WO2014192645A1 - アルミニウム多孔体の製造方法、アルミニウム多孔体、集電体、電極、及び電気化学デバイス - Google Patents
アルミニウム多孔体の製造方法、アルミニウム多孔体、集電体、電極、及び電気化学デバイス Download PDFInfo
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- WO2014192645A1 WO2014192645A1 PCT/JP2014/063652 JP2014063652W WO2014192645A1 WO 2014192645 A1 WO2014192645 A1 WO 2014192645A1 JP 2014063652 W JP2014063652 W JP 2014063652W WO 2014192645 A1 WO2014192645 A1 WO 2014192645A1
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- Prior art keywords
- aluminum
- electrode
- resin
- porous
- resin structure
- Prior art date
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 196
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 132
- 239000011347 resin Substances 0.000 claims abstract description 132
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 82
- 238000000034 method Methods 0.000 description 57
- 239000003990 capacitor Substances 0.000 description 40
- 229910052744 lithium Inorganic materials 0.000 description 39
- 238000000576 coating method Methods 0.000 description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 29
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- 239000011230 binding agent Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- -1 nickel metal hydride Chemical class 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 20
- 238000007747 plating Methods 0.000 description 20
- 239000007784 solid electrolyte Substances 0.000 description 19
- 238000011049 filling Methods 0.000 description 17
- 239000011255 nonaqueous electrolyte Substances 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000002482 conductive additive Substances 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003273 ketjen black Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910000528 Na alloy Inorganic materials 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000004693 imidazolium salts Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000000230 xanthan gum Substances 0.000 description 4
- 229920001285 xanthan gum Polymers 0.000 description 4
- 229940082509 xanthan gum Drugs 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
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- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007610 electrostatic coating method Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
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- 238000005443 coulometric titration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
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- ALMAEWAETUQTEP-UHFFFAOYSA-N sodium;chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Cr+3] ALMAEWAETUQTEP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- UYYXEZMYUOVMPT-UHFFFAOYSA-J 1-ethyl-3-methylimidazol-3-ium;tetrachloroalumanuide Chemical compound [Cl-].Cl[Al](Cl)Cl.CCN1C=C[N+](C)=C1 UYYXEZMYUOVMPT-UHFFFAOYSA-J 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910013574 LiCo0.3Ni0.7O2 Inorganic materials 0.000 description 1
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013302 LiMS Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 229910052786 argon Inorganic materials 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 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
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
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- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0469—Electroforming a self-supporting electrode; Electroforming of powdered electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a method for producing a porous aluminum body having a three-dimensional network structure, an aluminum porous body, a current collector, an electrode, and an electrochemical device.
- Metal porous bodies having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes.
- Celmet manufactured by Sumitomo Electric Industries, Ltd .: registered trademark
- nickel porous body is an electrode material for batteries such as nickel metal hydride batteries and nickel cadmium batteries. It is used as Celmet is a metal porous body having continuous air holes, and has a feature of high porosity (90% or more) compared to other porous bodies such as a metal nonwoven fabric.
- Such a nickel porous body is obtained by forming a nickel layer on the surface of a porous resin skeleton having continuous vents such as foamed urethane, then heat-treating it to decompose the foamed resin molded body, and further reducing the nickel. It is done.
- the formation of the nickel layer is performed by depositing nickel by electroplating after applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment.
- aluminum In addition to nickel, aluminum also has excellent characteristics such as conductivity, corrosion resistance, and light weight.
- a positive electrode of a lithium ion battery is coated with an active material such as lithium cobalt oxide on the surface of an aluminum foil. Is used.
- Patent Document 1 has an internal communication space as a method for producing a porous aluminum body having a three-dimensional network structure with a large aluminum surface area (hereinafter referred to as “aluminum porous body”). A method is described in which a metal aluminum layer having a thickness of 2 to 20 ⁇ m is formed by subjecting a three-dimensional network plastic substrate to an aluminum vapor deposition process by an arc ion plating method.
- Patent Document 2 discloses a film made of a metal (such as copper) that forms a eutectic alloy below the melting point of aluminum on the skeleton of a foamed resin molding having a three-dimensional network structure. After forming, an aluminum paste is applied, and heat treatment is performed at a temperature of 550 ° C. or higher and 750 ° C. or lower in a non-oxidizing atmosphere to eliminate the organic component (foamed resin) and to sinter the aluminum powder. Is described.
- a metal such as copper
- JP 2011-225950 A (Patent Document 3) describes a method of performing aluminum plating on a foamed resin molded body having a three-dimensional network structure. According to the method described in Patent Document 3, it is possible to uniformly plate high-purity aluminum on a porous resin molded body having a three-dimensional network structure, and to produce a high-quality aluminum porous body Can do.
- an aluminum porous body having a thickness of 2 to 20 ⁇ m is obtained.
- it is a production method by a vapor phase method, it is difficult to produce a large area, and it is difficult to form a uniform layer up to the inside depending on the thickness and porosity of the substrate.
- problems such as a slow formation rate of the aluminum layer and an increase in manufacturing cost due to expensive equipment.
- a thick film is formed, there is a risk that the film may crack or aluminum may fall off.
- An electrochemical device using a non-aqueous electrolyte such as the above-described lithium ion battery or capacitor needs to be manufactured in an environment where moisture is sufficiently removed. Therefore, it is necessary to sufficiently dry the current collector used as the electrode.
- the aluminum porous body described in Patent Document 3 adsorbs a relatively large amount of moisture on the surface of the skeleton, and it is necessary to perform a sufficient drying process in order to use it as an electrode for the electrochemical device as described above. There is.
- This ⁇ -alumina is also used as a hygroscopic agent and has been studied for its hygroscopic properties (for example, “Kazuro Kawamura, Haruo Endo,“ Hygroscopic properties of boehmite and anhydrous alumina ”, Journal of Ceramic Society of Japan 107 [4] pp 335-338) (1998) ”,“ Yi Haiyue, Sadafumi Isshiki, “On the Transformation of ⁇ -Alumina”, Production Research, Vol. 11, No. 2, pp. 25-29, 1959 ”).
- the present inventors have improved a conventional method for producing a porous aluminum body having a three-dimensional network structure by plating (for example, Japanese Patent Application Laid-Open No. 2011-225950).
- a conventional method for producing a porous aluminum body having a three-dimensional network structure by plating for example, Japanese Patent Application Laid-Open No. 2011-225950.
- a manufacturing method includes (1) a step of manufacturing a resin structure by forming an aluminum film on a surface of a resin base material having a three-dimensional network structure by molten salt electroplating; It is a manufacturing method of the aluminum porous body which has the process of removing a water
- an aluminum film is formed on the surface of a resin base material having a three-dimensional network structure by molten salt electroplating to produce a resin structure.
- a method for producing a porous aluminum body comprising: a step; a step of removing moisture from the resin structure; and a step of heat-treating the resin structure from which the moisture has been removed to remove the substrate.
- the manufacturing method of the said aluminum porous body heat-processes the said resin structure at the temperature of 50 degreeC or more and 300 degrees C or less in the process of removing a water
- the base material is preferably removed by heat-treating the resin structure at a temperature of 370 ° C. or higher and lower than the melting point of aluminum.
- the manufacturing method of the said aluminum porous body WHEREIN In the process of removing a water
- the aluminum porous body production method has a three-dimensional network structure in which the surface of the hollow portion of the skeleton is smooth and the amount of moisture adsorption is small Can be manufactured.
- An aluminum porous body according to an aspect of the present invention is an aluminum porous body obtained by the method for producing an aluminum porous body according to any one of (1) to (3) above.
- the porous aluminum body according to one embodiment of the present invention can be used for an electrode of an electrochemical device, for example.
- the skeleton of the porous aluminum body according to one embodiment of the present invention has a three-dimensional network structure, a large amount of active material can be held in the pores, and the utilization rate of the active material per unit volume can be increased. A high and large capacity electrode can be provided.
- the electrical power collector which concerns on 1 aspect of this invention is the electrical power collector for electrochemical devices which consists of an aluminum porous body as described in said (4).
