TW201419329A - 電容器 - Google Patents
電容器 Download PDFInfo
- Publication number
- TW201419329A TW201419329A TW102128463A TW102128463A TW201419329A TW 201419329 A TW201419329 A TW 201419329A TW 102128463 A TW102128463 A TW 102128463A TW 102128463 A TW102128463 A TW 102128463A TW 201419329 A TW201419329 A TW 201419329A
- Authority
- TW
- Taiwan
- Prior art keywords
- pores
- capacitor
- diamino
- benzene
- porous carbon
- Prior art date
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- 239000003990 capacitor Substances 0.000 title claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000004044 response Effects 0.000 claims abstract description 20
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- -1 organic acid salt Chemical class 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000002003 electrode paste Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229960005336 magnesium citrate Drugs 0.000 description 5
- 239000004337 magnesium citrate Substances 0.000 description 5
- 235000002538 magnesium citrate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052731 fluorine Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 108010039918 Polylysine Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000656 polylysine Polymers 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- JJXCFGQGYHQZGO-UHFFFAOYSA-N 2,3,5-trifluoro-6-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound NC1=C(F)C(F)=C(N)C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1F JJXCFGQGYHQZGO-UHFFFAOYSA-N 0.000 description 1
- WMHAEENCHDGGLT-UHFFFAOYSA-N 2,3,5-trifluoro-6-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,4-diamine Chemical compound NC1=C(C(=C(C(=C1F)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N)F)F WMHAEENCHDGGLT-UHFFFAOYSA-N 0.000 description 1
- PLUXMKCQQWTNQL-UHFFFAOYSA-N 2,4,6-trifluoro-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-diamine Chemical compound NC1=C(F)C(N)=C(F)C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1F PLUXMKCQQWTNQL-UHFFFAOYSA-N 0.000 description 1
- ARYYWMGGSUEOSY-UHFFFAOYSA-N 2,4,6-trifluoro-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,3-diamine Chemical compound NC1=C(C(=C(C(=C1F)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)F)N)F ARYYWMGGSUEOSY-UHFFFAOYSA-N 0.000 description 1
