composite ink on a current collector. Alternatively, the composite ink can be formed by coating on a base layer formed on the current collector. Alternatively, the composite ink can be formed by applying a composite ink on a peelable sheet to form a composite layer, and transferring the composite layer onto a current collector or a base layer.
For the application of the composite ink, the coating method described in the formation of the underlayer can be used.
合材層の厚さは、通常１〜５００μｍが好ましい。 The thickness of the composite layer is usually preferably 1 to 500 μm.
本発明の蓄電デバイス電極は、集電体、下地層および合材層を備えた場合、蓄電デバイスの充放電サイクル特性が向上する。なお蓄電デバイス電極は、下地層および合材層に本発明の蓄電デバイス用樹脂を使用することが最も好ましいが、下地層ないし合材層のいずれか一方に使用するだけでも電池特性が向上できる。 When the electricity storage device electrode of the present invention includes a current collector, an underlayer and a composite layer, the charge / discharge cycle characteristics of the electricity storage device are improved. In addition, although it is most preferable that the electricity storage device electrode uses the resin for an electricity storage device of the present invention for the underlayer and the composite layer, the battery characteristics can be improved only by using it for either the underlayer or the composite material layer.
本発明の蓄電デバイス電極は、合材層上に本発明の蓄電デバイス用樹脂を使用して形成した樹脂層を備えることもできる。蓄電デバイス電極が樹脂層を備えると、電解液中に生成したデンドライド粒子の衝突による合材層の損傷を低減できる。前記樹脂層は、下地層および合材層に本発明の蓄電デバイス用樹脂を使用することが最も好ましいが、両者のいずれにも含まない態様で使用する場合も電池性能が向上する。前記樹脂層の厚みは、０．１〜１０μｍ程度である。 The electrical storage device electrode of this invention can also be equipped with the resin layer formed using the resin for electrical storage devices of this invention on the compound material layer. When the electricity storage device electrode includes the resin layer, damage to the composite layer due to the collision of the dendriide particles generated in the electrolytic solution can be reduced. The resin layer most preferably uses the resin for an electricity storage device of the present invention for the base layer and the composite layer, but the battery performance is improved even when the resin layer is used in a mode not included in either of them. The resin layer has a thickness of about 0.1 to 10 μm.
本発明の蓄電デバイス分離膜用樹脂組成物は、本発明の蓄電デバイス用樹脂と無機粒子を含む。本発明の蓄電デバイス分離膜用樹脂組成物は、リチウムイオン二次電池に代表される二次電池内部に設置される分離膜を保護する保護層として使用できる。前記保護層に蓄電デバイス用樹脂を使用すると例えばリチウムイオン二次電池が過熱した際に電極のショートによる爆発の危険性を抑制できることに加え、無機粒子をより微細に、より均一に分散できるため分離膜との密着性および柔軟性が優れており、ならびにデンドライド粒子の衝突による分離膜の損傷を低減できる。 The resin composition for an electricity storage device separation membrane of the present invention includes the resin for an electricity storage device of the present invention and inorganic particles. The resin composition for an electricity storage device separation membrane of the present invention can be used as a protective layer for protecting a separation membrane installed in a secondary battery represented by a lithium ion secondary battery. When resin for electricity storage devices is used for the protective layer, for example, when lithium ion secondary batteries are overheated, the risk of explosion due to short-circuiting of electrodes can be suppressed, and inorganic particles can be dispersed more finely and more uniformly. Adhesion and flexibility with the membrane are excellent, and damage to the separation membrane due to collision of dendritic particles can be reduced.
無機粒子は、例えば酸化アルミニウム、酸化ジルコニウム、酸化チタン、シリカ、およびイオン伝導性ガラスが好ましい。 The inorganic particles are preferably, for example, aluminum oxide, zirconium oxide, titanium oxide, silica, and ion conductive glass.
無機粒子の平均一次粒子径は、０．０１〜１０μｍが好ましい。前記平均一次粒子径により、保護層の被膜強度とリチウムイオンの伝導性をより高いレベルで両立できる。 The average primary particle diameter of the inorganic particles is preferably 0.01 to 10 μm. With the average primary particle size, both the coating strength of the protective layer and the lithium ion conductivity can be achieved at a higher level.
蓄電デバイス用樹脂は、無機粒子１００重量部に対して、０．１〜１０重量部を使用することが好ましく、０．１〜５重量部がより好ましい。０．１〜１０重量部を使用することで、無機粒子同士の密着性および分離膜への密着性と柔軟性を維持しつつ、リチウムイオンの伝導性をより向上できる。 It is preferable that 0.1-10 weight part is used for resin for electrical storage devices with respect to 100 weight part of inorganic particles, and 0.1-5 weight part is more preferable. By using 0.1 to 10 parts by weight, the conductivity of lithium ions can be further improved while maintaining the adhesion between inorganic particles and the adhesion and flexibility to the separation membrane.
本発明の蓄電デバイス分離膜用樹脂組成物には、さらに成膜助剤、消泡剤、レベリング剤、防腐剤、ｐＨ調整剤、粘性調整剤等を配合できる。 The resin composition for an electricity storage device separation membrane of the present invention can further contain a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjuster, a viscosity adjuster, and the like.
分離膜は、電解液に溶解しない膜でありプラスチック膜を使用するのが一般的である。 The separation membrane is a membrane that does not dissolve in the electrolytic solution, and a plastic membrane is generally used.
プラスチック膜の素材は、例えばポリエチレンおよびポリプロピレン等ポリオレフィン、およびポリアミド、ならびにそれらに親水性処理を施した膜が挙げられる。またプラスチック膜の形態は、不織布、細孔を有する膜等イオンが通過できる穴を有すること一般的である。 Examples of the material of the plastic film include polyolefins such as polyethylene and polypropylene, and polyamides, and films obtained by subjecting them to hydrophilic treatment. Moreover, the form of the plastic membrane is generally provided with holes through which ions can pass, such as a nonwoven fabric or a membrane having pores.
プラスチック膜の厚みは、１〜５０μｍ程度である。 The thickness of the plastic film is about 1 to 50 μm.
本発明の蓄電デバイス分離膜は、プラスチック膜と、本発明の蓄電デバイス分離膜用樹脂組成物から形成された保護層を備えている。 The electricity storage device separation membrane of the present invention includes a plastic film and a protective layer formed from the resin composition for an electricity storage device separation membrane of the present invention.
前記保護層の形成は、例えばプラスチック膜上に蓄電デバイス分離膜用樹脂組成物を塗工することで形成できる。または、例えば剥離性シート上に蓄電デバイス分離膜用樹脂組成物を塗工して形成した保護層をプラスチック膜上に転写することで形成できる。保護層 The protective layer can be formed, for example, by coating a resin composition for an electricity storage device separation film on a plastic film. Alternatively, for example, it can be formed by transferring a protective layer formed by coating a resin composition for an electricity storage device separation film on a peelable sheet onto a plastic film. Protective layer
前記塗工は、下地層の塗工で説明した塗工方法を使用できる。保護層の厚みは、０．１〜１０μｍが好ましい。 For the coating, the coating method described in the application of the underlayer can be used. As for the thickness of a protective layer, 0.1-10 micrometers is preferable.