- the aluminum porous body according to one embodiment of the present invention as a current collector for an electrochemical device, an electrochemical device having a large capacity can be manufactured.
- the porous aluminum body according to one embodiment of the present invention has a small amount of moisture adsorption, when used in an electrochemical device using a non-aqueous electrolyte, the burden on the electrode drying process can be reduced.
- the electrode which concerns on 1 aspect of this invention is an electrode for electrochemical devices which has an active material in the pore part of the aluminum porous body as described in said (4).
- an electrode having a large capacity can be obtained.
- the burden concerning the drying process of an electrode can be reduced.
- the electrochemical device which concerns on 1 aspect of this invention is an electrochemical device using the electrode as described in said (6). Since the electrochemical device according to one embodiment of the present invention uses the electrode according to one embodiment of the present invention, which has a high utilization rate of the active material per unit volume, the capacity can be increased. In addition, in the case of an electrochemical device using a non-aqueous electrolyte, the manufacturing cost can be reduced because the burden required for the electrode drying step is reduced.
- an aluminum film is formed on a surface of a resin base material having a three-dimensional network structure by molten salt electroplating to form a resin structure.
- a resin molded body having a three-dimensional network structure and communication holes is prepared.
- Any resin can be selected as the material of the resin molded body.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a resin molded body having an arbitrary shape can be selected as long as it has continuous pores (communication holes). For example, what has a shape like a nonwoven fabric entangled with a fibrous resin can be used instead of the foamed resin molded body.
- Urethane foam and foamed melamine can be preferably used as foamed resin moldings because they have high porosity, have pore connectivity and are excellent in thermal decomposability. Foamed urethane is preferable in terms of uniformity of pores, availability, and the like, and in addition, a product having a small pore diameter can be obtained.
- the resin molded body has a three-dimensional network structure as a skeleton, continuous pores are formed as a whole.
- the urethane skeleton has a triangular or substantially triangular shape in a cross section perpendicular to the extending direction.
- the foamed resin molded article preferably has a porosity of 80% to 98% and a pore diameter of 50 ⁇ m to 500 ⁇ m.
- Electrode conductive resin molding surface In order to electroplat aluminum on the surface of the resin molded body, the surface of the resin molded body is subjected to a conductive treatment in advance.
- a conductive treatment There is no restriction
- any method such as electroless plating of a conductive metal such as nickel, vapor deposition and sputtering of aluminum or the like, or application of a conductive paint containing conductive particles such as carbon can be selected.
- the conductive treatment As examples of the conductive treatment, a method of conducting the conductive treatment by sputtering of aluminum and a method of conducting the conductive treatment of the surface of the resin molded body using carbon as conductive particles will be described below.
- the sputtering treatment using aluminum is not limited as long as aluminum is the target, and may be performed according to a conventional method. For example, after attaching a resin molded body to a substrate holder, while applying an inert gas, a DC voltage is applied between the holder and a target (aluminum) to cause the ionized inert gas to collide with aluminum. The aluminum particles sputtered off are deposited on the surface of the resin molding to form a sputtered aluminum film.
- the sputtering treatment is preferably performed at a temperature at which the resin molded body does not dissolve. Specifically, the sputtering treatment may be performed at about 100 to 200 ° C., preferably about 120 to 180 ° C.
- a carbon paint as a conductive paint is prepared.
- the suspension as the conductive paint preferably contains carbon particles, a binder, a dispersant and a dispersion medium.
- the suspension In order to uniformly apply the conductive particles, the suspension needs to maintain a uniform suspension state. For this reason, the suspension is preferably maintained at 20 ° C. to 40 ° C. The reason is that when the temperature of the suspension is lower than 20 ° C., the uniform suspension state is lost, and only the binder is concentrated on the surface of the skeleton forming the network structure of the porous resin body to form a layer. Because there are cases. In this case, the applied carbon particle layer is easy to peel off, and it is difficult to form a metal plating that is firmly adhered.
- the particle size of the carbon particles is preferably 0.01 to 5 ⁇ m, more preferably 0.01 to 2 ⁇ m.
- the application of the carbon particles to the resin molded body can be performed by immersing the target resin molded body in the suspension and performing squeezing and drying.
- a plating method using a molten salt bath is employed as a method for forming an aluminum film on the surface of the resin molded body.
- -Molten salt plating- Electrolytic plating is performed in a molten salt to form an aluminum film on the surface of the resin molded body.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and aluminum as an anode.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- electrolytic plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used, and specifically, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable. Since the molten salt deteriorates when moisture or oxygen is mixed in the molten salt, the plating is preferably performed in an atmosphere of an inert gas such as nitrogen or argon and in a sealed environment.
- an inert gas such as nitrogen or argon
- a molten salt bath containing nitrogen is preferable, and among them, an imidazolium salt bath is preferably used.
- an imidazolium salt bath is preferably used.
- the resin dissolves or decomposes in the molten salt faster than the growth of the plating film, and the plating film cannot be formed on the surface of the resin molded body.
- the imidazolium salt bath can be used without affecting the resin even at a relatively low temperature.
- a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- an aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) -based molten salt is used. It is most preferably used because it is highly stable and hardly decomposes. Plating onto foamed urethane resin or foamed melamine resin is possible, and the temperature of the molten salt bath is 10 ° C to 100 ° C, preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate on the entire surface of the resin molded body.
- the manufacturing method of the aluminum porous body which concerns on 1 aspect of this invention has the process of removing a water
- moisture content By removing moisture from the resin structure, moisture is also removed from the surface of the aluminum film, thereby preventing the formation of boehmite by the reaction between aluminum and water.
- the method for producing a porous aluminum body according to one aspect of the present invention prevents the formation of ⁇ -alumina on the surface of the skeleton by suppressing the formation of boehmite that is the cause of the formation of ⁇ -alumina. is there.
- the water removal from the resin structure is preferably performed by heat-treating the resin structure at a temperature of 50 ° C. or higher and 300 ° C. or lower.
- a temperature of 50 ° C. or higher and 300 ° C. or lower By performing the heat treatment at 50 ° C. or higher, moisture can be efficiently removed from the resin structure. Moreover, it can suppress that aluminum and water react by heat-processing at 300 degrees C or less.
- the heat treatment temperature of the resin structure is more preferably 50 ° C. or more and 200 ° C. or less, and further preferably 50 ° C. or more and 150 ° C. or less.
- the heat treatment for heating the resin structure to a temperature range of 50 ° C. or higher and 300 ° C. or lower is performed in a dry atmosphere having a dew point temperature of 0 ° C. or lower. It is preferable to carry out with. Thereby, water can be removed more efficiently.
- the dew point temperature of the atmosphere in the heat treatment is more preferably ⁇ 5 ° C. or lower, and further preferably ⁇ 10 ° C. or lower. Since the dehydration temperature is about ⁇ 30 ° C. and the water removal efficiency is almost saturated, heat treatment may be performed at a dew point temperature of ⁇ 30 ° C. or higher.
- the atmosphere at the time of removing the water is not particularly limited, and can be appropriately selected from the air, a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, and the like.
- the time for removing moisture from the resin structure may be appropriately changed depending on the temperature and the dew point temperature of the atmosphere. For example, when the resin structure is introduced into a furnace heated to 50 ° C. in an atmosphere with a dew point temperature of ⁇ 2 ° C., water can be sufficiently removed in about 30 minutes.
- the resin structure from which moisture has been removed as described above can be further heat-treated to remove the base material to obtain an aluminum porous body.
- the substrate can be removed, for example, by heat-treating the resin structure from which the moisture has been removed at a temperature of 370 ° C. or higher and lower than the melting point of aluminum. As a result, the resin is burned out, and an aluminum porous body having a hollow skeleton can be obtained.
- the resin base material can be burned out efficiently.
- the heat treatment temperature when removing the substrate is more preferably 500 ° C. or more and 660 ° C. or less, and further preferably 580 ° C. or more and 630 ° C. or less. .
- the atmosphere at the time of removing the substrate may be under air or the like, but it is preferably performed in a dry atmosphere in order to suppress the reaction between moisture in the atmosphere and aluminum.
- the dew point temperature when removing the substrate is more preferably ⁇ 5 ° C. or lower, and further preferably ⁇ 10 ° C. or lower.