- CTWCYWKOAJZTIX-UHFFFAOYSA-N 2-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 CTWCYWKOAJZTIX-UHFFFAOYSA-N 0.000 description 1
- XUHNHXZALSOLIQ-UHFFFAOYSA-N 2-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,4-diamine Chemical compound NC1=CC(=C(C=C1)N)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F XUHNHXZALSOLIQ-UHFFFAOYSA-N 0.000 description 1
- XWDQRGKPFYELMD-UHFFFAOYSA-N 2-bromo-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound NC1=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C(N)C=C1Br XWDQRGKPFYELMD-UHFFFAOYSA-N 0.000 description 1
- SZCXZNPLUDQXKI-UHFFFAOYSA-N 2-bromo-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,4-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N)Br SZCXZNPLUDQXKI-UHFFFAOYSA-N 0.000 description 1
- XDAFONKQYWGHSR-UHFFFAOYSA-N 2-chloro-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound NC1=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C(N)C=C1Cl XDAFONKQYWGHSR-UHFFFAOYSA-N 0.000 description 1
- LQWQECJMNSXWQB-UHFFFAOYSA-N 2-chloro-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,4-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N)Cl LQWQECJMNSXWQB-UHFFFAOYSA-N 0.000 description 1
- BZJUXNXPOYDDOQ-UHFFFAOYSA-N 2-methoxy-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound COC1=CC(N)=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1N BZJUXNXPOYDDOQ-UHFFFAOYSA-N 0.000 description 1
- AGQWBPFXZWJCDM-UHFFFAOYSA-N 2-methoxy-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,4-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N)OC AGQWBPFXZWJCDM-UHFFFAOYSA-N 0.000 description 1
- QQVPPQNNGXRYJL-UHFFFAOYSA-N 2-methyl-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,4-diamine Chemical compound CC1=CC(N)=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1N QQVPPQNNGXRYJL-UHFFFAOYSA-N 0.000 description 1
- FHAKHYJXZGAQNS-UHFFFAOYSA-N 3,4,6-trifluoro-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,2-diamine Chemical compound NC1=C(N)C(F)=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)=C1F FHAKHYJXZGAQNS-UHFFFAOYSA-N 0.000 description 1