本発明の蓄電デバイスは、蓄電デバイス用樹脂を正極、負極および分離膜の少なくともいずれかを使用することが好ましい。具体的には、本発明の蓄電デバイスは、本発明の蓄電デバイス電極、および本発明の蓄電デバイス分離膜の少なくともいずれかを備えている。本発明の蓄電デバイス用樹脂を使用した被膜を有する蓄電デバイスは、蓄電デバイス電極を備えた場合は、電池特性が向上し、蓄電デバイス分離膜を備えた場合は、デンドライト粒子による損傷を抑制できる。 In the electricity storage device of the present invention, it is preferable to use at least one of a positive electrode, a negative electrode, and a separation membrane as the resin for the electricity storage device. Specifically, the power storage device of the present invention includes at least one of the power storage device electrode of the present invention and the power storage device separation membrane of the present invention. An electricity storage device having a film using the resin for an electricity storage device of the present invention has improved battery characteristics when provided with an electricity storage device electrode, and can suppress damage due to dendrite particles when provided with an electricity storage device separation membrane.
蓄電デバイスのうち二次電池は、リチウムイオン二次電池の他、ナトリウムイオン二次電池、マグネシウムイオン二次電池、アルカリ二次電池、鉛蓄電池、ナトリウム硫黄二次電池、およびリチウム空気二次電池等が挙げられる。これらの二次電池は、従来から知られている、電解液や分離膜等を適宜用いることができる。
キャパシターは、電気二重層キャパシター、リチウムイオンキャパシターなどが挙げられる。これらのキャパシターで従来から知られている、電解液や分離膜等を適宜用いることができる。
Among storage devices, secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium ion secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, and lithium air secondary batteries. Is mentioned. For these secondary batteries, conventionally known electrolytes, separation membranes, and the like can be used as appropriate.
Examples of the capacitor include an electric double layer capacitor and a lithium ion capacitor. Conventionally known electrolytes and separation membranes for these capacitors can be used as appropriate.
リチウムイオン二次電池を例に電解液を説明する。電解液は、リチウムを含んだ電解質を非水系の溶剤に溶解した液体を用いる。なお、非水系の溶剤とは、水を含有しない溶剤である。 The electrolytic solution will be described taking a lithium ion secondary battery as an example. As the electrolytic solution, a liquid in which an electrolyte containing lithium is dissolved in a non-aqueous solvent is used. The non-aqueous solvent is a solvent that does not contain water.
電解質は、例えばＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）2Ｎ、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）3Ｃ、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ2、ＬｉＳＣＮ、およびＬｉＢＰｈ4等が挙げられる。
また、電解液は、ポリマーマトリクスに電解液を保持しゲル状とした高分子電解質として使用することが好ましい。具体的には、例えばポリアルキレンオキシドセグメントを有するアクリレート系樹脂、ポリアルキレンオキシドセグメントを有するポリホスファゼン系樹脂、およびポリアルキレンオキシドセグメントを有するポリシロキサン等が挙げられる。
Examples of the electrolyte include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C. , LiI, LiBr, LiCl, LiAlCl , LiHF 2, LiSCN, and LiBPh 4, and the like.
Further, the electrolytic solution is preferably used as a polymer electrolyte that is gelled by holding the electrolytic solution in a polymer matrix. Specific examples include acrylate resins having a polyalkylene oxide segment, polyphosphazene resins having a polyalkylene oxide segment, and polysiloxane having a polyalkylene oxide segment.
非水系の溶剤としては特に限定はされないが、例えばエチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、およびジエチルカーボネート等のカーボネート；γ−ブチロラクトン、γ−バレロラクトン、およびγ−オクタノイックラクトン等のラクトン；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−メトキシエタン、１，２−エトキシエタン、および１，２−ジブトキシエタン等のグライム；メチルフォルメート、メチルアセテート、およびメチルプロピオネート等のエステル；ジメチルスルホキシド、およびスルホラン等のスルホキシド；並びに、 アセトニトリル等のニトリル等が挙げられる。これらの溶剤は、単独でまたは２種以上を使用できる。 Although it does not specifically limit as a non-aqueous solvent, For example, carbonates, such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ-octano Lactones such as iclactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2-dibutoxy Glymes such as ethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. It is. These solvents can be used alone or in combination of two or more.
本発明の蓄電デバイス用樹脂を使用した蓄電デバイス（例えば、リチウムイオン二次電池、電気二重層キャパシター、リチウムイオンキャパシター）の構造は、公知の構造が使用できるため限定されない。例えば、通常は、正極および負極、ならびに必要に応じて設けられる分離膜とから構成され、その形状は、ペーパー型、円筒型、ボタン型、積層型等使用する目的に応じた形状を採用できる。また、本発明の蓄電デバイス用樹脂は、空気二次電池、ナトリウム二次電池、マグネシウム二次電池等の二次電池等の内部に被膜を必要とする蓄電デバイスに使用することも可能である。 The structure of an electricity storage device (for example, a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor) using the resin for an electricity storage device of the present invention is not limited because a known structure can be used. For example, it is usually composed of a positive electrode and a negative electrode, and a separation membrane provided as necessary, and the shape can be selected according to the purpose of use, such as a paper type, a cylindrical type, a button type, and a laminated type. The resin for an electricity storage device of the present invention can also be used for an electricity storage device that requires a coating inside a secondary battery such as an air secondary battery, a sodium secondary battery, or a magnesium secondary battery.
以下に、実施例により、本発明をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。なお、部は重量部、％は重量％をそれぞれ意味する。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, a part means a weight part and% means weight%, respectively.
