WO2001086674A1 - Carbone active pour condensateur electrique a couche double - Google Patents
Carbone active pour condensateur electrique a couche double Download PDFInfo
- Publication number
- WO2001086674A1 WO2001086674A1 PCT/JP2001/003820 JP0103820W WO0186674A1 WO 2001086674 A1 WO2001086674 A1 WO 2001086674A1 JP 0103820 W JP0103820 W JP 0103820W WO 0186674 A1 WO0186674 A1 WO 0186674A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- activated carbon
- electric double
- double layer
- less
- electrode
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 239000003990 capacitor Substances 0.000 title claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 24
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 9
- 230000002459 sustained effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910018286 SbF 6 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- 240000006108 Allium ampeloprasum Species 0.000 description 1
- 235000005254 Allium ampeloprasum Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- H01G11/42—Powders or particles, e.g. composition thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
-
- 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
- H01G11/34—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
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an activated carbon for electric double layer capacity. More specifically, the present invention relates to activated carbon for electric double layer capacity, which has high output density and excellent durability, using coconut as a raw material. Background art
- Electric double layer capacity is based on the principle that electric charge is stored in the electric double layer formed at the interface between the polarizable electrode and the electrolyte, and compared to secondary batteries such as lead-acid batteries and nickel-hydrogen secondary batteries.
- secondary batteries such as lead-acid batteries and nickel-hydrogen secondary batteries.
- the advantage is that rapid charging and discharging with a large current is possible.
- Activated carbon is usually used as the material of the polarizable electrode because of its large interface and excellent conductivity.
- the electric double layer capacity required for hybrid vehicles and electric vehicles is not only the capacitance (F), but also the high output (W) that can be repeatedly charged and discharged with a large current of the order of 100 amperes. And many technical issues remain. Therefore, in order to increase the output density, the thickness of the porous electrode mainly composed of activated carbon, the current collector, and the thickness of the separator can be optimized (Japanese Patent Application Laid-Open No. Hei 11-317332). Electrode manufacturing techniques such as using a composite electrode of activated carbon impregnated with aluminum as a polarizable electrode (Japanese Patent Application Laid-Open No. 10-59060) have been proposed.
- JP-A-1-321620 discloses that powdered activated carbon heat-treated at 1000 ° C. is used as an electrode material for a capacitor
- JP-A-3-180001 discloses that the activated carbon containing oxygen is contained therein. It is stated that by setting the amount to 25 to 35% by weight, it is possible to improve the capacitance of the electric double layer capacity.
- Japanese Patent Publication No. 4-77070 discloses that an activated carbon having an average pore diameter of 1.5 nm (15 A) or more as an electrode material for a capacitor is excellent in temperature characteristics. -According to Japanese Patent No.
- powdered activated carbon exhibiting high capacitance has a specific surface area of 1800 to 3500 m 2 Zg, an average pore diameter of 0.5 to 1.5 nm (5 to 15 A), and occupies the entire pore volume. It is said that the pore volume having a diameter of 2.Onm (2 OA) or more is 20 to 40% of the total pore volume, but these publications disclose an average pore diameter of 1.95 nm ( Select a specific range from 19.5 A) to 2.20 nm (22 A) and set the pore volume between 5.Onm (5 OA) and 30.Onm (300 A) to 0. . 05 ⁇ 3111 3 or more and 0.15 cm 3 Zg or less is not described.
- Japanese Patent Publication No. 60-15138 discloses that fibrous carbon obtained by carbonizing phenolic fiber and then activating it is suitable as an electrode material for a capacitor.
- the 56827 discloses, use the concentration of 1.0 meq / g or less of carbon fiber or carbon powder acidic functional group on the surface as a Capacity evening electrode material Irare, those 500 m 2 Zg or more specific surface area It is described that it is preferable, specifically, to use a phenolic resin-based activated carbon fiber.
- Japanese Patent Publication No. 44444 / JP describes that a specific phenol resin foam activated by carbonization is used as an electrode material for a capacitor.