- VUYHYDUDLLHPIR-UHFFFAOYSA-N 4-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,2-diamine Chemical compound NC1=C(C=C(C=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N VUYHYDUDLLHPIR-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- BARGXQMKUMQJOB-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(C1=C(C=CC(=C1)N)C1=C(C=C(C=C1)N)C(F)(F)F)(F)F.FC(F)(F)C1=C(C=CC(=C1)N)C1=CC=C(N)C=C1 BARGXQMKUMQJOB-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- VWMOGMQRFKPYKF-UHFFFAOYSA-N 4-bromo-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,2-diamine Chemical compound NC1=CC(Br)=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1N VWMOGMQRFKPYKF-UHFFFAOYSA-N 0.000 description 1
- IFBJUKSAQYELMN-UHFFFAOYSA-N 4-bromo-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(N)=C(Br)C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 IFBJUKSAQYELMN-UHFFFAOYSA-N 0.000 description 1
- POZMZTLSKYVPBZ-UHFFFAOYSA-N 4-bromo-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)Br)N POZMZTLSKYVPBZ-UHFFFAOYSA-N 0.000 description 1
- MFPDSUQDFDNVQL-UHFFFAOYSA-N 4-chloro-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1N MFPDSUQDFDNVQL-UHFFFAOYSA-N 0.000 description 1
- AAOUKQKPWNBPGR-UHFFFAOYSA-N 4-chloro-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(N)=C(Cl)C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 AAOUKQKPWNBPGR-UHFFFAOYSA-N 0.000 description 1
- ZUOFKMKOWBNENK-UHFFFAOYSA-N 4-chloro-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,2-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)Cl)N ZUOFKMKOWBNENK-UHFFFAOYSA-N 0.000 description 1
- SOZZIITZWOPOPE-UHFFFAOYSA-N 4-chloro-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)Cl)N SOZZIITZWOPOPE-UHFFFAOYSA-N 0.000 description 1
- XJDVKHODDNDBQL-UHFFFAOYSA-N 4-methoxy-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,2-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)OC)N XJDVKHODDNDBQL-UHFFFAOYSA-N 0.000 description 1
- XCELKIWECGGABR-UHFFFAOYSA-N 4-methoxy-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)OC)N XCELKIWECGGABR-UHFFFAOYSA-N 0.000 description 1
- GAPUGKJSCQEVST-UHFFFAOYSA-N 4-methyl-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,2-diamine Chemical compound CC1=CC(N)=C(N)C=C1OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GAPUGKJSCQEVST-UHFFFAOYSA-N 0.000 description 1