＜合成例１＞蓄電デバイス用樹脂の合成
カルボキシル基含有モノマー（ｂ１）としてアクリル酸４０部、架橋性モノマー（ｂ２）としてフタル酸ジアリル０．５部、その他モノマー（ｂ３）としてブチルアクリレート５９．５部、界面活性剤としてアニオン性界面活性剤のエレミノールＣＬＳ‐２０（三洋化成工業社製）１．５部、イオン交換水５３．１部の混合液を乳化することでモノマープレエマルションを作成し、滴下槽に仕込んだ。
別途、還流冷却器、攪拌機、温度計、窒素導入管、原料投入口を備えた容積２Ｌの４つ口フラスコを反応容器とし、当該反応容器にイオン交換水８９．４部を仕込んだ。次いで、窒素雰囲気下、攪拌しながら、液温を６０℃に加熱した。そして、反応容器中に、界面活性剤としてエレミノールＣＬＳ−２０を０．２部添加し、滴下槽から上記モノマープレエマルションを５時間かけて連続的に滴下し、過硫酸アンモニウム０．３部使用することで液温を約６０℃に保ちつつ乳化重合を行った。滴下終了後、液温を６０℃に保ち、３時間乳化重合を継続した。その後、５０℃まで冷却し、溶液を１８０メッシュのポリエステル製の濾布で濾過することでバインダー樹脂分散液を得た。濾布に残った凝集物はなく、重合安定性は良好であった。得られたバインダー樹脂分散液を、２５％のアンモニア水を用いてｐＨが８．０になるように中和した。得られたバインダー樹脂分散液の不揮発分は４０％であった。
Synthesis Example 1 Synthesis of Resin for Electricity Storage Device 40 parts of acrylic acid as carboxyl group-containing monomer (b1), 0.5 part of diallyl phthalate as crosslinkable monomer (b2), and 59.5 as butyl acrylate as other monomer (b3) A monomer pre-emulsion is prepared by emulsifying a mixed solution of 1.5 parts of anionic surfactant Eleminol CLS-20 (manufactured by Sanyo Chemical Industries) and 53.1 parts of ion-exchanged water as a surfactant. The dropping tank was charged.
Separately, a 2 L four-necked flask equipped with a reflux condenser, a stirrer, a thermometer, a nitrogen inlet tube, and a raw material inlet was used as a reaction vessel, and 89.4 parts of ion-exchanged water was charged into the reaction vessel. Next, the liquid temperature was heated to 60 ° C. with stirring in a nitrogen atmosphere. Then, 0.2 part of Eleminol CLS-20 as a surfactant is added to the reaction vessel, and the monomer pre-emulsion is continuously dropped over 5 hours from the dropping tank, and 0.3 part of ammonium persulfate is used. The emulsion polymerization was carried out while maintaining the liquid temperature at about 60 ° C. After completion of the dropwise addition, the liquid temperature was kept at 60 ° C. and emulsion polymerization was continued for 3 hours. Then, it cooled to 50 degreeC and the binder resin dispersion liquid was obtained by filtering a solution with the filter cloth made from a 180 mesh polyester. There was no aggregate remaining on the filter cloth, and the polymerization stability was good. The resulting binder resin dispersion was neutralized with 25% aqueous ammonia to a pH of 8.0. The nonvolatile content of the obtained binder resin dispersion was 40%.
＜合成例２〜１０＞蓄電デバイス用樹脂の合成
表１に示す配合組成に変更した以外は合成例１と同様の方法で行うことで合成例２〜１０のバインダー樹脂分散液を得た。なお、合成例８はカルボキシル基含有モノマー（ｂ１）の使用量が過剰であったため、重合安定性が低下したことで、乳化重合時にエマルションが凝集してしまい、バインダー樹脂分散液が得られなかった。また、合成例１０は架橋性モノマー（ｂ２）の使用量が過剰であったため、重合安定性が低下し、乳化重合時にエマルションが凝集してしまい、バインダー樹脂分散液が得られなかった。
<Synthesis Examples 2 to 10> Synthesis of Resin for Electricity Storage Device Binder resin dispersions of Synthesis Examples 2 to 10 were obtained by the same method as Synthesis Example 1 except that the composition shown in Table 1 was changed. In addition, since the usage-amount of the carboxyl group-containing monomer (b1) was excessive in Synthesis Example 8, the emulsion was agglomerated during emulsion polymerization due to a decrease in polymerization stability, and a binder resin dispersion was not obtained. . Moreover, since the usage-amount of the crosslinking | crosslinked monomer (b2) was excessive in the synthesis example 10, superposition | polymerization stability fell, the emulsion aggregated at the time of emulsion polymerization, and the binder resin dispersion liquid was not obtained.
＜下地層の作製＞
合成例１で得たバインダー樹脂分散液２５部（不揮発分換算で１０部）、導電材料としてアセチレンブラック(デンカブラックＨＳ−１００）１０部、分散剤としてポリアリルアミン２０％水溶液を５部（固形分として１部）、水２１５部をミキサーに入れて混合した上、サンドミルに投入し分散処理することで蓄電デバイス用樹脂組成物を得た。
<Preparation of underlayer>
25 parts of binder resin dispersion obtained in Synthesis Example 1 (10 parts in terms of non-volatile content), 10 parts of acetylene black (Denka Black HS-100) as a conductive material, and 5 parts (solid content) of a 20% aqueous solution of polyallylamine as a dispersant 1 part) and 215 parts of water were mixed in a mixer, and then charged into a sand mill and dispersed to obtain a resin composition for an electricity storage device.
得られた蓄電デバイス電極用樹脂組成物を、集電体（厚さ２０μｍのアルミ箔）上に乾燥後の厚みが１．２μｍになるようにバーコーターを用いて塗布した後、加熱乾燥することで下地層付き集電体（１）を得た。 The obtained resin composition for an electricity storage device electrode is coated on a current collector (aluminum foil having a thickness of 20 μm) using a bar coater so that the thickness after drying is 1.2 μm, and then dried by heating. Thus, a current collector (1) with an underlayer was obtained.
下地層付き集電体（１）で使用したバインダー樹脂分散液および導電材料を表２の原料に変更した以外は、下地層付き集電体（１）の作成と同様に行なうことで下地層付き集電体（２）〜（１３）を得た。 Underlying layer with current collector (1), except that the binder resin dispersion and conductive material used in current collector with underlayer (1) were changed to the raw materials shown in Table 2 Current collectors (2) to (13) were obtained.
得られた下地層付き集電体について下記の耐溶剤性試験を行った。 The following solvent resistance test was performed on the obtained collector with an underlayer.
（耐溶剤性）
下地層付き集電体の表面を、ＮＭＰ（Ｎ−メチルピロリドン）で湿らせた綿布で擦り耐溶剤性を評価した。なお耐溶剤性は、下地層の上へ合材インキを塗工する際に、合材インキに含まれる溶剤で下地層が崩壊しないために重要である。評価基準を下記に示す。
◎：「下地層に異常がない（良好）」
○：「下地層がわずかに削れたが、集電体は露出しない（実用可）」
△：「下地層が一部削れ、集電体が部分的に露出している（実用不可）」
×：「下地層が削れ、集電体が全面的に露出している（不良）」
(Solvent resistance)
The surface of the current collector with the underlayer was rubbed with a cotton cloth moistened with NMP (N-methylpyrrolidone) to evaluate the solvent resistance. The solvent resistance is important because the base layer does not collapse with the solvent contained in the composite ink when the composite ink is applied onto the base layer. The evaluation criteria are shown below.