- the dew point temperature when removing the base material is about -30 ° C., the reaction between moisture in the atmosphere and aluminum can be sufficiently suppressed. Therefore, the dew point temperature should be -30 ° C. or higher to remove the base material. Can be done.
- the atmosphere at the time of removing the said base material is not specifically limited, Air
- the time for removing the substrate from the resin structure from which the moisture has been removed may be appropriately changed according to the heat treatment temperature.
- the substrate can be sufficiently removed in about 20 minutes.
- the resin structure is produced by forming an aluminum film on the surface of the substrate
- the resin is used in an atmosphere having a dew point temperature of 0 ° C. or lower.
- a step of removing moisture from the resin structure and a step of removing the substrate can be performed.
- the dew point temperature of the atmosphere for heat treatment is more preferably ⁇ 5 ° C. or lower. More preferably, it is ⁇ 10 ° C. or lower. Since the dehydration temperature is about ⁇ 30 ° C. and the water removal efficiency is almost saturated, heat treatment may be performed at a dew point temperature of ⁇ 30 ° C. or higher.
- the heat treatment temperature is preferably 500 ° C. or less, more preferably 480 ° C. or less. preferable.
- porous aluminum body The porous aluminum body according to one embodiment of the present invention obtained as described above is smooth because ⁇ -alumina is not formed on the surface of the skeleton, and thus the porous aluminum body has a very low moisture adsorption amount. .
- the moisture adsorption amount of the porous aluminum body according to one embodiment of the present invention is 30 mg / m 2 or less.
- an aluminum porous body having a moisture adsorption amount of 20 mg / m 2 or less and an aluminum porous body having a content of 15 mg / m 2 or less can be obtained.
- the moisture adsorption amount of the aluminum porous body means the water amount per apparent area of the aluminum porous body after being exposed to an atmosphere having a dew point temperature of ⁇ 20 ° C. for 24 hours.
- the porous aluminum body according to one embodiment of the present invention has a three-dimensional network structure as a skeleton, for example, when the aluminum porous body is used for an electrode of an electrochemical device, the amount of active material retained is increased to a unit volume. The utilization factor of the active material can be increased, and an electrode having a large capacity can be obtained.
- the porous aluminum body according to one embodiment of the present invention has a small amount of moisture adsorption as described above, for example, when used in an environment where moisture is removed, such as a battery using a non-aqueous electrolyte or a capacitor electrode. In addition, it is possible to reduce the burden of the moisture drying and removing process.
- the aluminum porous body according to one embodiment of the present invention is manufactured by a method of plating aluminum on the surface of a resin porous body having a three-dimensional network structure, and the resin base material is subsequently removed.
- the aluminum porous body from which the base material has been removed has a hollow inside of the skeleton, so that the strength of the skeleton is relatively weak. Therefore, for example, when the porous aluminum body is used as an electrode for an electrochemical device, the thickness of the electrode can be easily adjusted because it can be deformed relatively easily after filling the pores with the active material. be able to.
- the porous aluminum body according to one embodiment of the present invention can be used as a current collector for an electrochemical device, and can be used as an electrode for an electrochemical device by filling a pore with an active material. .
- the aluminum porous body according to one embodiment of the present invention has a small amount of moisture adsorption as described above, when it is used for an electrochemical device using a non-aqueous electrolyte, it is dried. The burden on the process can be reduced.
- heat treatment at 150 ° C. and 5 Torr or less for 16 hours or more is required.
- the heat treatment can be performed at 150 ° C. and 5 Torr or less for 2 hours or less.
- Lithium battery A lithium battery will be described as an example of an electrochemical device using the porous aluminum body according to one embodiment of the present invention.
- a lithium battery including a lithium ion secondary battery
- lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), and lithium nickelate (LiNiO 2 ) are used as active materials.
- the active material is used in combination with a conductive additive and a binder.
- the conventional positive electrode material for a lithium battery uses an electrode in which an active material is applied to the surface of an aluminum foil.
- Lithium batteries have higher capacities than nickel metal hydride batteries and capacitors, but there is a need for higher capacities in automobile applications, and the active material coating thickness is set to improve battery capacity per unit area. It is thick.
- the active material is used in a mixture with a conductive additive.
- the porous aluminum body according to one embodiment of the present invention has a high porosity and a large surface area per unit area. Therefore, since the contact area between the current collector and the active material is increased, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive additive can be reduced.
- the above positive electrode material is used as a positive electrode, and a copper or nickel foil, a punching metal, a porous body, or the like is used as a current collector for the negative electrode.
- An alloy system such as Si or Si, or a negative electrode active material such as lithium metal is used.
- a negative electrode active material is also used in combination with a conductive additive and a binder.
- the energy density of the battery can be made higher than that of a lithium battery using a conventional aluminum foil.
- the effect on the secondary battery has been mainly described above.
- the effect of increasing the contact area when the porous aluminum body is filled with the active material is the same as that of the secondary battery in the primary battery. Can be improved.
- FIG. 3 is a longitudinal sectional view of an all-solid lithium battery using a solid electrolyte.
- the all solid lithium battery 60 includes a positive electrode 61, a negative electrode 62, and a solid electrolyte layer (SE layer) 63 disposed between both electrodes.
- the positive electrode 61 includes a positive electrode layer (positive electrode body) 64 and a positive electrode current collector 65
- the negative electrode 62 includes a negative electrode layer 66 and a negative electrode current collector 67.
- a non-aqueous electrolyte described later is used as the electrolyte.
- a separator porous polymer film, nonwoven fabric, paper, etc.
- the non-aqueous electrolyte is impregnated in both electrodes and the separator.
- the aluminum porous body When the aluminum porous body is used for a positive electrode of a lithium battery, a material capable of removing and inserting lithium can be used as an active material. By filling such a material in a porous aluminum body, an electrode suitable for a lithium secondary battery can be obtained.
- the material for the positive electrode active material include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium nickel cobaltate (LiCo 0.3 Ni 0.7 O 2 ), and lithium manganate (LiMn 2 O 4).
- Lithium titanate Li 4 Ti 5 O 12
- lithium manganate compound LiM y Mn 2-y O 4
- M Cr, Co, Ni
- lithium acid or the like
- the active material is used in combination with a conductive additive and a binder.
- examples of other positive electrode active materials include transition metal oxides.
- conventionally used lithium iron phosphate (LiFePO 4 ) and its compounds for example, LiFe 0.5 Mn 0.5 PO 4 ). And olivine compounds.
- the transition metal element contained in these materials may be partially substituted with another transition metal element.
- Still other positive electrode active materials include, for example, TiS 2 , V 2 S 3 , FeS, FeS 2 , LiMS x (M is a transition metal element such as Mo, Ti, Cu, Ni, Fe, or Sb, Sn. , Pb), and metal oxides such as TiO 2 , Cr 3 O 8 , V 2 O 5 , and MnO 2 .
- the above-described lithium titanate ((Li 4 Ti 5 O 12 ) can also be used as a negative electrode active material.
- a polar aprotic organic solvent is used, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and the like are used.
- the supporting salt lithium tetrafluoroborate, lithium hexafluorophosphate, and an imide salt are used.
- concentration of the supporting salt serving as an electrolyte is high, a concentration around 1 mol / L is generally used because there is a limit to dissolution.
- a solid electrolyte may be added and filled.
- the proportion of the active material in the material filled in the aluminum porous body is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of securing the discharge capacity.
- a sulfide-based solid electrolyte having high lithium ion conductivity is preferably used.
- a sulfide-based solid electrolyte having high lithium ion conductivity examples include a sulfide-based solid electrolyte containing lithium, phosphorus, and sulfur. It is done.
- the sulfide solid electrolyte may further contain an element such as O, Al, B, Si, and Ge.
- Such a sulfide-based solid electrolyte can be obtained by a known method.
- lithium sulfide (Li 2 S) and diphosphorus pentasulfide (P 2 S 5 ) are prepared as starting materials, and the ratio of Li 2 S and P 2 S 5 is about 50:50 to 80:20 in molar ratio.