- OQXJVLJLQRDYOP-UHFFFAOYSA-N 4-methyl-5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-diamine Chemical compound CC1=C(N)C=C(N)C=C1OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OQXJVLJLQRDYOP-UHFFFAOYSA-N 0.000 description 1
- IQLPTYMQGVOOOB-UHFFFAOYSA-N 4-methyl-5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,2-diamine Chemical compound NC1=C(C=C(C(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)C)N IQLPTYMQGVOOOB-UHFFFAOYSA-N 0.000 description 1
- TXNDGSMEJYOFDC-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 TXNDGSMEJYOFDC-UHFFFAOYSA-N 0.000 description 1
- UAEWELUCQFGWLM-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodec-1-enoxy)benzene-1,3-diamine Chemical compound NC1=CC(=CC(=C1)OC(=C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)N UAEWELUCQFGWLM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 239000011271 tar pitch Substances 0.000 description 1
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- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/145—Liquid electrolytic capacitors
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
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- 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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
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- 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- 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
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Abstract
本發明之目的為提供頻率響應速度高,能夠以高速充放電之電容器。本發明之特徵為具備含有碳材料之分極性電極、與電解液,且使用40質量%之硫酸作為上述電解液時的頻率響應速度為0.7Hz以上,作為上述碳材料,係使用具備細孔與構成此細孔之輪廓的碳質壁,上述細孔為開放氣孔,且採取氣孔部分為連續之構成的多孔質碳。
Description
本發明係關於電容器,特別係關於使用了多孔質碳作為電極材料之電雙層電容器。
作為儲存電能的裝置,係有藉由於電極之化學反應而儲存電能的蓄電池、與藉由電解質離子對電極之物理吸附而儲存電能的電容器。如此,電容器係為離子分子儲存電荷的構成,因此充放電所致之劣化少,顯示出優良的循環特性。因此,使用於各種電氣機器等。
此處,伴隨著近年來電氣機器之發達,係有使電容器高容量化的需求,有許多關於高容量化之提案(例如參照下述專利文獻1)。
但是,為了圖謀電容器進一步的特性提高或多用途化,僅高容量化並不充分。再者,關於電容器之論文,雖有記載顯示相位角與頻率之關係的波德圖(參照下述非專利文獻1、2),但事實上該文獻中對於電容器之電化學特性,並未充分探討。
[專利文獻1]日本特開2010-114356號公報[非專利文獻]
[非專利文獻1]Electrochimica Acta55(2010)2817-2823
[非專利文獻2]Electrochemistry78 No.11(2010)929-933
因而本發明者等人努力研究後,發現了欲謀求電容器進一步的特性提高或多用途化,必須謀求頻率響應速度之提高。然而,以往並無關於電容器之頻率響應速度之提案。又,上述非專利文獻1、2中,雖有關於電容成分之解析,但關於電容器之頻率響應速度並未解析。因而,本發明者,由非專利文獻1、2記載之波德圖進行判讀後,該電容器中之頻率響應速度為0.05~0.35Hz之程度。但是,以如此之值,則頻率響應速度極低,係有無法高速充放電之課題。
因而,本發明之目的為提供頻率響應速度高、能夠高速充放電之電容器。