A: “Underlying layer is normal (good)”
○: “Underlayer is slightly removed, but the current collector is not exposed (practical)”
Δ: “Part of the underlying layer is scraped and the current collector is partially exposed (unusable)”
×: “The underlayer is scraped and the current collector is exposed entirely (defect)”
表２の略号は以下の通りである。
ＨＳ−１００：デンカブラックＨＳ−１００（アセチレンブラック、平均一次粒子径３５ｎｍ、電気化学工業社製）
＃３０５０Ｂ：ミツビシカーボン＃３０５０Ｂ（カーボンブラック、平均一次粒子径４０ｎｍ、三菱化学社製）
ＵＰ−５： グラファイトパウダーＵＰ−５（葉状黒鉛粒子、平均一次粒子径５μｍ、日本黒鉛社製）
Abbreviations in Table 2 are as follows.
HS-100: Denka black HS-100 (acetylene black, average primary particle size 35 nm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
# 3050B: Mitsubishi Carbon # 3050B (carbon black, average primary particle size 40 nm, manufactured by Mitsubishi Chemical Corporation)
UP-5: Graphite powder UP-5 (leaf-like graphite particles, average primary particle diameter of 5 μm, manufactured by Nippon Graphite Co., Ltd.)
「リチウムイオン二次電池用正極の作成」
＜正極用合材インキの作成＞
正極活物質としてＬｉＦｅＰＯ4 ４４部、アセチレンブラック（ＨＳ−１００）３部、バインダー（ＰＶＤＦ：ポリフッ化ビニリデン）３部、ＮＭＰ５０部を混合して、正極用合材インキ（Ａ）を作製した。
"Creation of positive electrode for lithium ion secondary battery"
<Creation of positive electrode mixture ink>
As a positive electrode active material, 44 parts of LiFePO 4 , 3 parts of acetylene black (HS-100), 3 parts of a binder (PVDF: polyvinylidene fluoride) and 50 parts of NMP were mixed to prepare a positive electrode mixture ink (A).
正極用合材インキ（Ａ）の原料を表３に記載した素材および配合部に変更した以外は、正極用合材インキ（Ａ）の作成と同様に行なうことで正極用合材インキ（Ｂ）および（Ｃ）、負極用合材インキ（Ｄ）、（Ｅ）および（Ｆ）を作成した。 The positive electrode mixture ink (B) is the same as the preparation of the positive electrode mixture ink (A) except that the raw material of the positive electrode mixture ink (A) is changed to the materials and blending parts shown in Table 3. And (C), composite inks for negative electrode (D), (E) and (F) were prepared.
表３の原料は以下の通りである。
人造黒鉛：ＳＣＭＧ（昭和電工社製）
The raw materials in Table 3 are as follows.
Artificial graphite: SCMG (Showa Denko)
＜分離膜用樹脂組成物の作成＞
無機粒子（アルミナ、平均一次粒子径０．５μｍ）１００部と、合成例１で得たバインダー樹脂分散液を不揮発分換算で３部とを混合し、さらに水、高分子型分散剤、レベリング剤を加えて不揮発分が２０％になるように調整した上で混合した。次いでビーズミルに投入し分散することで分離膜用樹脂組成物（Ｇ）を得た。
<Preparation of resin composition for separation membrane>
100 parts of inorganic particles (alumina, average primary particle size 0.5 μm) and 3 parts of the binder resin dispersion obtained in Synthesis Example 1 in terms of non-volatile content are mixed, and further water, a polymeric dispersant, and a leveling agent are mixed. Was added to adjust the non-volatile content to 20% and mixed. Subsequently, the resin composition for separation membranes (G) was obtained by throwing into a bead mill and dispersing.
＜正極の作成＞
得られた正極用合材インキ（Ａ）を、下地層付き集電体（１）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥して電極全体の厚みが１００μｍとなるよう調整した。さらに、ロールプレスによる圧延処理を行い、厚みが８５μｍの正極１を作製した。
<Creation of positive electrode>
The obtained positive electrode mixture ink (A) was applied onto the current collector (1) with an underlayer using a doctor blade, and then heated and dried under reduced pressure to adjust the thickness of the entire electrode to 100 μm. . Furthermore, the rolling process by a roll press was performed and the positive electrode 1 with a thickness of 85 micrometers was produced.
正極１の正極用合材インキ（Ａ）および下地層付き集電体（１）を表４に記載した部材に置き換えた以外は、正極１と同様に行なうことで正極２〜１５を作成した。 The positive electrodes 2 to 15 were prepared in the same manner as the positive electrode 1 except that the positive electrode mixture ink (A) and the current collector with base layer (1) of the positive electrode 1 were replaced with the members described in Table 4.
＜対極（正極）の作成＞
評価用負極の対極（正極）を以下の通り作成した。得られた正極用合材インキ（Ａ）を、集電体となる厚さ２０μｍのアルミ箔上にドクターブレードを用いて塗布した後、減圧下加熱乾燥して電極の厚みが１００μｍとなるよう調整した。さらに、ロールプレスによる圧延処理を行い、厚みが８５μｍの正極を作製した。なお前記正極を比較例１の評価用電極として使用した。
<Creation of counter electrode (positive electrode)>
A counter electrode (positive electrode) of the negative electrode for evaluation was prepared as follows. The obtained mixture ink for positive electrode (A) was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, and then heated and dried under reduced pressure to adjust the electrode thickness to 100 μm. did. Furthermore, the rolling process by a roll press was performed and the positive electrode with a thickness of 85 micrometers was produced. The positive electrode was used as an evaluation electrode of Comparative Example 1.
＜負極の作成＞
得られた負極用合材インキ（Ｄ）を、下地層付き集電体（１１）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥して電極の厚みが８２μｍとなるよう調整した。ロールプレスによる圧延処理を行い、厚みが７０μｍの負極１を作製した
<Creation of negative electrode>
The obtained negative electrode mixture ink (D) was applied onto a current collector (11) with an underlayer using a doctor blade, and then heated and dried under reduced pressure to adjust the electrode thickness to 82 μm. A negative electrode 1 having a thickness of 70 μm was produced by rolling using a roll press.
負極１の負極用合材インキ（Ｄ）および下地層付き集電体（１１）を表４に記載した部材に置き換えた以外は、負極１と同様に行なうことで負極２〜５を作成した。 Negative electrodes 2 to 5 were prepared in the same manner as in the negative electrode 1 except that the negative electrode mixture ink (D) and the current collector with base layer (11) of the negative electrode 1 were replaced with the members described in Table 4.
＜対極（負極）の作成＞
評価用正極の対極（負極）を以下の通り作成した。得られた負極用合材インキ（Ｄ）を、集電体（厚さ２０μｍの銅箔）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥して電極全体の厚みが８２μｍとなるよう調整した。さらに、ロールプレスによる圧延処理を行い、厚みが７０μｍの負極を作製した。なお、前記負極を比較例６の評価用電極として使用した。
<Creation of counter electrode (negative electrode)>
A counter electrode (negative electrode) of the positive electrode for evaluation was prepared as follows. The obtained mixture ink for negative electrode (D) was applied on a current collector (copper foil having a thickness of 20 μm) using a doctor blade, and then dried by heating under reduced pressure so that the thickness of the entire electrode became 82 μm. It was adjusted. Furthermore, the rolling process by a roll press was performed and the negative electrode with a thickness of 70 micrometers was produced. The negative electrode was used as an evaluation electrode of Comparative Example 6.
