WO2005071702A1 - レドックスキャパシタ用電極材料及びその製造方法 - Google Patents
レドックスキャパシタ用電極材料及びその製造方法 Download PDFInfo
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- WO2005071702A1 WO2005071702A1 PCT/JP2005/001157 JP2005001157W WO2005071702A1 WO 2005071702 A1 WO2005071702 A1 WO 2005071702A1 JP 2005001157 W JP2005001157 W JP 2005001157W WO 2005071702 A1 WO2005071702 A1 WO 2005071702A1
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- Prior art keywords
- electrode material
- electrode
- nanostructure
- conductive polymer
- potential scanning
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- 239000007772 electrode material Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000003990 capacitor Substances 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 claims abstract description 81
- 238000004070 electrodeposition Methods 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 17
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000011135 tin Substances 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 52
- 150000004706 metal oxides Chemical class 0.000 claims description 52
- 229920000767 polyaniline Polymers 0.000 claims description 46
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 229910001220 stainless steel Inorganic materials 0.000 claims description 24
- 239000010935 stainless steel Substances 0.000 claims description 24
- 150000002739 metals Chemical class 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 95
- 239000002659 electrodeposit Substances 0.000 description 41
- 239000002131 composite material Substances 0.000 description 25
- 125000004122 cyclic group Chemical group 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000012491 analyte Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 241001619461 Poria <basidiomycete fungus> Species 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000001177 diphosphate Substances 0.000 description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 6
- 235000011180 diphosphates Nutrition 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- -1 / dium Chemical compound 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241001504519 Papio ursinus Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000711 polarimetry Methods 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000272165 Charadriidae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- UPEMTJWJZGTCKB-UHFFFAOYSA-N chloric acid perchloric acid Chemical compound OCl(=O)=O.OCl(=O)(=O)=O UPEMTJWJZGTCKB-UHFFFAOYSA-N 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 238000004520 electroporation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 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
- H01G11/02—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 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/48—Conductive polymers
-
- 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 a novel electrode material for redox capacity with high specific capacity, high power density, high energy density, high stability, and low cost, and a method for producing the same.
- Supercapacity is usually classified into two types according to its mechanism. That is, (1) an electric double layer capacitor (ELDC) utilizing the capacitance generated by the polarization phenomenon at the electrode / electrolyte interface, and (2) a charge transfer pseudo capacitance generated by a reversible Faraday reaction generated on the electrode surface. It is a redox capacitor. Since the capacity of ELDC is in principle proportional to the specific surface area of the electrode that can be brought into contact with the electrolyte, a carbon material with a high specific surface area (about 2000 m 2 / g or more) is usually used as the electrode material. You. However, since the specific surface area of the electrode material is limited, its specific capacity is at most about 200 FZg in an aqueous electrolyte solution.
- ELDC electric double layer capacitor
- the capacity of the redox capacity is considered to be due to the reversible redox change of the electrode material, and metal oxides and conductive polymers having various oxidation states are used or considered as electrode materials.
- metal oxides and conductive polymers having various oxidation states are used or considered as electrode materials.
- Ru0 2 has high reversibility, shows excellent charge and discharge property, showing a 720 FZG ones high specific capacity in an acidic aqueous electrolyte solution such as sulfuric acid. And then force, Ru_ ⁇ 2 is a material of high cost, there is a downside as toxic.
- the electrode material of these metal oxides of metal oxides is lower than the material of the electrode material of RR uu 00 22. Although it has the advantages of being able to be used with a neutral electrolysis solution, it is still unsatisfactory in terms of specific capacity. In order to be insufficient, an even higher specific capacity is required, and at the same time, high output power, high density, Nenergulgi-high density and high and high stability are also required. .
- the conductive and conductive polypolymer is also known.
- the polyporinylamine obtained by the precipitation method is 77 00 FF ZZ gg ((11 perchlorate chlorate + 33 It has been reported that this has a specific specific volume of (in a solution of a lithium solution)) ((Non-Patent Literature Document 33)).
- the specific specific capacity here is the value at the rededock Kusskikyapachashita with acid-acidic electrolysis solution. In the case of a neutral neutral electrolytic solution that is advantageous in terms of use, the electroporation chemical activity of popolyryanilinylin is low. Only lower __tt baboon capacities should be shown. .
- Patent Document 33 discloses that the surface of an electrode material for an electrode of any metal oxide of a metal, such as mangangan, is chemically or Electrored vapor-chemical means of rededo-coating coated with conductive and conductive polypolymers.
- G electrode materials are disclosed.
- the method for producing the metal oxide used here is not clear, and the specific capacity of the electrode material achieved is as high as 685 FZ g, but its evaluation method, particularly the potential scanning speed, is unknown. Therefore, they cannot be simply compared.
- Non-Patent Document 1 J. Electrochem. Soc., 150, A107 (2003)
- Non-Patent Document 2 Electrochem. Solid-State Lett., ⁇ , A145 (2 0 0 1)
- Non-Patent Document 3 J. Electrochem. Soc., 144, 292 (20000)
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2000-93365
- Patent Document 2 Japanese Unexamined Patent Application Publication No. 2000-2898468
- Patent Document 3 Japanese Unexamined Patent Publication No. 2003-450570 Disclosure of the Invention
- An object of the present invention is to provide a novel electrode material for redox capacity comprising a metal oxide having a high specific capacity, a high power density, a high energy density, a high stability, and a low cost, and It is to provide a manufacturing method.