為了達成上述目的,本發明之電容器,其特
徵為具備含有碳材料之分極性電極、與電解液,且使用40質量%之硫酸作為上述電解液時的頻率響應速度為0.7Hz以上。
頻率響應速度若為0.7Hz以上,於碳材料表面之離子的吸脫附即變得迅速,因此放電時可快速地取出電流,另一方面,充電時可快速地完成充電。因此,能夠以高速充放電。
再者,雖有使用40質量%之硫酸作為電解液
的情況,但依據該記載,本發明之電解液並不限定為硫酸。亦即,使用40質量%之硫酸作為電解液的情況,係因為頻率響應速度係隨著電解液之種類而不同,而必需敘明使用了何種電解液之故,該記載並未意圖性地將電解液種類限定為硫酸。
作為上述碳材料,期望使用具備細孔與構成
此細孔之輪廓的碳質壁,上述細孔為開放氣孔,且採取氣孔部分為連續之構成的多孔質碳。
如上述構成,只要細孔為開放氣孔,且採取氣孔部分為連續之構成(就碳質壁之形狀的觀點來表述時,只要碳質壁呈現3次元網目構造),則電解液對碳材料內之擴散會順利地進行,因此離子之吸脫附會迅速地進行。
再者,本說明書中,亦有將細孔直徑為2nm以上者稱為介孔(mesoporous),且將細孔直徑未達2nm者稱為微孔的情況。
又,上述細孔,係表示形成3次元網目構造之細孔,
例如表示以酸溶液溶出模板之痕跡所產生之大致反映了模板材料大小的細孔(介孔)者,並不包含由該細孔之壁面向碳壁內所產生之細孔(微孔)。而且,本說明書中之細孔,若無特別指明,並不包含微孔。
上述細孔直徑較佳為2nm以上、150nm以下。
細孔直徑未達2nm時,電解液對碳材料內之擴散可能變得不會順利進行,另一方面,細孔直徑超過150nm時,變得無法保持碳質壁之形狀。
上述細孔之容量較佳為0.2ml/g以上。
細孔容量未達0.2ml/g時,變得難以確保比表面積。再者,細孔容量較佳為3.0ml/g以下。其係因碳質壁必須保持3次元網目構造。
上述多孔質碳之比表面積較佳為200m2/g以上。
比表面積未達200m2/g時,會有難以形成三次元網目構造之問題,會有氣孔之形成量不充分,電解液對碳材料內之擴散變差的情形。再者,比表面積之上限較佳為2500m2/g以下。比表面積超過2500m2/g時,可能變得無法保持碳質壁之形狀,會有無法充分形成細孔的可能性。
依照本發明,係發揮可提供頻率響應速度高,能夠高速充放電之電容器的優良效果。
1‧‧‧聚醯胺酸樹脂(醯亞胺系樹脂)
2‧‧‧氧化鎂
3‧‧‧碳質壁
4‧‧‧細孔
5‧‧‧多孔質碳
[圖1]係顯示本發明之製造步驟的圖,同圖(a)係顯示混合聚醯胺酸樹脂與氧化鎂之狀態的說明圖、同圖(b)係顯示將混合物熱處理之狀態的說明圖、同圖(c)係顯示多孔質碳之說明圖。
[圖2]單元A1所用之多孔質碳的TEM(穿透電子顯微鏡)照片。
[圖3]係顯示單元A1~A4、Z中,頻率與相位角之關係的圖。
[圖4]係顯示單元A1、A2、A4之複平面導納圖(admittance plot)的圖。
[圖5]係顯示單元Z之複平面導納圖的圖。
以下說明本發明之實施形態。
將作為電極活性物質之多孔質碳、導電助劑、與結著劑,在溶劑(例如水)中混合而製作電極糊料後,將此電極糊料塗佈於集電體,進而乾燥,藉以製作評估用電極。接著,將此評估用電極使用於正電極材料,作為相對電極(負極),例如使用鉑板,作為電解液,例如使用硫酸水溶液,可製作電雙層電容器。
使用於本發明之電極活性物質的多孔質碳,
可如以下方式製作。首先,將含有有機質樹脂之流動性材料;與由鹼土類金屬之氧化物、氫氧化物、碳酸鹽、有機酸鹽等之鹼土類金屬化合物所構成之模板粒子,予以濕式或乾式混合,而製作混合物。接著,將此混合物於非氧化環境或減壓環境下,例如於500℃以上之溫度碳化。最後,藉由洗淨處理,去除模板粒子,藉此,可製作多孔質碳。如此方式所製作之多孔質碳,係具有大小約略同等之多數的細孔。
此處,藉由改變模板粒子之直徑或有機質樹
脂之種類,可調整細孔直徑、多孔質碳之細孔分布、及碳質壁之厚度。因此,藉由適當選擇模板粒子之直徑與有機質樹脂之種類,亦可製作具有更均勻的細孔直徑,且具有更大之細孔容量的多孔質碳。
具體而言,作為上述有機質樹脂,較佳可使
用於單位構造中含有至少一個以上之氮或氟原子的聚醯亞胺。該聚醯亞胺,可藉由酸成分與二胺成分之聚縮合而得到。惟此情況時,酸成分及二胺成分之任一者或兩者中,必須包含一個以上之氮原子或氟原子。
具體而言,係藉由使聚醯亞胺之前驅物的聚醯胺酸成膜,將溶劑加熱去除而得到聚醯胺酸膜。接著,可藉由將所得之聚醯胺酸膜在200℃以上熱醯亞胺化,來製造聚醯亞胺。
前述二胺,可舉例2,2-雙(4-胺基苯基)六氟丙烷[2,2-Bis(4-aminophenyl)hexafluoropropane]、2,2-雙