＜保護層付き分離膜の作成＞
得られた分離膜用樹脂組成物（Ｇ）をドクターブレードを用いて乾燥後の厚みが５μｍになるように厚さ１０μｍの多孔質ポリプロピレンフィルムの片面に塗布することで保護層（Ｇ）を形成し、次いで減圧下で加熱乾燥を行い保護層付き分離膜を得た。
<Creation of separation membrane with protective layer>
A protective layer (G) is formed by applying the obtained resin composition for separation membrane (G) to one side of a 10 μm-thick porous polypropylene film using a doctor blade so that the thickness after drying becomes 5 μm. Then, it was heated and dried under reduced pressure to obtain a separation membrane with a protective layer.
[実施例１]
正極１を直径１６ｍｍに打ち抜き、同様に対極（負極）も直径１６ｍｍに打ち抜いた。得られた両電極と、分離膜（厚さ１０μｍの多孔質ポリプロピレンフィルム）と、電解液（エチレンカーボネートとジエチルカーボネートを１：１（体積比）の割合で混合した混合溶媒にＬｉＰＦ6を１Ｍの濃度で溶解した。）とを使用してアルゴンガス置換したグロ−ブボックス内でコイン型リチウムイオン二次電池を作製した。
[Example 1]
The positive electrode 1 was punched to a diameter of 16 mm, and similarly the counter electrode (negative electrode) was punched to a diameter of 16 mm. Both electrodes obtained, a separation membrane (a porous polypropylene film having a thickness of 10 μm), and an electrolyte (a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio)) were mixed with 1M LiPF 6 . A coin-type lithium ion secondary battery was produced in a glove box substituted with argon gas.
[実施例２〜１３、比較例１〜８]
実施例１で使用した正極、負極および分離膜を表４に記載した部材に置き換えた以外は、実施例１と同様に行なうことで実施例２〜１３および比較例１〜８のコイン型リチウムイオン二次電池を作製した。
[Examples 2 to 13, Comparative Examples 1 to 8]
The coin-type lithium ions of Examples 2 to 13 and Comparative Examples 1 to 8 were obtained in the same manner as in Example 1 except that the positive electrode, negative electrode, and separation membrane used in Example 1 were replaced with the members described in Table 4. A secondary battery was produced.
（密着性）
リチウムイオン二次電池の評価用電極ついて、合材層と集電体(下地層)との密着性を評価した。まずにナイフを用いて合材層表面から集電体に達する深さまでの切込み（ハーフカット）を２ｍｍ間隔で縦方向に６本、および横方向に６本の切込みを碁盤の目状に入れた（計３６個の正方形の枡が形成した）。この切込み部に市販のセロハンテープを貼り付けて、直ちに引き剥がすことで被膜の脱落を目視で評価した。評価基準を以下に示す。
◎：「被膜の脱落がない（良好）」
○：「被膜の枡のうち５個以下が脱落した（実用可）」
△：「被膜の枡のうち６個以上３０個未満が脱落した（実用不可）」
×：「被膜の枡のうち３０個以上が脱落した（不良）」
(Adhesion)
Regarding the electrode for evaluation of the lithium ion secondary battery, the adhesion between the composite material layer and the current collector (underlayer) was evaluated. First, using a knife, incisions (half cuts) from the surface of the composite material layer to the depth reaching the current collector were made in a grid pattern with 6 incisions in the vertical direction and 6 in the lateral direction at intervals of 2 mm. (A total of 36 square folds formed). A commercially available cellophane tape was affixed to the cut portion, and the film was peeled off immediately to visually evaluate the falling of the coating. Evaluation criteria are shown below.
A: “No drop off of coating (good)”
○: “Five or less of the wrinkles of the coating have fallen off (practical)”
Δ: “6 or more and less than 30 of the coating folds have fallen off (unusable)”
X: “30 or more of the wrinkles of the film have fallen off (defect)”
（充放電サイクル特性）
得られたリチウムイオン二次電池について、充放電装置（北斗電工社製ＳＭ−８）を用い、充放電測定を行った。
充電電流１．０ｍＡ（０．２Ｃ）にて充電終止電圧４．０Ｖで定電流定電圧充電（カットオフ電流０．１ｍＡ）を行った後、放電電流１．０ｍＡで放電終止電圧２．０Ｖに達するまで定電流放電を行った。これらの充電・放電サイクルを１サイクルとして５サイクルの充電・放電を繰り返し、５サイクル目の放電容量を初回放電容量とした。（初回放電容量を維持率１００％とする）。
次に、５０℃恒温槽にて充電電流５．０ｍＡにて充電終止電圧４．０Ｖで定電流定電圧充電（カットオフ電流０．５ｍＡ）を行った後、放電電流５．０ｍＡで放電終止電圧２．０Ｖに達するまで定電流放電を行った。この充放電サイクルを２００回行い放電容量維持率の変化率を算出した（１００％に近いほど良好）。
◎：「変化率が９０％以上。優れている。」
○：「変化率が８５％以上、９０％未満。良好。」
△：「変化率が８０％以上、８５％未満。実用上問題なし。」
×：「変化率が８０％未満。実用上問題あり、使用不可。」
(Charge / discharge cycle characteristics)
About the obtained lithium ion secondary battery, charging / discharging measurement was performed using the charging / discharging apparatus (Hokuto Denko SM-8).
After performing a constant current and constant voltage charge (cutoff current 0.1 mA) at a charge end voltage of 4.0 V at a charge current of 1.0 mA (0.2 C), the discharge end voltage is 2.0 V at a discharge current of 1.0 mA. The constant current discharge was performed until it reached. These charge / discharge cycles are defined as one cycle, and 5 cycles of charge / discharge are repeated, and the discharge capacity at the fifth cycle is defined as the initial discharge capacity. (The initial discharge capacity is assumed to be 100% maintenance rate).
Next, after performing constant current and constant voltage charging (cutoff current 0.5 mA) at a charging current 5.0 mA at a charging current 5.0 mA in a 50 ° C. constant temperature bath, a discharge final voltage is discharged at a discharge current 5.0 mA. Constant current discharge was performed until 2.0V was reached. This charge / discharge cycle was repeated 200 times, and the rate of change of the discharge capacity retention rate was calculated (the closer to 100%, the better).
A: “Change rate is 90% or more. Excellent”
○: “Change rate is 85% or more and less than 90%. Good”.
Δ: “Change rate is 80% or more and less than 85%. No problem in practical use.”
X: “Change rate is less than 80%.