- a method of melting and quenching the mixture melting and quenching method
- a method of mechanically milling the mixture (nocical milling method).
- the sulfide-based solid electrolyte obtained by the above method is amorphous. Although it can be used in this amorphous state, it may be heat-treated to obtain a crystalline sulfide solid electrolyte. Crystallization can be expected to improve lithium ion conductivity.
- a known method such as an immersion filling method or a coating method can be used.
- the coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive or a binder is added as necessary, and an organic solvent or water is mixed with the mixture to prepare a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- the conductive assistant for example, carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT) can be used.
- the binder for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- FIG. 4 is a schematic cross-sectional view showing an example of a capacitor using a capacitor electrode material.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the polarizable electrode 141 is connected to the lead wire 144. All of these are housed in a case 145.
- the aluminum porous body as a current collector, the surface area of the current collector is increased and the contact area with the activated carbon as the active material is increased, so that a capacitor capable of high output and high capacity can be obtained. .
- activated carbon is filled as an active material in an aluminum porous body current collector.
- Activated carbon is used in combination with a conductive aid and a binder.
- the activated carbon is preferably 90% or more in terms of the composition ratio after drying (after removal of the solvent).
- a conductive support agent and a binder are necessary, it is a factor of a capacity
- the conductive assistant is preferably 10% by mass or less, and the binder is preferably 10% by mass or less.
- Activated carbon has a specific surface area of preferably 1000 m 2 / g or more because the larger the surface area, the larger the capacity of the capacitor.
- the activated carbon plant-derived coconut shells, petroleum-based materials, and the like can be used.
- An activated carbon paste can be obtained by mixing and stirring the electrode material mainly composed of activated carbon.
- the activated carbon paste is filled in the current collector, dried, and compressed by a roller press or the like as necessary, thereby improving the density and obtaining a capacitor electrode.
- Coating methods include, for example, roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive and a binder are added as necessary, and an organic solvent and water are mixed therewith to prepare a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- the conductive assistant for example, carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT) can be used.
- the binder for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- the electrodes obtained as described above are punched out to a suitable size, and are opposed to each other with a separator interposed therebetween.
- the separator is preferably a porous film or a non-woven fabric made of cellulose or polyolefin resin.
- an electrode and a separator are accommodated in a cell case, and an electrolyte solution is impregnated into an electrode and a separator.
- the electric double layer capacitor can be manufactured by sealing the case with an insulating gasket.
- a non-aqueous material it is preferable to sufficiently dry materials such as electrodes in order to reduce the moisture in the capacitor as much as possible.
- the capacitor may be manufactured in an environment with little moisture, and the sealing may be performed in a reduced pressure environment. Note that the capacitor is not particularly limited as long as the current collector and the electrode according to one embodiment of the present invention are used, and the capacitor may be manufactured by other methods.
- Electrolyte can be used for both aqueous and non-aqueous, but non-aqueous electrolyte is preferable because the voltage can be set higher.
- An aqueous potassium hydroxide solution or the like can be used as the aqueous electrolyte solution.
- An ionic liquid can be used as the non-aqueous electrolyte.
- cations and anions of ionic liquids As the cation, lower aliphatic quaternary ammonium, lower aliphatic quaternary phosphonium, imidazolinium and the like are used.
- Known anions include metal chloride ions, metal fluoride ions, and imide compounds such as bis (fluorosulfonyl) imide.
- non-aqueous electrolyte solution there are polar aprotic organic solvents, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, and the like are used.
- polar aprotic organic solvents ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, and the like are used.
- supporting salt in the non-aqueous electrolyte lithium tetrafluoroborate, lithium hexafluorophosphate, or the like is used.
- FIG. 5 is a schematic cross-sectional view showing an example of a lithium ion capacitor using a lithium ion capacitor electrode material.
- an electrode material carrying a positive electrode active material on a porous aluminum body is arranged as a positive electrode 146
- an electrode material carrying a negative electrode active material on a current collector is arranged as a negative electrode 147.
- the positive electrode 146 and the negative electrode 147 are connected to lead wires 148 and 149, respectively. All of these are housed in a case 145.
- the aluminum porous body as a current collector, the surface area of the current collector is increased. Therefore, even if the activated carbon as the active material is thinly applied, a lithium ion capacitor capable of high output and high capacity can be obtained.
- activated carbon is filled as an active material in an aluminum porous body current collector.
- Activated carbon is used in combination with a conductive aid and a binder.
- the activated carbon is preferably 90% or more in terms of the composition ratio after drying (after solvent removal).
- a conductive support agent and a binder are necessary, it is a factor of a capacity
- the conductive assistant is preferably 10% by mass or less, and the binder is preferably 10% by mass or less.
- the specific surface area is preferably 1000 m 2 / g or more.
- the activated carbon plant-derived coconut shells, petroleum-based materials, and the like can be used. In order to improve the surface area of the activated carbon, it is preferable to activate the activated carbon using water vapor or alkali.
- ketjen black, acetylene black, carbon fiber, or a composite material thereof can be used as the conductive auxiliary.
- the binder polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethylcellulose, xanthan gum and the like can be used.
- water or an organic solvent may be appropriately selected depending on the kind of the binder.
- organic solvents N-methyl-2-pyrrolidone is often used.
- surfactant when using water for a solvent, you may use surfactant in order to improve a filling property.
- An activated carbon paste can be obtained by mixing and stirring the electrode material mainly composed of activated carbon.
- the activated carbon paste is filled in the current collector, dried, and compressed by a roller press or the like as necessary to improve the density, thereby obtaining an electrode for a lithium ion capacitor.
- the activated carbon can be filled using a known method such as a dip filling method or a coating method.
- a coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- a conductive additive and a binder are added as necessary, and an organic solvent and water are mixed therewith to prepare a positive electrode mixture slurry.
- This slurry is filled into an aluminum porous body using the above method.
- the conductive assistant for example, carbon black such as acetylene black (AB) and ketjen black (KB) and carbon fiber such as carbon nanotube (CNT) can be used.
- the binder for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), xanthan gum and the like can be used.
- the organic solvent used when preparing the positive electrode mixture slurry has an adverse effect on the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the aluminum porous body. If not, it can be selected as appropriate.
- organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- the negative electrode is not particularly limited, and a conventional negative electrode for a lithium battery can be used.
- the conventional electrode using a copper foil as a current collector has a small capacity, it is made of copper or nickel such as the aforementioned foamed nickel.
- An electrode in which a porous material is filled with an active material is preferable.
- the negative electrode is doped with lithium ions in advance. A known method can be used as the doping method.
- the remaining capacity of the negative electrode is smaller than the positive electrode capacity, the capacity of the lithium ion capacitor is reduced, so the positive electrode capacity is not doped. It is preferable to leave it in
- -Electrolyte used in lithium ion capacitors The same electrolyte as the nonaqueous electrolyte used for the lithium battery is used.
- a polar aprotic organic solvent is used, and specifically, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and the like are used.
- the supporting salt lithium tetrafluoroborate, lithium hexafluorophosphate, and an imide salt are used.
- the electrode obtained as described above is punched out to an appropriate size and is made to face the negative electrode with a separator interposed therebetween.
- the negative electrode may be doped with lithium ions by the method described above.
- an electrode connected with lithium metal may be arranged in the cell.
- the separator it is preferable to use a porous film or a nonwoven fabric made of cellulose, polyolefin resin, or the like. And using a required spacer, an electrode and a separator are accommodated in a cell case, and an electrolyte solution is impregnated into an electrode and a separator.
- the case is covered and sealed with an insulating gasket, so that a lithium ion capacitor can be produced.
- the material such as the electrode is sufficiently dried.
- the lithium ion capacitor may be manufactured in an environment with little moisture, and the sealing may be performed in a reduced pressure environment. Note that the lithium ion capacitor is not particularly limited as long as the current collector and the electrode according to one embodiment of the present invention are used, and the lithium ion capacitor may be manufactured by other methods.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating cations of a molten salt serving as an electrolyte such as sodium chromite (NaCrO 2 ) and titanium disulfide (TiS 2 ) as an active material Is used.
- the active material is used in combination with a conductive additive and a binder.