- the phenolic resin-based materials described in Japanese Patent Publication No. 60-15138, Japanese Patent Publication No. 6-56827 and Japanese Patent Publication No. 4-44407 were carbonized.
- the activated carbon obtained by the activation treatment is substantially the same as that in the present invention in terms of the specific surface area, but generally, the phenol resin-based carbonized material used as the activation raw material is a uniform amorphous carbon. Most of the pores formed in the activated carbon obtained by activating this have a pore diameter of 15 A or less.
- the average pore diameter is usually about 18 A or less, which is smaller than the average pore diameter in the present invention, and is a relatively large fine pore of 5.0 to 3.0 nm.
- the pore region has no substantial pore distribution.
- the electrode materials for electric double layer capacitors described in these publications are all aimed at increasing the capacitance per volume or per weight (F / g, F / cm 3 ).
- the discharge current density per unit area of the electrode is 0. 1 is rather small castings and 2 mA / cm 2 or so, a high current density, for example, 1 O mA No effect as an electrode material at large current densities of / cm 2 or more has been confirmed, and they do not disclose any activated carbon suitable for the above-mentioned high-power applications.
- 60-151538 has a lower electrical resistance than an electrode obtained by molding or coating powdered activated carbon. This is a feature, and in that sense it is preferable because high output can be expected.
- the electrode has a low bulk density, has a large output per weight, but has a small capacity per volume.
- the features required for the electric double layer capacity are high durability such as a larger number of charge / discharge cycles that can be used and a small decrease in capacity during continuous voltage application tests compared to conventional secondary batteries. It is.
- the electric double layer capacity using activated carbon containing a large amount of oxygen as the electrode material described in the above-mentioned Japanese Patent Application Laid-Open No. H3-180013 a large decrease in capacity due to an increase in resistance and the like during charging and discharging.
- Even with the above-mentioned electrode materials using known activated carbon it is possible to reduce the internal resistance of the electrodes and increase the output density to some extent by improving the electrode manufacturing method, but there is a high output density.
- the present invention provides an electric power supply having a large output density per volume and a small decrease in output density even when charging and discharging cycles under a large current are repeated or a constant voltage is continuously applied for a long time.
- the purpose is to provide activated carbon suitable for multi-layer capacity. Disclosure of the invention
- the present inventors have conducted intensive studies to solve the above problems, and as a result, activated carbon obtained by activating a specific raw material under appropriate conditions has an appropriate pore distribution, specific surface area, surface state
- the present invention has been found to have high thermal power, high power density per unit volume, and excellent durability.
- the gist of the present invention is an activated carbon obtained by carbonizing coconut, having a BET specific surface area of 200 On ⁇ Zg or more and 2500 m 2 / g or less, and an average pore diameter of 1.95 nm ( 12.5 A) or more and 2.20 nm (22 A) or less, and pore diameter calculated by the Clanton inclay method 5.
- Pore volume between Onm (5 OA) and 30.0 nm (30 OA) Is not less than 0.05 cm 3 / g and not more than 0.15 cm 3 Z g.
- the oxygen content per 1 g of activated carbon is lmg or more and 2Omg or less, and the natural potential at the counter electrode lithium in the non-aqueous electrolytic solution is 2. 85 V or more and 3.03 V or less, and that the activated carbon is obtained by activating steamed coconut charcoal.
- the activated carbon for electric double layer capacity is activated carbon obtained by carbonizing coconut shell, having a BET specific surface area of 2,000 m 2 / g or more and 2500 m 2 / g or less, and an average pore diameter of 1.95 nm (19.5 A) or more 2.20 nm (22 A) or less, and pore diameter calculated by the Cranston inclay method 5.0 nm (50 A) to 30.0 nm (300 A) It is essential to satisfy each physical property that the pore volume is 0.05 cm 3 / g or more and 0.15 cm 3 / g or less, and preferably, the oxygen content per 1 g of activated carbon is 1 mg or more. This is to further satisfy the physical property of being 2 Omg or less and having a natural potential of 2.85 V or more and 3.03 V or less at the counter electrode lithium in the non-aqueous electrolyte.