「電気二重層キャパシターの作成」
＜合材インキの作成＞
活物質として活性炭（比表面積１８００ｍ2／ｇ）８８部、導電助剤（アセチレンブラック ＨＳ−１００）５部、バインダー（ＰＶＤＦ）７部、ＮＭＰ（Ｎ−メチルピロリドン）２３０部を混合して、合材インキ（Ｈ）を作製した。なお合材インキ（Ｈ）は、正極および負極に使用できる。
"Creation of electric double layer capacitor"
<Creation of composite ink>
As active materials, 88 parts of activated carbon (specific surface area 1800 m 2 / g), 5 parts of conductive auxiliary agent (acetylene black HS-100), 7 parts of binder (PVDF), 230 parts of NMP (N-methylpyrrolidone) are mixed together. Material ink (H) was produced. The mixed material ink (H) can be used for the positive electrode and the negative electrode.
＜正極および負極の作成＞
得られた合材インキ（Ｈ）を下地層付き集電体（１）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥した後に、ロールプレスによる圧延処理を行い、電極全体の厚みが５０μｍの正極（１６）を作製した。
<Creation of positive electrode and negative electrode>
After applying the obtained composite ink (H) on the current collector (1) with the underlayer using a doctor blade, heating and drying under reduced pressure, and then performing a rolling process by a roll press, the thickness of the entire electrode is A 50 μm positive electrode (16) was produced.
正極（１６）の下地層付き集電体（１）を表５に記載した部材に置き換えた以外は、正極（１６）の作製と同様に行なうことで、正極１７〜２３および負極６〜９を作製した。なお、正極２１および負極８の集電体は、厚さ２０μｍのアルミ箔を使用し、電極全体の厚みを５０μｍとした以外は正極１６の作製と同様に行なった。 The positive electrodes 17 to 23 and the negative electrodes 6 to 9 were formed in the same manner as the production of the positive electrode (16) except that the collector (1) with the underlayer of the positive electrode (16) was replaced with the members described in Table 5. Produced. The current collectors of the positive electrode 21 and the negative electrode 8 were the same as the production of the positive electrode 16 except that an aluminum foil having a thickness of 20 μm was used and the thickness of the entire electrode was 50 μm.
＜対極（正極）および対極（負極）の作成＞
得られた合材インキ（Ｈ）を、集電体となる厚さ２０μｍのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥した後にロールプレスによる圧延処理を行い、電極の厚みが５０μｍの正極を作製した。なお前記正極は、対極（負極）としても使用した。
<Creation of counter electrode (positive electrode) and counter electrode (negative electrode)>
The obtained composite ink (H) was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, dried by heating under reduced pressure, and then subjected to a rolling process using a roll press, so that the thickness of the electrode was A 50 μm positive electrode was produced. The positive electrode was also used as a counter electrode (negative electrode).
[実施例１４]
正極１６を直径１６ｍｍに打ち抜き、対極の負極も同様に直径１６ｍｍに打ち抜いた。次いで分離膜（厚さ１０μｍの多孔質ポリプロピレンフィルム）と、電解液（プロピレンカーボネート溶媒に（ＴＥＭＡＢＦ4（四フッ化ホウ素トリエチルメチルアンモニウム）を１Ｍの濃度で溶解させた非水系電解液）とを使用してアルゴンガス置換したグロ−ブボックス内でコイン型の電気二重層キャパシターを作製した。
[Example 14]
The positive electrode 16 was punched to a diameter of 16 mm, and the counter electrode negative electrode was similarly punched to a diameter of 16 mm. Next, a separation membrane (a porous polypropylene film having a thickness of 10 μm) and an electrolytic solution (a nonaqueous electrolytic solution in which (TEMABF 4 (boron trifluoride triethylmethylammonium) is dissolved at a concentration of 1 M) in a propylene carbonate solvent) are used. Then, a coin-type electric double layer capacitor was produced in a glove box substituted with argon gas.
[実施例１５〜２０、比較例９〜１３]
実施例１４で使用した正極１６および対極の負極を表５に記載された部材に置き換えた以外は、実施例１４と同様に行なうことでそれぞれ実施例１５〜２０、および比較例９〜１３の電気二重層キャパシターを作製した。
[Examples 15 to 20, Comparative Examples 9 to 13]
Except that the positive electrode 16 and the negative electrode of the counter electrode used in Example 14 were replaced with the members described in Table 5, the same operations as in Example 14 were carried out, so that the electricity of Examples 15 to 20 and Comparative Examples 9 to 13 were respectively obtained. A double layer capacitor was fabricated.
（密着性）
得られた電気二重層キャパシターの評価用電極についてリチウムイオン二次電池と同様の方法で密着性を評価した。
(Adhesion)
The adhesion of the obtained electrode for evaluation of the electric double layer capacitor was evaluated in the same manner as the lithium ion secondary battery.
（充放電サイクル特性）
得られた電気二重層キャパシターについて、充放電装置を用い、以下の通り充放電測定を行った。
(Charge / discharge cycle characteristics)
About the obtained electric double layer capacitor, the charging / discharging measurement was performed as follows using the charging / discharging apparatus.
充電電流１０Ｃレートにて充電終止電圧２．０Ｖまで充電を行った後、放電電流１０Ｃレートで放電終止電圧０Ｖに達するまで定電流放電を行った。これらの充電・放電サイクルを１サイクルとして５サイクルの充電・放電を繰り返し、５サイクル目の放電容量を初回放電容量とした。（初回放電容量を維持率１００％とする）。また、充放電電流レートは、セル容量を１時間で放電出来る電流の大きさを１Ｃとした。 After charging to a charge end voltage of 2.0 V at a charge current of 10 C, constant current discharge was performed until the discharge end voltage of 0 V was reached at a discharge current of 10 C. These charge / discharge cycles are defined as one cycle, and 5 cycles of charge / discharge are repeated, and the discharge capacity at the fifth cycle is defined as the initial discharge capacity. (The initial discharge capacity is assumed to be 100% maintenance rate). In addition, the charge / discharge current rate was 1 C, which is the magnitude of current that can discharge the cell capacity in one hour.
次に、５０℃恒温槽にて充電電流１０Ｃレートにて充電終止電圧２．０Ｖで充電を行った後、放電電流１０Ｃレートで放電終止電圧０Ｖに達するまで定電流放電を行った。この充放電サイクルを５００回行い放電容量維持率の変化率を算出した（１００％に近いほど良好）。なお評価基準は、リチウムイオン二次電池の場合と同様である。 Next, charging was performed at a charging current 10C rate in a 50 ° C. constant temperature bath at a charging end voltage of 2.0 V, and then constant current discharging was performed at a discharging current of 10 C rate until reaching a discharging end voltage of 0 V. This charge / discharge cycle was repeated 500 times to calculate the rate of change of the discharge capacity maintenance rate (the closer to 100%, the better). The evaluation criteria are the same as in the case of the lithium ion secondary battery.