- Acetylene black etc. can be used as a conductive support agent.
- the binder polytetrafluoroethylene (PTFE) or the like can be used.
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to use an alloy of sodium and another metal (Si, Sn, In, etc.).
- an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal alloy (such as Si) to be alloyed with sodium is attached to the aluminum porous body by a method such as plating, and then charged in a molten salt battery to form a sodium alloy.
- FIG. 6 is a schematic sectional view showing an example of a molten salt battery using the battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature can be 90 ° C. or lower.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, a porous porous resin body, etc. can be used for it.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- Example 1 A urethane foam having a porosity of 96%, a number of cells of 46 / inch, a pore diameter of about 550 ⁇ m, and a thickness of 1.0 mm was prepared as a resin molded body, and this was cut into 100 mm ⁇ 100 mm squares. A conductive layer was formed on the surface of the polyurethane foam by sputtering to form aluminum with a basis weight of 10 g / m 2 .
- the urethane foam having a conductive layer formed on the surface was set as a workpiece on a jig having a power feeding function, and then placed in a glove box having an argon atmosphere and low moisture (dew point -30 ° C. or lower). It was immersed in a molten salt aluminum plating bath (33 mol% EMIC-67 mol% AlCl 3 ). The jig on which the workpiece was set was connected to the cathode side of the rectifier, and a counter electrode aluminum plate (purity 99.99 mass%) was connected to the anode side.
- a resin structure in which an aluminum film having a mass of 140 g / m 2 was formed on the surface of the urethane foam was obtained by plating by applying a direct current having a current density of 6.5 A / dm 2 for 20 minutes. Stirring was performed with a stirrer using a Teflon (registered trademark) rotor.
- the current density is a value calculated from the apparent area of the urethane foam.
- the resin structure obtained above was taken out of the plating bath, and washed with water having a liquid temperature of 10 ° C. in a state where the amount of plating solution deposited was 18 mL / m 2 . Thereafter, moisture was removed from the resin structure by a blower.
- the resin structure was introduced into an atmospheric furnace having a dew point temperature of ⁇ 15 ° C., and heat treatment was performed at 150 ° C. for 60 minutes. As a result, the resin structure was dried, and water was sufficiently removed. Subsequently, the resin structure from which the moisture had been removed was heat-treated at 600 ° C. for 20 minutes in an air atmosphere furnace having a dew point temperature of ⁇ 15 ° C. Thereby, the resin-made base material was removed from the resin structure, and an aluminum porous body A having a hollow three-dimensional network structure inside the skeleton could be obtained.
- Example 2 In the same manner as in Example 1, an aluminum film was formed on the surface of the urethane foam to produce a resin structure, the plating solution adhering to the resin structure was removed by washing with water, and water was removed with a blower. Subsequently, the resin structure was introduced into an air atmosphere furnace having a dew point temperature of ⁇ 15 ° C., and heat treatment was performed at 500 ° C. for 20 minutes. Thereby, the aluminum porous body B from which the water
- Example 1 In the same manner as in Example 1, an aluminum film was formed on the surface of the urethane foam to produce a resin structure, and the plating solution adhering to the resin structure was removed by washing with water. Subsequently, the resin structure was introduced into an air atmosphere furnace having a dew point temperature of 20 ° C., and heat treatment was performed at 600 ° C. for 20 minutes. Thereby, the aluminum porous body C was obtained.
- Example 2 In the same manner as in Example 1, an aluminum film was formed on the surface of the urethane foam to produce a resin structure, and the plating solution adhering to the resin structure was removed by washing with water. Subsequently, the resin structure was introduced into an air atmosphere furnace having a dew point temperature of 2 ° C., and heat treatment was performed at 600 ° C. for 20 minutes. Thereby, the aluminum porous body D was obtained.