(三氟甲基)-聯苯胺[2,2’-Bis(trifluoromethyl)-benzidine]、4,4’-二胺基八氟聯苯基,或3,3’-二氟-4,4’-二胺基二苯基甲烷、3,3’-二氟-4,4’-二胺基二苯基醚、3,3’-二(三氟甲基)-4,4’-二胺基二苯基醚、3,3’-二氟-4,4’-二胺基二苯基丙烷、3,3’-二氟-4,4’-二胺基二苯基六氟丙烷、3,3’-二氟-4,4’-二胺基二苯甲酮、3,3’,5,5’-四氟-4,4’-二胺基二苯基甲烷、3,3’,5,5’-四(三氟甲基)-4,4’-二胺基二苯基甲烷、3,3’,5,5’-四氟-4,4’-二胺基二苯基丙烷、3,3’,5,5’-四(三氟甲基)-4,4’-二胺基二苯基丙烷、3,3’,5,5’-四氟-4,4-二胺基二苯基六氟丙烷、1,3-二胺基-5-(全氟壬烯基氧基)苯、1,3-二胺基-4-甲基-5-(全氟壬烯基氧基)苯、1,3-二胺基-4-甲氧基-5-(全氟壬烯基氧基)苯、1,3-二胺基-2,4,6-三氟-5-(全氟壬烯基氧基)苯、1,3-二胺基-4-氯-5-(全氟壬烯基氧基)苯、1,3-二胺基-4-溴-5-(全氟壬烯基氧基)苯、1,2-二胺基-4-(全氟壬烯基氧基)苯、1,2-二胺基-4-甲基-5-(全氟壬烯基氧基)苯、1,2-二胺基-4-甲氧基-5-(全氟壬烯基氧基)苯、1,2-二胺基-3,4,6-三氟-5-(全氟壬烯基氧基)苯、1,2-二胺基-4-氯-5-(全氟壬烯基氧基)苯、1,2-二胺基-4-溴-5-(全氟壬烯基氧基)苯、1,4-二胺基-3-(全氟壬烯基氧基)苯、1,4-二胺基-2-甲基-5-(全氟壬烯基氧基)苯、1,4-二胺基-2-甲氧基-5-(全氟壬烯基氧基)苯、1,4-二胺基-2,3,6-三氟-5-(全氟壬烯基氧基)苯、1,4-二胺基-2-氯-5-(全氟壬烯基氧基)苯、1,4-二胺基-2-溴-5-(全氟壬烯基氧基)苯、1,3-二胺基-5-(全氟己烯基氧基)苯、
1,3-二胺基-4-甲基-5-(全氟己烯基氧基)苯、1,3-二胺基-4-甲氧基-5-(全氟己烯基氧基)苯、1,3-二胺基-2,4,6-三氟-5-(全氟己烯基氧基)苯、1,3-二胺基-4-氯-5-(全氟己烯基氧基)苯、1,3-二胺基-4-溴-5-(全氟己烯基氧基)苯、1,2-二胺基-4-(全氟己烯基氧基)苯、1,2-二胺基-4-甲基-5-(全氟己烯基氧基)苯、1,2-二胺基-4-甲氧基-5-(全氟己烯基氧基)苯、1,2-二胺基-3,4,6-三氟-5-(全氟己烯基氧基)苯、1,2-二胺基-4-氯-5-(全氟己烯基氧基)苯、1,2-二胺基-4-溴-5-(全氟己烯基氧基)苯、1,4-二胺基-3-(全氟己烯基氧基)苯、1,4-二胺基-2-甲基-5-(全氟己烯基氧基)苯、1,4-二胺基-2-甲氧基-5-(全氟己烯基氧基)苯、1,4-二胺基-2,3,6-三氟-5-(全氟己烯基氧基)苯、1,4-二胺基-2-氯-5-(全氟己烯基氧基)苯、1,4-二胺基-2-溴-5-(全氟己烯基氧基)苯或不含氟原子之p-苯二胺(PPD)、二氧基二苯胺等之芳香族二胺。又,上述二胺成分,可組合上述各芳香族二胺2種以上來使用。
另一方面,酸成分可列舉含有氟原子之4,4-
六氟異亞丙基二鄰苯二甲酸酐(6FDA)、及不含氟原子之3,4,3’,4’-聯苯基四羧酸二酐(BPDA)、苯均四酸二酐(PMDA)等。
又,作為聚醯亞胺前驅物之溶劑所使用之有機溶劑,可列舉N-甲基-2-吡咯啶酮、二甲基甲醯胺等。
作為醯亞胺化之手法,遵照如公知方法[例如參照高分子學會編「新高分子實驗學」共立出版、1996
年3月28日、第3卷高分子之合成.反應(2)158頁]所示之加熱或化學醯亞胺化之任意方法均可,本發明並不受此醯亞胺化之方法所左右。
上述聚醯亞胺以外之樹脂,除了可使用碳化
產率為40質量%以上、85質量%以下之樹脂,例如酚樹脂或石油系焦油瀝青等之外,亦可充分使用碳化產率為4質量%以上、40質量%以下之有機樹脂。例如,作為如此之碳化產率低的有機樹脂,可使用聚乙烯醇或乙酸乙烯酯、或該等2種樹脂之混合物、或檸檬酸鈣、檸檬酸鎂、檸檬酸鋇、草酸鈣、草酸鎂、草酸鋇、乙酸鈣、乙酸鎂、乙酸鋇或該等9種有機酸鹽之n水合物(n=1~10)。
再者,模板粒子之直徑較佳為大致同樣直
徑。模板粒子之直徑若成為大致同樣直徑,模板粒子會在基質中(燒成物中)均勻地分散,因此模板粒子間之間隔的不均會變小。因此,碳質壁之厚度為接近均勻的三次元網目構造,而成為形成同一尺寸之連續孔的構成之故。
又,將鹼土類金屬化合物作為模板粒子使
用,鹼土類金屬化合物可藉由弱酸或熱水去除(亦即,可不使用強酸來去除模板粒子),因此於去除模板粒子之步驟中,可抑制多孔質碳本身的性狀變化之故。再者,使用弱酸時,係有去除速度變快的優點,另一方面,使用熱水時,係有可防止酸殘留而成為雜質的不良狀況的優
點。又,於去除模板粒子之步驟中,溶出之氧化物溶液可再度作為原料使用,可減低多孔質碳之製造成本。
進一步地,前述混合物之碳化,較佳為在非
氧化環境或減壓環境,以500℃以上、1500℃以下之溫度進行。因為高碳產率之樹脂為高分子,故未達500℃則可能有碳化不充分,細孔之發達不充分的情況,另一方面,1500℃以上則收縮變大,氧化物燒結而粗大化,因此細孔之尺寸變小,且比表面積變小之故。非氧化性環境,係指氬環境或氮環境等,減壓環境係指133Pa(1torr)以下之環境。
再者,上述多孔質碳之容積密度較佳為
0.1g/cc以上、1.0g/cc以下。容積密度未達0.1g/cc時,可能難以確保比表面積,變得無法保持碳質壁之形狀,另一方面,容積密度超過1.0g/cc以下時,可能難以形成三次元網目構造,細孔之形成變得不充分。
又,作為電解液,不限定於硫酸水溶液,可
使用硫酸鈉、硫酸鉀、硫酸鋰、氫氧化鈉、氫氧化鉀等之水系電解液,或碳酸伸丙酯、碳酸伸乙酯、碳酸二甲酯、碳酸二乙酯、乙腈等之有機電解液,四氟化硼酸四乙基銨、三乙基甲基銨雙(三氟甲烷磺醯基)醯亞胺、四乙基銨雙(三氟甲烷磺醯基)醯亞胺等之一般作為電解液使用之離子液體等。