「リチウムイオンキャパシターの作成」
＜正極の作成＞
合材インキ（Ｈ）を下地層付き集電体（１）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥してロールプレスによる圧延処理を行った後、厚みが６０μｍの正極２４を作製した。
"Creation of lithium ion capacitor"
<Creation of positive electrode>
The mixture ink (H) was applied onto the current collector (1) with the underlayer using a doctor blade, heated and dried under reduced pressure, and rolled by a roll press, and then the positive electrode 24 having a thickness of 60 μm was formed. Produced.
正極２４の下地層付き集電体（１）を表６に記載された部材に置き換えた以外は、正極２４の作製と同様に行なうことで正極２５〜３１を作製した。なお正極２９の集電体は、厚さ２０μｍのアルミ箔を使用した。 The positive electrodes 25 to 31 were produced in the same manner as the production of the positive electrode 24 except that the collector (1) with the underlayer of the positive electrode 24 was replaced with the members described in Table 6. The current collector of the positive electrode 29 was an aluminum foil having a thickness of 20 μm.
＜負極用合材インキの作成＞
負極活物質として黒鉛９０部、導電助剤（アセチレンブラック ＨＳ−１００）５部、バインダー（ＰＶＤＦ）５部、ＮＭＰ２００部を混合して、合材インキ（Ｉ）を作製した。
<Creating ink for negative electrode>
As a negative electrode active material, 90 parts of graphite, 5 parts of conductive additive (acetylene black HS-100), 5 parts of binder (PVDF), and 200 parts of NMP were mixed to prepare a composite ink (I).
＜負極の作成＞
合材インキ（Ｈ）を、下地層付き集電体（９）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥してロールプレスによる圧延処理を行った後、厚みが４５μｍの負極１０を作製した。
<Creation of negative electrode>
The composite ink (H) was applied onto the current collector with an underlayer (9) using a doctor blade, dried by heating under reduced pressure and rolled by a roll press, and then the negative electrode 10 having a thickness of 45 μm. Was made.
負極１０の下地層付き集電体（９）を表６に記載された部材に置き換えた以外は、負極１０の作製と同様に行なうことで負極１１および１３をそれぞれ作製した。 Negative electrodes 11 and 13 were produced in the same manner as in the production of the negative electrode 10 except that the current collector with the underlayer (9) of the negative electrode 10 was replaced with the members described in Table 6.
＜対極(負極)の作成＞
合材インキ（Ｉ）を集電体（厚さ２０μｍの銅箔）上にドクターブレードを用いて塗布した後、減圧下加熱乾燥してロールプレスによる圧延処理を行った後、負極全体の厚みが４５μｍの対極（負極）を作製した。なお、前記負極は、比較例１７の評価用電極（負極１２）として使用した。
<Creation of counter electrode (negative electrode)>
The mixture ink (I) was applied onto a current collector (copper foil having a thickness of 20 μm) using a doctor blade, then heated and dried under reduced pressure, and subjected to a rolling process using a roll press. A 45 μm counter electrode (negative electrode) was prepared. The negative electrode was used as an evaluation electrode (negative electrode 12) of Comparative Example 17.
＜対極(正極)の作成＞
得られた合材インキ（Ｈ）を、集電体となる厚さ２０μｍのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥した後にロールプレスによる圧延処理を行い、電極の厚みが６０μｍの正極を作製した。
<Creation of counter electrode (positive electrode)>
The obtained composite ink (H) was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, dried by heating under reduced pressure, and then subjected to a rolling process using a roll press, so that the thickness of the electrode was A positive electrode of 60 μm was produced.
[実施例２１]
正極２４を直径１６ｍｍの大きさに打ち抜いた。また、対極の負極にリチウムイオンをハーフドープ処理を行なった後、直径１６ｍｍの大きさに打ち抜いた。両電極と、分離膜（厚さ１０μｍの多孔質ポリプロピレンフィルム）と、電解液（エチレンカーボネートとジメチルカーボネートとジエチルカーボネートを１：１：１（体積比）の割合で混合した混合溶媒にＬｉＰＦ6を１Ｍの濃度で溶解させた非水系電解液）とをアルゴンガス置換したグロ−ブボックス内でリチウムイオンキャパシターを作製した。なお前記ハーフドープ処理は、ビーカーセル中で負極とリチウム金属の間に分離膜を挟み、負極容量の約半分の量となるようリチウムイオンを負極にドープして行った。
[Example 21]
The positive electrode 24 was punched into a diameter of 16 mm. The negative electrode of the counter electrode was half-doped with lithium ions and then punched out to a diameter of 16 mm. LiPF 6 was mixed into a mixed solvent in which both electrodes, a separation membrane (a porous polypropylene film having a thickness of 10 μm), and an electrolytic solution (ethylene carbonate, dimethyl carbonate, and diethyl carbonate were mixed at a ratio of 1: 1: 1 (volume ratio)). A lithium ion capacitor was produced in a glove box in which argon gas was replaced with a non-aqueous electrolyte solution dissolved at a concentration of 1M. The half-doping treatment was performed by interposing a separation membrane between the negative electrode and lithium metal in a beaker cell and doping the negative electrode with lithium ions so as to be about half the negative electrode capacity.
［実施例２２〜２７、比較例１４〜１８］
実施例２１の正極および対極（負極）を表６に記載された部材に置き換えた以外を実施例２１と同様に行なうことでそれぞれ実施例２２〜２７、および比較例１４〜１８のリチウムイオンキャパシターを作製した。
[Examples 22 to 27, Comparative Examples 14 to 18]
The lithium ion capacitors of Examples 22 to 27 and Comparative Examples 14 to 18 were obtained in the same manner as in Example 21 except that the positive electrode and counter electrode (negative electrode) in Example 21 were replaced with the members described in Table 6. Produced.
（密着性）
得られたリチウムイオンキャパシターの評価用電極についてリチウムイオン二次電池と同様の方法で密着性を評価した。
(Adhesion)
The adhesion of the obtained evaluation electrode for the lithium ion capacitor was evaluated in the same manner as the lithium ion secondary battery.
（充放電サイクル特性）
得られたリチウムイオンキャパシターについて、充放電装置を用い、以下の通り充放電測定を行った。
充電電流１０Ｃレートにて充電終止電圧４．０Ｖまで充電を行った後、放電電流１０Ｃレートで放電終止電圧２．０Ｖに達するまで定電流放電を行った。これらの充電・放電サイクルを１サイクルとして５サイクルの充電・放電を繰り返し、５サイクル目の放電容量を初回放電容量とした。（初回放電容量を維持率１００％とする）。
(Charge / discharge cycle characteristics)
About the obtained lithium ion capacitor, the charging / discharging measurement was performed as follows using the charging / discharging apparatus.