- the moisture adsorption amount of the aluminum porous bodies A to D obtained as described above was measured by the Karl Fischer coulometric titration method. First, porous aluminum bodies A to D were cut into 10 mm ⁇ 50 mm squares for measurement, and five test pieces A to D were prepared. Then, these test pieces A to D were sufficiently dried by heat treatment for 10 minutes in an inert atmosphere of 300 ° C., for example, nitrogen or argon atmosphere. Thereafter, the test piece was exposed to an atmosphere having a dew point of ⁇ 20 ° C. for 24 hours.
- the moisture adsorption amount of the test pieces A to D pretreated as described above was measured by the Karl Fischer coulometric titration method using a moisture vaporizer heated to 300 ° C.
- the end condition of the titration was the time when the detected water content became “background value + 0.1 ⁇ g / sec”.
- the moisture adsorption amount (mg / m 2 ) of the aluminum porous bodies A and B is compared with the moisture adsorption amount of the aluminum porous bodies C and D. It was confirmed that the number was extremely low.
- the results are shown in Table 1.
- the porous aluminum bodies A and B had a small amount of re-adsorbing moisture in the atmosphere.
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Abstract
Description
(1)本発明の一態様に係るアルミニウム多孔体の製造方法は、三次元網目状構造を有する樹脂製の基材の表面に溶融塩電解めっきによってアルミニウム膜を形成して樹脂構造体を製造する工程と、前記樹脂構造体から水分を除去する工程と、前記水分が除去された樹脂構造体を熱処理して前記基材を除去する工程と、を有するアルミニウム多孔体の製造方法、である。
(3)また、前記アルミニウム多孔体の製造方法は、前記樹脂構造体から水分を除去する工程において、露点温度が0℃以下の雰囲気中で、前記樹脂構造体を370℃以上、500℃以下の温度で熱処理することが好ましい。
本発明の一態様に係るアルミニウム多孔体は、例えば、電気化学デバイスの電極に用いることができる。この場合、本発明の一態様に係るアルミニウム多孔体は骨格が三次元網目状構造であるため、空孔部分に多量の活物質を保持することができ、単位体積当たりの活物質の利用率が高く、容量の大きな電極を提供することができる。
前記本発明の一態様に係るアルミニウム多孔体を電気化学デバイス用の集電体として用いることで、容量の大きな電気化学デバイスを製造することができる。また、本発明の一態様に係るアルミニウム多孔体は水分吸着量が少ないため、非水電解質を利用する電気化学デバイスに用いる場合には、電極の乾燥工程の負担を減らすことができる。
前記アルミニウム多孔体の気孔部に活物質を充填することで、容量の大きな電極を得ることができる。また、非水電解質を利用する電気化学デバイスに用いる場合には、電極の乾燥工程にかかる負担を軽減することができる。
本発明の一態様に係る電気化学デバイスは、単位体積当たりの活物質の利用率が高い前記本発明の一態様に係る電極を用いているため、容量を大きくすることができる。また、非水電解質を用いる電気化学デバイスの場合には、電極の乾燥工程に要する負担が軽減されるため、製造コストを低減させることができる。
本発明の一態様に係るアルミニウム多孔体の製造方法等の具体例を以下に説明する。
なお、本発明はこれらの例示に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
前記のように、本発明の一態様に係るアルミニウム多孔体の製造方法は、三次元網目状構造を有する樹脂製の基材の表面に溶融塩電解めっきによってアルミニウム膜を形成して樹脂構造体を製造する工程と、前記樹脂構造体から水分を除去する工程と、前記水分が除去された樹脂構造体を熱処理して前記基材を除去する工程と、を有する。
以下、各工程についてより詳細に説明する。
まず、三次元網目状構造を有し連通孔を有する樹脂成形体を準備する。樹脂成形体の素材は任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。発泡樹脂成形体と表記したが、連続した気孔(連通孔)を有するものであれば任意の形状の樹脂成形体を選択できる。例えば繊維状の樹脂を絡めて不織布のような形状を有するものも、発泡樹脂成形体に代えて使用可能である。
気孔率は、次式で定義される。
気孔率=(1-(多孔質材の重量[g]/(多孔質材の体積[cm3]×素材密度)))×100[%]
また、気孔径は、樹脂成形体表面を顕微鏡写真等で拡大し、1インチ(25.4mm)あたりの気孔数をセル数として計数して、平均孔径=25.4mm/セル数として平均的な値を求める。
樹脂成形体の表面にアルミニウムを電解めっきするために、樹脂成形体の表面をあらかじめ導電化処理する。導電化処理としては、樹脂成形体の表面に導電性を有する層を設けることができる処理である限り特に制限はない。例えば、ニッケル等の導電性金属の無電解めっき、アルミニウム等の蒸着及びスパッタ、又はカーボン等の導電性粒子を含有した導電性塗料の塗布等、任意の方法を選択することができる。
アルミニウムを用いたスパッタリング処理としては、アルミニウムをターゲットとする限り限定的でなく、常法に従って行えばよい。例えば、基板ホルダーに樹脂成形体を取り付けた後、不活性ガスを導入しながら、ホルダーとターゲット(アルミニウム)との間に直流電圧を印加することにより、イオン化した不活性ガスをアルミニウムに衝突させて、はじき飛ばされたアルミニウム粒子を樹脂成形体表面に堆積することによってアルミニウムのスパッタ膜を形成する。なお、スパッタリング処理は樹脂成形体が溶解しない温度下で行うことが好ましく、具体的には、100~200℃程度、好ましくは120~180℃程度で行えばよい。
まず、導電性塗料としてのカーボン塗料を準備する。導電性塗料としての懸濁液は、好ましくは、カーボン粒子、粘結剤、分散剤および分散媒を含む。導電性粒子の塗布を均一に行うには、懸濁液が均一な懸濁状態を維持している必要がある。このため、懸濁液は、20℃~40℃に維持されていることが好ましい。その理由は、懸濁液の温度が20℃未満になった場合、均一な懸濁状態が崩れ、樹脂多孔体の網状構造をなす骨格の表面に粘結剤のみが集中して層を形成する場合があるからである。この場合、塗布されたカーボン粒子の層は剥離し易く、強固に密着した金属めっきを形成し難い。一方、懸濁液の温度が40℃を越えた場合は、分散剤の蒸発量が大きく、塗布処理時間の経過とともに懸濁液が濃縮されてカーボンの塗布量が変動しやすい。また、カーボン粒子の粒径は、0.01~5μmであることが好ましく、より好ましくは0.01~2μmである。粒径が大きいと樹脂成形体のセルを詰まらせたり、平滑なめっきを阻害したりする要因となり、また、小さすぎると十分な導電性を確保することが難しくなる。
樹脂成形体へのカーボン粒子の塗布は、上記懸濁液に対象となる樹脂成形体を浸漬し、絞りと乾燥を行うことで行うことができる。
樹脂成形体の表面にアルミニウム膜を形成する方法としては、溶融塩浴を用いためっき法を採用する。
-溶融塩めっき-
溶融塩中で電解めっきを行い、前記樹脂成形体の表面にアルミニウム膜を形成する。
溶融塩浴中でアルミニウムのめっきを行うことにより特に三次元網目状構造を有する樹脂成形体のように複雑な骨格構造の表面に均一に厚いアルミニウム膜を形成することができる。表面が導電化された樹脂成形体を陰極とし、アルミニウムを陽極として溶融塩中で直流電流を印加する。
また、溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなく電解めっきすることができる。有機系ハロゲン化物としてはイミダゾリウム塩、ピリジニウム塩等が使用でき、具体的には1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。
溶融塩中に水分や酸素が混入すると溶融塩が劣化するため、めっきは窒素、アルゴン等の不活性ガス雰囲気下で、かつ密閉した環境下で行うことが好ましい。
従来のアルミニウム多孔体の製造方法は、上記のようにして得られた樹脂多孔体を熱処理することにより樹脂を除去していたが、本発明者等の鋭意検討の結果、この工程に改良を加えることで、骨格の表面にγ-アルミナが形成されないようにアルミニウム多孔体を製造することができることを見出した。
なお、前記露点温度が-30℃程度で、前記の水分除去の効率はほぼ飽和するため、前記露点温度は-30℃以上で熱処理を行えばよい。
また、前記水分を除去する際の雰囲気は特に限定されず、大気下、窒素雰囲気下、アルゴン雰囲気、ヘリウム雰囲気等、適宜選択可能である。
上記のように水分が除去された樹脂構造体を、更に加熱処理することで前記基材を除去して、アルミニウム多孔体を得ることができる。前記基材の除去は、例えば、前記水分が除去された樹脂構造体を370℃以上、アルミニウムの融点未満で熱処理することにより行うことができる。これにより樹脂が焼失し、中空の骨格を有するアルミニウム多孔体を得られる。前記基材を除去する際の熱処理を370℃以上で行うことにより、効率よく樹脂製の基材を焼失させることができる。また、前記基材を除去する際の熱処理温度をアルミニウムの融点未満で行うことにより、アルミニウムが熔けて多孔体の構造が崩壊することを抑制することができる。これらの観点から、前記基材を除去する際の熱処理温度は、500℃以上、660℃以下の温度範囲で行うことがより好ましく、580℃以上、630℃以下の温度範囲で行うことが更に好ましい。
なお、前記基材を除去する際の露点温度は-30℃程度で充分に雰囲気中の水分とアルミニウムとの反応を抑制することができるため、前記露点温度は-30℃以上で基材の除去を行えばよい。
また、前記基材を除去する際の雰囲気は特に限定されず、大気下、窒素雰囲気下、アルゴン雰囲気、ヘリウム雰囲気等、適宜選択可能である。