- the bulk density of the activated carbon is high, and the electrolyte ions and solvent molecules of the electrolyte present in the pores of the activated carbon are reduced.
- the ionic conductivity increases, and a sufficiently high output can be exhibited even when charging and discharging with a large current.
- the oxygen content in the activated carbon to an appropriate amount and adjusting the natural potential of the activated carbon electrode in the non-aqueous electrolyte to an appropriate range, the durability of the electric double layer capacity is improved. Can be further improved.
- the present invention can exhibit such excellent characteristics from activated carbon made from coconut husk, so that productivity and cost efficiency are higher than those using expensive synthetic resin such as phenol resin as raw material. It has excellent characteristics.
- the specific surface area of the activated carbon is too large, the bulk density is reduced and the output per unit volume is reduced. is to mandatory that the 2 / g or less under 2000 m 2 / g or more 2500 m, preferably not more than 2000 m 2 / g or more 240 On ⁇ Zg, more preferably not more than 2050M 2 / g or more 2250 m 2 / g . If the specific surface area is smaller than this range, the output per unit weight decreases, which is not preferable.
- the activated carbon for electric double layer capacity of the present invention is required to have an average pore diameter of 1.95 nm (19.5 A) or more and 2.2 Onm (22 A) or less. average If the pore diameter is too small, the electric resistance, which is thought to be due to the diffusion resistance of electrolytic ions in the pores during charging and discharging under a large current, increases, which is not suitable for high-output applications. This is not preferable because the bulk density decreases and the output per unit volume decreases.
- the activated carbon for electric double layer capacity of the present invention has a pore volume between 5.0 nm (50 A) and 30.0 nm (300 A), calculated by the Cranston inkle method, of 0 nm. It must be between 05 cm 3 / g and 0.15 cm 3 Zg. If the pore volume is too large, the bulk density of the electrode is reduced, and the output per volume is undesirably reduced. On the other hand, if it is too small, the internal resistance of the electrode increases, and as a result, the power density decreases. It is preferably from 0.07 to 0.13 cm 3 / g, more preferably from 0.08 to 0.12 cm 3 Zg.
- the activated carbon for electromagnetic double layer capacity of the present invention requires that the raw material be palm.
- the raw materials of activated carbon other than palm are petroleum pitch, petroleum coke, fiber spun from tar pitch, synthetic polymer, phenolic resin, furan resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyimide
- resins such as resin, polyamide resin, liquid crystal polymer, plastic waste, and waste tires.
- a phenol resin is used as a raw material for activated carbon, a resin having a specific surface area of 2000 m 2 Zg or more is obtained.
- the activated carbon of the present invention can be obtained by carbonizing a coconut shell and then activating it.
- Activation methods are roughly classified into a gas activation method and a chemical activation method.
- gas activation method chemical activation is chemical activation
- physical activation is also called physical activation
- the carbonized raw material is contacted at high temperature with steam, carbon dioxide, oxygen, other oxidizing gases, etc. This produces activated carbon.
- chemical activation method a raw material is evenly impregnated with an activation chemical, heated in an inert gas atmosphere, and activated carbon is obtained by dehydration and oxidation of the chemical. You.
- Chemicals used include zinc chloride, phosphoric acid, sodium phosphate, calcium chloride, potassium sulfide, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium sulfate, potassium sulfate, calcium carbonate, etc. .
- the method for producing activated carbon is not particularly limited, and is not limited to the above methods, as long as the generated activated carbon satisfies the above characteristics.
- activated carbon obtained by the steam activation method is an electric double layer capacity.
- the steam activation method is advantageous because it has the features of excellent evening durability and low production cost.
- the activated carbon has various shapes such as a crushed shape, a granular shape, a granule, a fiber, a felt, a woven fabric and a sheet shape, and any of them can be used in the present invention.