首先,如圖1(a)所示,作為起始物質,以有機酸鹽n水合物(具體而言係檸檬酸鎂9水合物之檸檬酸部分)1為碳酸前驅物,與檸檬酸鎂9水合物(和光純藥工業股份有限公司製之化學用試藥)中之鎂部分2作為模板前驅物。接著,如圖1(b)所示,將此起始物質在氮環境中、800℃進行1小時熱處理,使有機酸鹽熱分解,藉以得到具備碳質壁3之燒成物。接著,如圖1(c)所示,將所得之燒成物以添加為1mol/l比例之硫酸水溶液洗淨,藉由使鎂化合物大致完全地溶出,得到具有多數細孔4之多孔質碳5。再者,圖1中,係將多孔質碳5平面地(示意地)表示,因此細孔4彼此雖看起來並未連通(氣孔部分未連續),但實際上如圖2所示,係成為細孔為開放氣孔,且氣孔部分連續的構成。
將作為電極活性物質之上述多孔質碳、作為導電助劑之科琴黑(KB)、與作為結著劑之橡膠系黏結劑(日本Zeon股份有限公司製、BM-400),以質量比成為80:10:10的方式混合,調製電極糊料。具體而言,將0.3g之多孔質碳、與0.0375g之KB混合,添加一定量之蒸餾水(標準品為2.5ml)並混合藉以得到混合物後,於此混
合物中添加0.0375g之BM-400,藉由迅速混練,調製電極糊料。
接著,將此電極糊料,塗佈於80網目之鉑網(塗佈於大約10×10mm兩面),進一步藉由於90℃乾燥機內乾燥12小時以上,製作評估用電極。此時,所塗佈之導電助劑、KB與多孔質碳之總量為30mg左右,藉由於電化學測定前秤量,而反映施加之電流密度。
之後,進行電解液之調製與單元之組立。
水系電容器之電解液,係使用40質量%之硫酸水溶液。此時,電解液中之溶存氧的存在,當陽極極化時,對產生氧之反應的電流量係重疊。結果,會妨礙估計精度良好之電容器容量。因而,採取40質量%之硫酸水溶液40ml,藉由進行1小時氬通氣以調製電解液。再者,通氣所用之氣體並不限定為氬,亦可使用氮。惟,較佳為使用氧去除能力更高之氬。
單元係使用三極式單元。具體而言,係如以下方式製作。於玻璃容器內,配置工作電極、夾住此工作電極2枚相對電極、與參考電極。作為上述工作電極係使用上述評估用電極,作為上述相對電極係使用150網目之鉑網,作為上述參考電極係使用Ag/AgCl電極。接著,
將其使用真空泵抽真空至0.02MPa後,將上述通氣處理後之電解液導入單元內,藉進一步持續抽真空1小時以上,完成電極之脫氣。藉此完成三極式單元。
如此方式所製作之單元,以下稱為單元A1。
除了使起始物質為檸檬酸鎂,且使熱處理溫度為1000℃來製作多孔質碳以外,係與上述實施例1同樣方式來製作單元。
如此方式所製作之單元,以下稱為單元A2。
除了使起始物質為檸檬酸鎂來製作多孔質碳以外,係與上述實施例1同樣方式來製作單元。
如此方式所製作之單元,以下稱為單元A3。
除了使熱處理溫度為1000℃來製作多孔質碳以外,係與上述實施例1同樣方式來製作單元。
如此方式所製作之單元,以下稱為單元A4。
除了使用一般作為電容器用碳材料而評估之活性碳(Kuraray chemical股份有限公司製、YP-17)作為碳材料,
以取代多孔質碳以外,係與上述實施例1同樣方式來製作單元。
如此方式所製作之單元,以下稱為單元Z。
對上述單元A1~A4、Z所用之碳材料,求得比表面積(BET比表面積)、介孔容量、與介孔直徑,將其結果示於表1。再者,上述比表面積,係由吸附等溫線之結果,使用BET法來算出。又,介孔容量係由BET法求得,介孔直徑係以BJH(Berret-Joyner-Halenda)法求得。
進一步地,調查了上述單元A1~A4、Z之電
容器響應頻率與過渡頻率,其結果示於表1、圖3~圖5。電化學測定之機器,係使用Solartron 1287、1255B(東陽Technica股份有限公司製)。具體的測定,係使用定電壓阻抗測定法,對於浸漬電位,於100000~0.1Hz之頻率區域測定5mV之交流電壓。
此處,上述電容器響應頻率,係指圖3之-45°
時之頻率、及圖4及圖5中Y’之值=Y”之值時的頻率,相當於電容器之充電完成的頻率。又,過渡頻率,係相當於圖4及圖5中描繪的2個山峰(兩圖中,左邊的山峰為低頻區域、右邊的山峰為高頻區域)之邊界的頻率,可理解作為由物質移動速率限制至電容器之行為的響應頻率。再者,電容器響應頻率之值越高,越可期待充電快速地完成,過渡頻率之值越高,則可理解為顯示電解液快速地於
多孔質碳內所存在之細孔內擴散。
由表1、圖3~圖5明確可知,電容器Z中,
頻率響應速度為0.37Hz的低水準,相對於此,電容器A1~A4中,可觀察到頻率響應速度為0.80~1.15Hz的高水準。因此,電容器A1~A4相較於電容器Z,可知充電係迅速地完成。
又,電容器Z中,過渡頻率為100Hz之低水準,相對於此,電容器A1~A4中,可觀察到頻率響應速度為200~300Hz之高水準。因此,電容器A1~A4相較於電容器Z,可知電解液對電極所形成之細孔內的擴散速度變高。
進一步地,電容器Z相較於電容器A1~A4,比表面積雖大,但介孔僅以無法算出的程度存在,其結果,介孔容量亦特別小。因此,電容器Z相較於電容器A1~A4,因介孔容量小,故即使使用相同電解液時,時間常數亦為2倍不良。
本發明可使用作為電容器之電極材料等。
Claims (5)
- 一種電容器,其特徵為具備含有碳材料之分極性電極、與電解液,且使用40質量%之硫酸作為上述電解液時的頻率響應速度為0.7Hz以上。