また、本発明の一態様に係るアルミニウム多孔体の製造方法においては、前記基材表面にアルミニウム膜を形成して樹脂構造体を製造した後に、露点温度が0℃以下の雰囲気中で、前記樹脂構造体を370℃以上、500℃以下の温度で熱処理することにより、前記樹脂構造体から水分を除去する工程と、前記基材を除去する工程と、を行うができる。
一方、500℃を超える温度範囲に加熱をすると、前記樹脂構造体のアルミニウム膜の表面にベーマイト層が形成されやすくなるため、前記熱処理温度は500℃以下で行うことが好ましく、480℃以下がより好ましい。
以上のようにして得られる本発明の一態様に係るアルミニウム多孔体は骨格表面にγ-アルミナが形成されていないため平滑であり、これにより水分吸着量が非常に少ないアルミニウム多孔体となっている。
なお、アルミニウム多孔体の水分吸着量とは、露点温度が-20℃の雰囲気に24時間暴露した後のアルミニウム多孔体の見かけの面積当たりの水分量のことをいう。
また、本発明の一態様に係るアルミニウム多孔体は上記のように水分吸着量が少ないため、例えば、非水電解質を用いた電池やキャパシタの電極のように水分を除去した環境下で使用する場合に、水分の乾燥除去工程の負担を軽減することができる。
前記本発明の一態様に係るアルミニウム多孔体は、電気化学デバイス用の集電体として用いることができ、また、気孔部に活物質を充填することで電気化学デバイス用の電極として用いることができる。電気化学デバイスとしては特に制限されるものではないが、前記のように本発明の一態様に係るアルミニウム多孔体は水分吸着量が少ないため、非水電解質を利用する電気化学デバイスに用いると、乾燥工程の負担を軽減することができる。例えば、従来のめっき法により作製したアルミニウム多孔体を充分に乾燥させるためには、150℃、5Torr以下で16時間以上の熱処理が必要であったところ、本発明の一態様に係るアルミニウム多孔体は150℃、5Torr以下で2時間以下の熱処理で済ませることができる。
以下に、本発明の一態様に係るアルミニウム多孔体を好ましく利用することができる電気化学デバイスの一例を説明する。
本発明の一態様に係るアルミニウム多孔体を用いた電気化学デバイスの一例としてリチウム電池について説明する。例えばリチウム電池(リチウムイオン二次電池等を含む。)の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は導電助剤及びバインダーと組み合わせて使用する。
リチウム電池に使用される電解質には、非水電解液と固体電解質がある。
図3は、固体電解質を使用した全固体リチウム電池の縦断面図である。この全固体リチウム電池60は、正極61、負極62、および、両電極間に配置される固体電解質層(SE層)63を備える。正極61は、正極層(正極体)64と正極集電体65とからなり、負極62は、負極層66と負極集電体67とからなる。
電解質として、固体電解質以外に、後述する非水電解液が用いられる。この場合、両極間には、セパレーター(多孔質ポリマーフィルムや不織布、紙等)が配置され、非水電解液は両極およびセパレーター中に含浸される。
アルミニウム多孔体をリチウム電池の正極に使用する場合は、活物質としてリチウムを脱挿入できる材料を使用することができる。このような材料をアルミニウム多孔体に充填することでリチウム二次電池に適した電極を得ることができる。正極活物質の材料としては、例えばコバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、ニッケルコバルト酸リチウム(LiCo0.3Ni0.7O2)、マンガン酸リチウム(LiMn2O4)、チタン酸リチウム(Li4Ti5O12)、リチウムマンガン酸化合物(LiMyMn2-yO4);M=Cr、Co、Ni)、リチウム酸等を使用する。活物質は導電助剤及びバインダーと組み合わせて使用する。その他の正極活物質の材料としては遷移金属酸化物が挙げられ、例えば、従来から用いられているリチウムリン酸鉄(LiFePO4)及びその化合物(例えば、LiFe0.5Mn0.5PO4)などのオリビン化合物である。また、これらの材料の中に含まれる遷移金属元素を、別の遷移金属元素に一部置換してもよい。
非水電解液としては、極性非プロトン性有機溶媒で使用され、具体的にはエチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、プロピレンカーボネート、γ-ブチロラクトン及びスルホラン等が使用される。支持塩としては4フッ化ホウ酸リチウム、6フッ化リン酸リチウム、およびイミド塩等が使用されている。電解質となる支持塩の濃度は高い方が好ましいが、溶解に限度があるため1mol/L付近のものが一般に用いられる。
活物質の他に、さらに、固体電解質を加えて充填してもよい。アルミニウム多孔体に活物質と固体電解質とを充填することで、全固体リチウム電池の電極に適したものとすることができる。ただし、アルミニウム多孔体に充填する材料のうち活物質の割合は、放電容量を確保する観点から、50質量%以上、より好ましくは70質量%以上とすることが好ましい。
活物質(又は活物質と固体電解質)の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケーター塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコーター塗工法、バーコーター塗工法、ロールコーター塗工法、ディップコーター塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコーター塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
図4はキャパシタ用電極材料を用いたキャパシタの一例を示す断面模式図である。セパレーター142で仕切られた有機電解液143中に、アルミニウム多孔体に電極活物質を担持した電極材料を分極性電極141として配置している。分極性電極141はリード線144に接続している。これら全体がケース145中に収納されている。アルミニウム多孔体を集電体として使用することで、集電体の表面積が大きくなり、活物質としての活性炭との接触面積が大きくなるため、高出力、高容量化可能なキャパシタを得ることができる。
キャパシタの容量を大きくするためには主成分である活性炭の量が多い方が良く、乾燥後(溶媒除去後)の組成比で活性炭が90%以上あることが好ましい。また導電助剤やバインダーは必要ではあるが容量低下の要因であり、バインダーは更に内部抵抗を増大させる要因である。したがって、導電助剤やバインダーはできる限り少ない方がよい。導電助剤は10質量%以下、バインダーは10質量%以下が好ましい。
活性炭の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケーター塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコーター塗工法、バーコーター塗工法、ロールコーター塗工法、ディップコーター塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコーター塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
上記のようにして得られた電極を適当な大きさに打ち抜いて2枚用意し、セパレーターを挟んで対向させる。セパレーターはセルロースやポリオレフィン樹脂などで構成された多孔膜や不織布を用いるのが好ましい。そして、必要なスペーサを用いて、電極及びセパレーターをセルケースに収納し、電極及びセパレーターに電解液を含浸させる。最後に絶縁ガスケットを介してケースに蓋をして封口することにより電気二重層キャパシタを作製することができる。
非水系の材料を使用する場合は、キャパシタ内の水分を限りなく少なくするため、電極などの材料を十分乾燥することが好ましい。キャパシタの作製は水分の少ない環境下で行い、封止は減圧環境下で行ってもよい。なお、本発明の一態様に係る集電体、電極を用いていればキャパシタとしては特に限定されず、これ以外の方法により作製されるものでも構わない。
図5はリチウムイオンキャパシタ用電極材料を用いたリチウムイオンキャパシタの一例を示す断面模式図である。セパレーター142で仕切られた有機電解液143中に、アルミニウム多孔体に正極活物質を担持した電極材料を正極146として配置し、集電体に負極活物質を担持した電極材料を負極147として配置している。正極146及び負極147はそれぞれリード線148、149に接続している。これら全体がケース145中に収納されている。アルミニウム多孔体を集電体として使用することで、集電体の表面積が大きくなる。したがって、活物質としての活性炭を薄く塗布しても、高出力、高容量化可能なリチウムイオンキャパシタを得ることができる。
リチウムイオンキャパシタ用の電極を製造するには、アルミニウム多孔体集電体に活物質として活性炭を充填する。活性炭は導電助剤やバインダーと組み合わせて使用する。
リチウムイオンキャパシタの容量を大きくするためには主成分である活性炭の量が多い方が良く、乾燥後(溶媒除去後)の組成比で活性炭が90%以上であることが好ましい。また導電助剤やバインダーは必要ではあるが容量低下の要因であり、バインダーは更に内部抵抗を増大させる要因である。したがって、導電助剤やバインダーはできる限り少ない方がよい。導電助剤は10質量%以下、バインダーは10質量%以下が好ましい。
活性炭の充填は、例えば、浸漬充填法や塗工法などの公知の方法を用いることができる。塗工法としては、例えば、ロール塗工法、アプリケーター塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコーター塗工法、バーコーター塗工法、ロールコーター塗工法、ディップコーター塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコーター塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
負極は特に限定されず従来のリチウム電池用負極を使用可能であるが、銅箔を集電体に用いた従来の電極では容量が小さいため、前述の発泡状ニッケルのような銅やニッケル製の多孔体に活物質を充填した電極が好ましい。また、リチウムイオンキャパシタとして動作させるために、あらかじめ負極にリチウムイオンをドープしておくことが好ましい。ドープ方法としては公知の方法を用いることができる。たとえば、負極表面にリチウム金属箔を貼り付けて電解液中に浸してドープする方法や、リチウムイオンキャパシタ内にリチウム金属を取り付けた電極を配置し、セルを組み立ててから負極とリチウム金属電極の間で電流を流して電気的にドープする方法、あるいは負極とリチウム金属で電気化学セルを組み立て、電気的にリチウムをドープした負極を取り出して使用する方法などが挙げられる。