- the activated carbon obtained by the steam activation method according to the present invention is obtained by pulverizing and sizing coconut shells, carbonizing (dry-distilling) the coconut shells in an inert atmosphere, and obtaining 800 ° C. C to 130 ° C or lower, preferably 850 ° C to 120 ° C or lower, more preferably 900 ° C to 110 ° C or lower, and 30% by volume or higher It can be obtained by heat treatment in an inert gas such as nitrogen, argon, or combustion exhaust gas containing a water vapor gas atmosphere of 100% by volume or less.
- an inert gas such as nitrogen, argon, or combustion exhaust gas containing a water vapor gas atmosphere of 100% by volume or less.
- the activated charcoal or activated charcoal before activation and the activated carbon obtained by the activation treatment are washed in an aqueous acid solution such as hydrochloric acid, nitric acid, sulfuric acid, etc. to remove metal impurities contained in carbon, What removed ash etc. is also included in the present invention.
- an aqueous acid solution such as hydrochloric acid, nitric acid, sulfuric acid, etc. to remove metal impurities contained in carbon, What removed ash etc. is also included in the present invention.
- the activated carbon after the activation treatment is heat-treated at 500 to 250 ° C, preferably at 700 to 150 ° C, in an inert atmosphere such as nitrogen, argon, helium, and xenon.
- an inert atmosphere such as nitrogen, argon, helium, and xenon.
- unnecessary surface functional groups may be removed, or the crystallinity of carbon may be developed to increase electron conductivity.
- the average particle diameter is preferably 30 m or less, more preferably 7 to 20 zm, from the viewpoint of improving the bulk density of the electrode and reducing the internal resistance.
- the activated carbon for electric double layer capacity according to the present invention is characterized in that, in an electric double layer capacity using a non-aqueous electrolyte, when the natural potential in the electrolyte is Li / Li + as a counter electrode, 2.85 V It is preferably not less than 3.03 V, more preferably from 2.9 to 3.00 V. If the natural potential is too high, for example, using activated carbon as the positive electrode When 2.5 V or more is applied to the assembled electric double layer capacity, the potential of the positive electrode after charging becomes approximately 4.3 V (vs.
- the measurement of the spontaneous potential of the carbonaceous electrode of the positive electrode in the present invention is performed by using a usual electrochemical technique.
- the potential reference such as a standard hydrogen electrode in an aqueous solution is not strictly defined, but in practice, electrodes such as silver-silver chloride electrode, platinum electrode, and lithium electrode
- the method is generally performed widely using the method, and can be measured by the same method in the present invention.
- the oxygen content per 1 g of activated carbon is preferably from 1 mg to 20 mg, more preferably from 2 mg to 1 O mg.
- the oxygen content in the present invention is included in the decomposition gas generated by heat-treating activated carbon at about 100 ° C. in a vacuum or in an inert gas atmosphere such as argon gas or nitrogen gas. carbon monoxide (CO), to quantify the carbon dioxide (C 0 2), a value indicating the amount of oxygen contained in these molecules in total.
- CO carbon monoxide
- this oxygen amount corresponds to oxygen-containing functional groups in activated carbon, that is, carboxyl groups, phenol groups, ketones, and the like.
- the oxygen content in the present invention can be said to be an index indicating the total amount of oxygen-containing functional groups contained in the activated carbon.
- the oxygen content in 1 g of activated carbon exceeds the above range and is too large, the electric double layer capacity will cause gas decomposition, which is presumed to be due to decomposition of oxygen-containing functional groups in the cell or reaction with the electrolyte during charging and discharging. It is not preferable because the electrical resistance increases and the durability of the capacitor deteriorates.
- the amount is less than the above range, the affinity with the binder for the electrode is reduced during the production of the electrode, and as a result, the bulk density of the electrode is reduced, and the output per unit volume is undesirably reduced.