- 如申請專利範圍第1項之電容器,其係使用具備細孔與構成此細孔之輪廓的碳質壁,上述細孔為開放氣孔,且採取氣孔部分為連續之構成的多孔質碳,作為上述碳材料。
- 如申請專利範圍第2項之電容器,其中上述細孔之直徑為2nm以上、150nm以下。
- 如申請專利範圍第2或3項之電容器,其中上述細孔之容量為0.2ml/g以上。
- 如申請專利範圍第2~4項中任一項之電容器,其中上述多孔質碳之比表面積為200m2/g以上。
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US20110128671A1 (en) * | 2006-05-15 | 2011-06-02 | Yury Gogotsi | Supercapacitors and methods for producing same |
JP2008013394A (ja) * | 2006-07-05 | 2008-01-24 | Daido Metal Co Ltd | 活性炭およびその製造方法 |
JP2010105836A (ja) * | 2008-10-29 | 2010-05-13 | Jfe Chemical Corp | 電気二重層キャパシタ用活性炭およびその製造方法 |
JP2010114356A (ja) | 2008-11-10 | 2010-05-20 | National Univ Corp Shizuoka Univ | 電気化学キャパシタ |
JP2010208887A (ja) * | 2009-03-10 | 2010-09-24 | Toyo Tanso Kk | 多孔質炭素及びその製造方法 |
JP5678372B2 (ja) * | 2009-11-30 | 2015-03-04 | 独立行政法人産業技術総合研究所 | 窒素含有多孔質炭素材料とその製造方法、及び該窒素含有多孔質炭素材料を用いた電気二重層キャパシタ |
JP5931326B2 (ja) * | 2010-02-23 | 2016-06-08 | カルゴンカーボンジャパン株式会社 | 電気二重層キャパシタ用活性炭 |
CN103370756B (zh) * | 2010-12-28 | 2018-05-11 | 巴斯福股份公司 | 包含增强的电化学特性的碳材料 |
WO2012121363A1 (ja) * | 2011-03-09 | 2012-09-13 | 東洋炭素株式会社 | 多孔質炭素及びその製造方法 |
JP5688321B2 (ja) * | 2011-04-13 | 2015-03-25 | 東洋炭素株式会社 | 多孔質炭素及びその製造方法 |
JP6071261B2 (ja) * | 2012-06-15 | 2017-02-01 | 東洋炭素株式会社 | 多孔質炭素材料およびその製造方法、並びにそれを用いた電気二重層キャパシタ |
-
2012
- 2012-08-08 JP JP2012176495A patent/JP2014036113A/ja active Pending
-
2013
- 2013-08-07 US US14/413,390 patent/US20150162138A1/en not_active Abandoned
- 2013-08-07 CA CA2880530A patent/CA2880530A1/en not_active Abandoned
- 2013-08-07 WO PCT/JP2013/071368 patent/WO2014024921A1/ja active Application Filing
- 2013-08-07 KR KR20157005778A patent/KR20150041053A/ko not_active Application Discontinuation
- 2013-08-07 EP EP13827796.7A patent/EP2884512A1/en not_active Withdrawn
- 2013-08-07 CN CN201380031967.XA patent/CN104380409A/zh active Pending
- 2013-08-08 TW TW102128463A patent/TW201419329A/zh unknown
-
2015
- 2015-02-27 IN IN1690DEN2015 patent/IN2015DN01690A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN104380409A (zh) | 2015-02-25 |
KR20150041053A (ko) | 2015-04-15 |
US20150162138A1 (en) | 2015-06-11 |
CA2880530A1 (en) | 2014-02-13 |
JP2014036113A (ja) | 2014-02-24 |
WO2014024921A1 (ja) | 2014-02-13 |
EP2884512A1 (en) | 2015-06-17 |
IN2015DN01690A (zh) | 2015-07-03 |
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