いずれの方法でも、負極の電位を十分に下げるためにリチウムドープ量は多いほうがよいが、負極の残容量が正極容量より小さくなるとリチウムイオンキャパシタの容量が小さくなるため、正極容量分はドープせずに残しておく方が好ましい。
電解液はリチウム電池に使用する非水電解液と同じものが用いられる。非水電解液としては、極性非プロトン性有機溶媒で使用され、具体的にはエチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、プロピレンカーボネート、γ-ブチロラクトン及びスルホラン等が使用される。支持塩としては4フッ化ホウ酸リチウム、6フッ化リン酸リチウム、およびイミド塩等が使用されている。
上記のようにして得られた電極を適当な大きさに打ち抜き、セパレーターを挟んで負極と対向させる。負極は、前述の方法でリチウムイオンをドープしたものを用いても構わない。また、セルを組み立てた後にドープする方法をとる場合は、リチウム金属を接続した電極をセル内に配置すればよい。セパレーターとしては、セルロースやポリオレフィン樹脂などで構成された多孔膜や不織布を用いるのが好ましい。そして、必要なスペーサを用いて、電極及びセパレーターをセルケースに収納し、電極及びセパレーターに電解液を含浸させる。最後に絶縁ガスケットを介してケースに蓋をして封口することによりリチウムイオンキャパシタを作製することができる。
リチウムイオンキャパシタ内の水分を限りなく少なくするため、電極などの材料は十分乾燥することが好ましい。また、リチウムイオンキャパシタの作製は水分の少ない環境下で行い、封止は減圧環境下で行ってもよい。なお、本発明の一態様に係る集電体、電極を用いていればリチウムイオンキャパシタとしては特に限定されず、これ以外の方法により作製されるものでも構わない。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質として亜クロム酸ナトリウム(NaCrO2)、二硫化チタン(TiS2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は導電助剤及びバインダーと組み合わせて使用する。導電助剤としてはアセチレンブラック等を使用できる。またバインダーとしてはポリテトラフルオロエチレン(PTFE)等を使用できる。活物質として亜クロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、この両者をより強固に固着するために、PTFEを使用することが好ましい。
例えばカリウムビス(フルオロスルフォニル)アミド<K-N(SO2F)2;KFSA>とナトリウムビス(フルオロスルフォニル)アミド<Na-N(SO2F)2;NaFSA>とを組み合わせて使用すると、電池の動作温度を90℃以下とすることができる。
樹脂成形体として、気孔率96%、セル数46個/インチ、気孔径約550μm、厚さ1.0mmのウレタン発泡体を準備し、これを100mm×100mm角に切断した。このポリウレタンフォームの表面にスパッタリングによってアルミニウムを目付量10g/m2で成膜して導電層を形成した。
電流密度6.5A/dm2の直流電流を20分間印加してめっきすることにより、ウレタン発泡体表面に140g/m2の質量のアルミニウム膜が形成された樹脂構造体を得た。攪拌はテフロン(登録商標)製の回転子を用いてスターラーにて行った。なお、電流密度はウレタン発泡体の見かけの面積で計算した値である。
続いて、前記水分が除去された樹脂構造体について、露点温度が-15℃の大気雰囲気の炉内で、600℃で20分間の熱処理を行った。これにより、樹脂構造体から樹脂製の基材が除去されて、骨格の内部が中空の三次元網目状構造を有するアルミニウム多孔体Aを得ることができた。
実施例1と同様にして、ウレタン発砲体の表面にアルミニウム膜を形成して樹脂構造体を作製し、該樹脂構造体に付着しためっき液を水洗除去し、ブロワーによる水分除去を行った。
続いて、上記樹脂構造体を露点温度が-15℃の大気雰囲気の炉内に導入し、500℃で20分間の熱処理を行った。これにより、樹脂構造体から水分が除去され、かつ、樹脂製の基材が除去されたアルミニウム多孔体Bを得ることができた。
実施例1と同様にして、ウレタン発砲体の表面にアルミニウム膜を形成して樹脂構造体を作製し、該樹脂構造体に付着しためっき液を水洗除去した。
続いて、上記樹脂構造体を露点温度が20℃の大気雰囲気の炉内に導入し、600℃で20分間の熱処理を行った。これにより、アルミニウム多孔体Cを得た。
実施例1と同様にして、ウレタン発砲体の表面にアルミニウム膜を形成して樹脂構造体を作製し、該樹脂構造体に付着しためっき液を水洗除去した。
続いて、上記樹脂構造体を露点温度が2℃の大気雰囲気の炉内に導入し、600℃で20分間の熱処理を行った。これにより、アルミニウム多孔体Dを得た。
<水分吸着量>
上記のようにして得られたアルミニウム多孔体A~Dの水分吸着量をカールフィッシャー電量滴定法により測定した。
まず、測定用にアルミニウム多孔体A~Dをそれぞれ10mm×50mm角に切断し、試験片A~Dをそれぞれ5枚用意した。そして、これらの試験片A~Dを10分間、300℃の不活性雰囲気、例えば窒素やアルゴン雰囲気で熱処理をして十分に乾燥させた。その後、試験片を露点-20℃の雰囲気に24時間暴露した。
上記のようにして前処理を行った試験片A~Dの水分吸着量を、300℃に加熱した水分気化装置を用いてカールフィッシャー電量滴定法にて測定した。滴定の終了条件は、検出水分量が「バックグラウンド値+0.1μg/sec」となった時点とした。
アルミニウム多孔体Aを電子顕微鏡で観察したところ、図1に示すように、骨格表面に微小な凹凸が形成されていないことが確認された。同様に、アルミニウム多孔体Cを電子顕微鏡で観察したところ、図2に示すように、骨格表面に微小な凹凸が無数に形成されていることが確認された。
アルミニウム多孔体A~Dを集電体A~Dとして用い、アルミニウム多孔体A~Dの気孔部に活物質を充填して電極A~Dを作製した。電極A~Dを作製する際、150℃、5Torr、2時間の乾燥処理を行った。この電極A~Dを用いて前述のリチウムイオンキャパシタA~Dを作製し、評価をした。
その結果、アルミニウム多孔体A、Bを用いたリチウムイオンキャパシタA、Bからはガスの発生が確認されなかったが、アルミニウム多孔体C、Dを用いたリチウムイオンキャパシタC、Dからは副反応によるガスの発生が確認された。これは、アルミニウム多孔体C、Dを使用した場合の乾燥条件が充分ではなく、キャパシタ内で、水分と電解液とが反応してしまったためと考えられる。
61 正極
62 負極
63 固体電解質層(SE層)
64 正極層(正極体)
65 正極集電体
66 負極層
67 負極集電体
121 正極
122 負極
123 セパレーター
124 押さえ板
125 バネ
126 押圧部材
127 ケース
128 正極端子
129 負極端子
130 リード線
141 分極性電極
142 セパレーター
143 有機電解液
144 リード線
145 ケース
146 正極
147 負極
148 リード線
149 リード線
Claims (7)
- 三次元網目状構造を有する樹脂製の基材の表面に溶融塩電解めっきによってアルミニウム膜を形成して樹脂構造体を製造する工程と、
前記樹脂構造体から水分を除去する工程と、
前記水分が除去された樹脂構造体を熱処理して前記基材を除去する工程と、
を有するアルミニウム多孔体の製造方法。 - 前記樹脂構造体から水分を除去する工程において、前記樹脂構造体を50℃以上、300℃以下の温度で熱処理し、
前記基材を除去する工程において、前記樹脂構造体を370℃以上、アルミニウムの融点未満の温度で熱処理する
請求項1に記載のアルミニウム多孔体の製造方法。 - 前記樹脂構造体から水分を除去する工程において、露点温度が0℃以下の雰囲気中で、前記樹脂構造体を370℃以上、500℃以下の温度で熱処理する
請求項1に記載のアルミニウム多孔体の製造方法。 - 請求項1から請求項3のいずれか一項に記載のアルミニウム多孔体の製造方法によって得られるアルミニウム多孔体。
- 請求項4に記載のアルミニウム多孔体からなる電気化学デバイス用の集電体。
- 請求項4に記載のアルミニウム多孔体の気孔部に活物質を有する電気化学デバイス用の電極。
- 請求項6に記載の電極を用いた電気化学デバイス。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0892669A (ja) * | 1994-09-29 | 1996-04-09 | Achilles Corp | 金属多孔体の熱処理方法 |
JP2011249261A (ja) * | 2010-05-31 | 2011-12-08 | Sumitomo Electric Ind Ltd | 非水電解質電池用電極、及び非水電解質電池 |
WO2012111585A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友電気工業株式会社 | アルミニウム多孔体及びその製造方法 |
JP2012186160A (ja) * | 2011-02-18 | 2012-09-27 | Sumitomo Electric Ind Ltd | 電池 |
JP2012255185A (ja) * | 2011-06-08 | 2012-12-27 | Sumitomo Electric Ind Ltd | アルミニウム多孔体の製造方法及び製造装置 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0892669A (ja) * | 1994-09-29 | 1996-04-09 | Achilles Corp | 金属多孔体の熱処理方法 |
JP2011249261A (ja) * | 2010-05-31 | 2011-12-08 | Sumitomo Electric Ind Ltd | 非水電解質電池用電極、及び非水電解質電池 |
WO2012111585A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友電気工業株式会社 | アルミニウム多孔体及びその製造方法 |
JP2012186160A (ja) * | 2011-02-18 | 2012-09-27 | Sumitomo Electric Ind Ltd | 電池 |
JP2012255185A (ja) * | 2011-06-08 | 2012-12-27 | Sumitomo Electric Ind Ltd | アルミニウム多孔体の製造方法及び製造装置 |
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