- the polarizable electrode mainly composed of activated carbon is formed by an ordinary method, and is mainly composed of activated carbon and a binder, but a conductive substance may be further added to impart conductivity to the electrode. .
- Activated carbon can be formed by a conventionally known method. For example, a mixture of activated carbon and acetylene black is mixed with polytetrafluoroethylene, mixed, and then press-molded to obtain a molded body. Alternatively, activated carbon may be added and mixed with coal pitch having a relatively high softening point as a binder, and then molded and fired in an inert atmosphere up to the thermal decomposition temperature of the binder to obtain a molded body.
- the electrode may be any of a thin coating film, a sheet-shaped or plate-shaped formed body, and a plate-shaped formed body made of a composite.
- Activated carbon can be pulverized into desired granules prior to mixing with the binder.However, the activated carbon is mixed with the binder with a relatively large particle size and ground together to form a mixed slurry or dry pulverized product. You can also get.
- the conductive agent used in the activated carbon electrode is selected from the group consisting of metal fibers such as acetylene black, Ketjen black, etc., natural graphite, thermally expanded graphite, carbon fiber, ruthenium oxide, titanium oxide, aluminum, nickel and the like. At least one conductive agent selected is preferred. Acetylene black and Ketjen black are particularly preferred in that the conductivity is effectively improved with a small amount, and the amount of the activated carbon to be mixed depends on the bulk density of the activated carbon. Therefore, the content of activated carbon is preferably 5 to 50%, and more preferably about 10 to 30%.
- Binders include polytetrafluoroethylene, polyvinylidene fluoride, carboxycellulose, methylcellulose, fluorinated olefin copolymer crosslinked polymer, polyvinyl alcohol, polyacrylic acid, polyimide, petroleum pitch, and coal pitch. It is preferable to use at least one of phenol resins.
- the current collector is not particularly limited as long as it has electrochemical and chemical corrosion resistance.
- stainless steel, nickel, aluminum, copper and the like are preferably used.
- the electrolyte is preferably a non-aqueous electrolyte.
- triethyl methyl ammonium ion triethyl methyl ammonium ion.
- a quaternary Oniumukachion that, BF 4 _, PF 6 one, C10 4 _, SbF 6 - or CF 3 S0 3 _ comprising salts of a combination of a Anion, were or, a lithium salt cation is a lithium ion
- lithium salt LiBF 4, L iC10 4, L iPF 65 L i SbF 6, L i As F 6, L i CF 3 S0 3, LiC (CF 3 S0 2) 3, L iB (C 6 H 5) 4, L i C 4 F 9 S0 3, LiC 8 F 17 S0 3, LiN (CF 3 S0 2) 1 or more substances favored arbitrary selected from 2.
- a salt obtained by combining BF 4 ⁇ , PF 6 ⁇ , C 10 4 ⁇ , and SbF 6 is preferable.
- the solute concentration in these non-aqueous electrolytes is preferably from 0.3 to 2.0 mol / l, particularly from 0.7 mol / l or more to 1.9 so that the characteristics of the electric double layer capacitor can be sufficiently brought out.
- concentration is less than or equal to the molar Z, a high electric conductivity is obtained, which is preferable.
- a concentration of 2.0 mol / liter or more is not preferred because the electric conductivity of the electrolyte solution is reduced. If it is less than 0.3 mol / liter, the electric conductivity is low at both room temperature and low temperature, which is not preferable.
- Propylene carbonate solution of tetra-E chill ammonium Niu arm tetrafluoropropoxy O Lobo Les Ichito (E t 4 NB 4) is preferably an electrolytic solution, 0.1 as the concentration of E 1 4 NB 4 5 ⁇ 1. 0 mole / Ridzutoru Is preferred.
- the solvent of the non-aqueous electrolyte is not particularly limited, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, getyl carbonate, sulfolane, methyl sulfolane, aptyrolactone, avalerolactone, From at least one selected from N-methyloxazolidinone, dimethyl sulfoxide, and trimethyl sulfoxide.