After charging to a charge end voltage of 4.0 V at a charge current of 10 C, constant current discharge was performed until the discharge end voltage of 2.0 V was reached at a discharge current of 10 C. These charge / discharge cycles are defined as one cycle, and 5 cycles of charge / discharge are repeated, and the discharge capacity at the fifth cycle is defined as the initial discharge capacity. (The initial discharge capacity is assumed to be 100% maintenance rate).
次に、５０℃恒温槽にて充電電流１０Ｃレートにて充電終止電圧４．０Ｖで充電を行った後、放電電流１０Ｃレートで放電終止電圧２．０Ｖに達するまで定電流放電を行った。この充放電サイクルを５００回行い放電容量維持率の変化率を算出した（１００％に近いほど良好）。なお評価基準は、リチウムイオン二次電池の場合と同様である。 Next, after charging at a charging end voltage of 4.0 V at a charging current of 10 C in a constant temperature bath at 50 ° C., constant current discharging was performed until the discharging end voltage of 2.0 V was reached at a discharge current of 10 C. This charge / discharge cycle was repeated 500 times to calculate the rate of change of the discharge capacity maintenance rate (the closer to 100%, the better). The evaluation criteria are the same as in the case of the lithium ion secondary battery.
表２の結果から、本発明の蓄電デバイス用樹脂から形成された下地層は、耐溶剤性が優れている。
表４〜６の結果から、本発明の蓄電デバイス用樹脂から形成された下地層を用いた場合、下地層上へ合材インキを塗工して正極、あるいは負極を作製した場合に不具合を生じることなく、電極の密着性を大幅に改善することが出来た。さらに、本発明の蓄電デバイス用樹脂は、導電材料を良好に分散できるため導電性が向上することで二次電池、およびキャパシターの充放電サイクル特性を向上できた。
一方、電極の密着性が不十分な場合、電池やキャパシターの長期耐久性を維持することが困難であるために劣化を引き起こしてしまう。比較例１のように導電材料の分散が不良の場合、電極の密着性が不十分な傾向が見られており、充放電サイクル特性の劣化が顕著に見られている。
From the results in Table 2, the foundation layer formed from the resin for an electricity storage device of the present invention has excellent solvent resistance.
From the results shown in Tables 4 to 6, when the base layer formed from the resin for an electricity storage device of the present invention is used, a problem occurs when a mixture ink is applied onto the base layer to produce a positive electrode or a negative electrode. The electrode adhesion was greatly improved. Furthermore, since the resin for an electricity storage device of the present invention can disperse the conductive material satisfactorily, the chargeability / discharge cycle characteristics of the secondary battery and the capacitor can be improved by improving the conductivity.
On the other hand, when the adhesion of the electrodes is insufficient, it is difficult to maintain the long-term durability of the battery or the capacitor, thereby causing deterioration. When the dispersion of the conductive material is poor as in Comparative Example 1, the electrode adhesion tends to be insufficient, and the charge / discharge cycle characteristics are significantly deteriorated.
Claims (7)
前記架橋性モノマー（ｂ２）が、二重結合を２つ以上有するモノマーおよびアルコキシシリル基含有モノマーの少なくともいずれかである、蓄電デバイス用樹脂。 Carboxyl group-containing monomer (b1): 5 to 50% by weight, crosslinkable monomer (b2): 0.1 to 5% by weight, other monomer (b3): 45 to 94.9% by weight (provided that (b1) above) To (b3) is 100% by weight)
A resin for an electricity storage device, wherein the crosslinkable monomer (b2) is at least one of a monomer having two or more double bonds and an alkoxysilyl group-containing monomer.
前記導電材料がカーボンブラックおよび黒鉛粒子の少なくともいずれかである蓄電デバイス電極用樹脂組成物。 A resin composition for an electricity storage device electrode comprising the resin for an electricity storage device according to claim 1 and a conductive material, wherein the conductive material is at least one of carbon black and graphite particles.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016171028A1 (en) * | 2015-04-22 | 2016-10-27 | 東亞合成株式会社 | Binder for nonaqueous electrolyte secondary battery electrodes and use of same |
| JP2018044111A (en) * | 2016-09-16 | 2018-03-22 | 富士フイルム株式会社 | Polymer, solid electrolyte, solid electrolyte composition, inorganic solid electrolyte composition, solid electrolyte-containing sheet, secondary battery, total solid secondary battery, method for producing solid electrolyte-containing sheet, method for producing inorganic solid electrolyte-containing sheet, method for producing secondary battery and method for producing total solid secondary battery |
| JP2018166071A (en) * | 2017-03-28 | 2018-10-25 | Tdk株式会社 | Lithium secondary battery |
| WO2021177291A1 (en) * | 2020-03-04 | 2021-09-10 | 国立大学法人 東京大学 | Secondary battery electrode additive |
| WO2022131253A1 (en) * | 2020-12-15 | 2022-06-23 | 旭化成株式会社 | Non-aqueous secondary battery polymer composition and non-aqueous secondary battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011000832A (en) * | 2009-06-19 | 2011-01-06 | Asahi Kasei E-Materials Corp | Multilayered porous film |
| WO2012133030A1 (en) * | 2011-03-31 | 2012-10-04 | 東洋インキＳｃホールディングス株式会社 | Aqueous composition for forming secondary battery electrode, secondary battery electrode, and secondary battery |
-
2014
- 2014-06-06 JP JP2014117993A patent/JP2015230884A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011000832A (en) * | 2009-06-19 | 2011-01-06 | Asahi Kasei E-Materials Corp | Multilayered porous film |
| WO2012133030A1 (en) * | 2011-03-31 | 2012-10-04 | 東洋インキＳｃホールディングス株式会社 | Aqueous composition for forming secondary battery electrode, secondary battery electrode, and secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016171028A1 (en) * | 2015-04-22 | 2016-10-27 | 東亞合成株式会社 | Binder for nonaqueous electrolyte secondary battery electrodes and use of same |
| JPWO2016171028A1 (en) * | 2015-04-22 | 2018-02-08 | 東亞合成株式会社 | Nonaqueous electrolyte secondary battery electrode binder and use thereof |
| JP2018044111A (en) * | 2016-09-16 | 2018-03-22 | 富士フイルム株式会社 | Polymer, solid electrolyte, solid electrolyte composition, inorganic solid electrolyte composition, solid electrolyte-containing sheet, secondary battery, total solid secondary battery, method for producing solid electrolyte-containing sheet, method for producing inorganic solid electrolyte-containing sheet, method for producing secondary battery and method for producing total solid secondary battery |
| JP2018166071A (en) * | 2017-03-28 | 2018-10-25 | Tdk株式会社 | Lithium secondary battery |
| WO2021177291A1 (en) * | 2020-03-04 | 2021-09-10 | 国立大学法人 東京大学 | Secondary battery electrode additive |
| WO2022131253A1 (en) * | 2020-12-15 | 2022-06-23 | 旭化成株式会社 | Non-aqueous secondary battery polymer composition and non-aqueous secondary battery |
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