- Organic solvents are preferred.
- One or more organic solvents selected from the group consisting of a high melting point solvent such as ethylene carbonate alone cannot be used because it becomes a solid at a low temperature and must be used as a mixed solvent with propylene carbonate and a low melting point solvent.
- the water content in the non-aqueous electrolyte is preferably 20 O ppm or less, more preferably 5 O ppm or less, so as to obtain a high withstand voltage.
- the charcoal (5 Og) was put into a leek kiln through which nitrogen gas containing steam was passed, and steam activation was performed.
- the activation temperature, activation time, and water vapor concentration in the nitrogen gas are as shown in Table 11 below.
- the obtained activator was washed in hydrochloric acid and then repeatedly washed with demineralized water. After washing, the activator was dried. After drying, the activator was pulverized to obtain activated carbon powder having an average particle size of 10 to 20 m (Examples 1 to 6, Comparative Examples 1 and 3).
- Comparative Example 2 pulverized bituminous coal was used instead of coconut and charcoal.
- phenol resin (novolak) cured product was heated at 700 ° C in a nitrogen atmosphere.
- Activated carbon powder was produced under the same conditions as in Example 1 except that the carbide obtained by carbonization was used. Table 1
- the obtained activated carbon powder has a BET specific surface area, a pore volume between 5.0 nm (5 OA) and 30.0 nm (30 OA), and a total pore volume of Sotopmatic 1800 type ( The calculated value was calculated from the adsorption isotherm of activated carbon obtained by measuring the equilibrium adsorption amount of nitrogen gas at each relative pressure at the liquid nitrogen temperature of the activated carbon powder.
- the average pore diameter of the activated carbon powder was calculated from the total pore volume and the BET specific surface area determined from the above nitrogen gas adsorption isotherm, assuming that the activated carbon had a cylindrical pore shape.
- the oxygen content in the activated carbon was determined as follows.
- Table 12 shows the physical property values of the activated carbon calculated as described above.
- Table 1 2 Physical properties of activated carbon
- the positive and negative electrode moldings were vacuum impregnated with a propylene carbonate solution of (C 2 H 5 ) 4 NB F 4 as an electrolytic solution. did.
- the positive electrode molded body and the negative electrode molded body impregnated with the electrolytic solution are opposed to each other via a polyethylene separator, and then they are swaged and sealed in a stainless steel coin cell to form a coin cell type electric double layer capacitor. I got
- the coin cell type electric double layer capacity was obtained in a 25 ° C constant temperature bath, and HJ-2 After applying a voltage of 2.5 V with a 01 type charge / discharge test apparatus (manufactured by Hokuto Denko Corporation), the battery was discharged at a constant current of 2 OmA / cm 2 in current density.
- the initial capacitance (F) was determined from the gradient between 2.5 V and 1.0 V of the obtained discharge curve.
- the voltage drop (IR drop: IR drop) immediately after the discharge was read from the discharge curve. If the IR—drop is large, the resulting energy density will be low, which is not desirable. Table 1 shows the results.
- Table 1 3 Initial performance 2 5 ° CZ2.5V coin cell
- Distilled water is added to a mixture of 8 parts by weight of each activated carbon obtained in the production example of activated carbon, 3 parts by weight of conductive carbon black, and 3 parts by weight of cellulosic binder, and these are kneaded to obtain a paste for electrode coating.
- the obtained paste was applied to an etched aluminum foil and dried to obtain an electrode body having a activated carbon base film thickness of 40 m.
- Two electrode bodies having an effective electrode area of 7.07 cm ⁇ 7.07 cm (50 cm 2 ) were obtained from the above electrode bodies, and each was used as a positive electrode and a negative electrode. The positive electrode and the negative electrode were opposed to each other with the activated carbon electrode membrane inside through a cellulose separator to obtain an electrochemical device.
- the device was sandwiched between glass plates, and the outside of the glass plate was sandwiched between stainless steel plates. The device was then fixed with bolts and nuts to form an electric double layer capacity device.
- the obtained capacitor element was dried by heating in a vacuum to remove impurities.
- a device was impregnated with a propylene carbonate solution of (C 2 H 5 ) 4 NB F 4 as an electrolytic solution to obtain an electric double layer capacity.
- the obtained electric double layer capacity was discharged in a 25 ° C constant temperature bath by applying 2.5 V using a commercially available charge / discharge tester. From the discharge curve, the capacitance (FZcm 3 ), the internal resistance ( ⁇ ), and the output density (W / cm 3 ) when discharging between 2.5 to 1.5 V for 2 seconds were calculated. However, the capacity per unit volume (FZc m 3 , W / cm 3 ) is calculated by converting the capacitance (F) and output (W) obtained from the obtained discharge curve into the volume per activated carbon electrode membrane. It was calculated by the following. Table 4 shows the calculated capacity characteristics.
- the durability test of the electric double layer capacity was performed as follows.
- the positive and negative electrode moldings were vacuum impregnated with a propylene carbonate solution of (C 2 H 5 ) 4 NB F 4 as an electrolytic solution. did.
- the positive electrode molded body and the negative electrode molded body impregnated with the electrolytic solution are opposed to each other via a polyethylene separator, and then they are swaged and sealed in a stainless steel coin cell to form a coin cell-type electric double layer capacitor. I got
- the activated carbon electrode and the lithium metal foil were used.
- the current collector, the activated carbon electrode, and the separator are sandwiched between two Teflon plates with a thickness of 5 mm and four bolt holes from the outermost to make good contact with each other.
- propylene carbonate solution of LiBF 4 was crushed immersed in containing finely one car.
- the output density per volume is large and the current is large. It is possible to provide an electric double layer capacity with a small decrease in output density even when the charge / discharge cycle is repeated at a constant voltage or when a constant voltage is continuously applied for a long time.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP01926133A EP1211702B1 (en) | 2000-05-09 | 2001-05-07 | Activated carbon for electric double layer capacitor |
DE60121705T DE60121705T2 (de) | 2000-05-09 | 2001-05-07 | Aktivierter kohlenstoff für elektrischen doppelschichtkondensator |
US11/471,701 US7625839B2 (en) | 2000-05-09 | 2001-05-07 | Activated carbon for use in electric double layer capacitors |
US10/040,419 US7091156B2 (en) | 2000-05-09 | 2002-01-09 | Activated carbon for use in electric double layer capacitors |
Applications Claiming Priority (2)
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JP2000136253 | 2000-05-09 | ||
JP2000-136253 | 2000-05-09 |
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US10/040,419 Continuation US7091156B2 (en) | 2000-05-09 | 2002-01-09 | Activated carbon for use in electric double layer capacitors |
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WO2001086674A1 true WO2001086674A1 (fr) | 2001-11-15 |
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PCT/JP2001/003820 WO2001086674A1 (fr) | 2000-05-09 | 2001-05-07 | Carbone active pour condensateur electrique a couche double |
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US (2) | US7625839B2 (ja) |
EP (1) | EP1211702B1 (ja) |
DE (1) | DE60121705T2 (ja) |
WO (1) | WO2001086674A1 (ja) |
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US7091156B2 (en) | 2000-05-09 | 2006-08-15 | Mitsubishi Chemical Corporation | Activated carbon for use in electric double layer capacitors |
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Also Published As
Publication number | Publication date |
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US7625839B2 (en) | 2009-12-01 |
DE60121705D1 (de) | 2006-09-07 |
US20060240979A1 (en) | 2006-10-26 |
EP1211702A1 (en) | 2002-06-05 |
US20020114126A1 (en) | 2002-08-22 |
EP1211702B1 (en) | 2006-07-26 |
DE60121705T2 (de) | 2007-08-02 |
US7091156B2 (en) | 2006-08-15 |
EP1211702A4 (en) | 2005-08-17 |
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