- the present inventors have conducted intensive research to achieve the above object, and found that at least one specific material selected from the group consisting of manganese, nickel, tin, indium, tungsten, molybdenum, vanadium, cobalt, titanium and iron.
- Nanostructures with a size of 50 nm or less, consisting of metal amorphous stilts have potential scanning speeds of 7 OmVZs or more. It was found that it can be manufactured for the first time by the potential scanning electrodeposition method. Furthermore, they have found that the obtained nanostructures of amorphous oxides of these specific metals have extremely excellent properties as a novel electrode material for the above-mentioned redox capacitor.
- the form of the nanostructure of the amorphous oxidized product for the specific metal produced by the present invention varies depending on the type of the metal, but the average diameter is 50 nm or less, preferably 30 nm or less.
- whiskers having a diameter of 13 nm or less, preferably 10 nm or less, and a length of 100 nm or less, preferably 50 nm or less, can be produced.
- the nanostructures manufactured by the present invention can be produced by the conventional electrochemical synthesis methods such as the co-precipitation method and the sol-gel method.
- the potential scanning speed at the time of electrodeposition is 7 OmVZs or more, preferably 10 OmVZs or more, particularly preferably 15 OmVZs. This is a unique product that can be produced for the first time by the electrolysis method at the potential scanning speed described above.
- the nanostructures of the amorphous oxide of one or more specific metals of the present invention are used as an electrode material for a redox capacitor, for example, as shown in Examples described later, for example, cobalt-nickel
- the specific scanning capacity in the evaluation of specific capacity is 517 FZg at a potential scanning speed of 5 OmVZs, and the specific scanning rate is as high as 35 OFZg even at a potential scanning speed of 50 OmV / s.
- This is more than twice the value of the same type of highest specific capacity manganese oxide. At the same time, it has the excellent characteristics of high power density, high energy density, and high stability.
- a nanostructure having a size of 50 nm or less made of the above-mentioned specific metal oxide has excellent properties as an electrode material for a redox capacitor by itself, It has been found that when a composite electrode material containing a polymer porous material is used, it has extremely excellent electrode properties for redox capacitors.
- the specific capacity is 482 FZg (0.1 M, potential scanning rate of l OmVZs in an aqueous solution of sodium sulfate).
- the composite electrode material which combines this with a porous material of a conductive polymer of polyaniline, has an extremely high specific capacity of 715 FZg, high energy, high density, and high stability. Dramatically superior performance can be obtained as compared with the electrode material alone or with polyaniline alone.
- the present invention has the following features.
- At least one metal selected from the group consisting of manganese, nickel, tin, indium, tungsten, molybdenum, vanadium, cobalt, titanium and iron.
- An electrode material for redox capacity comprising nanostructures made of rufus oxide and having a size of 50 nm or less.
- nanostructure comprises an amorphous oxide of at least one metal selected from the group consisting of manganese, nickel, tin, indium, and cobalt.
- the nanostructure is an amorphous manganese oxide represented by ⁇ 0 2 ⁇ nH 2 0 (1) electrode material according to any one of - (3).
- a method for producing an electrode material for a dog dog capacity wherein the electrode material is produced by electrodeposition on an electrode surface by an electrodeposition method.
- aqueous solution of the at least one metal-containing compound is an aqueous solution having a concentration of a salt of an inorganic acid or an organic acid of the metal of 0.1 to 5 mol / L.
- a nanostructure having a size of 50 nm or less comprising an oxide force of at least one metal selected from manganese, nickel, tin, indium, tungsten, molybdenum, vanadium, cobalt, titanium, and iron;
- An electrode material for redox capacity comprising: a conductive polymer porous material;
- the conductive polymer is selected from polyanilines, polypyrroles, and polythiophenes.
- a method for producing an electrode material for redox capacity comprising: using an aqueous solution containing a monomer of the conductive polymer as an electrolytic solution; and conducting a potential scan at a potential scanning speed of 70 mVZs or more by a potential scanning electrodeposition method.
- a method for producing an electrode material for redox capacity comprising: a step of depositing a nanostructure.
- the electrode on which the nanostructure composed of the metal oxide is deposited or the electrode on which the porous substance of the conductive polymer is deposited is stainless steel, titanium or nickel, and the electrode is redox.
- a novel electrode material for redox capacity comprising a metal oxide having a high specific capacity, a high output density, a high stability and a low cost, and a method for producing the same.
- the specific capacity of a redox capacitor as an electrode material can be more than doubled as compared with a conventional electrode material of the same type, and can be further increased by increasing the thickness thereof. It has features that are sufficiently excellent in power density and stability.
- the electrode material for a redox capacitor comprising the amorphous oxide of at least one specific metal of the present invention has the above-described excellent properties. Although it is not clear, it seems to be caused by the high potential scanning speed in the potential scanning electrophoresis method that is the manufacturing method. That is, as described above, even with the same electrolysis method, the excellent characteristics as in the present invention cannot be obtained by the constant potential electrodeposition method and the constant current electrodeposition method. In the case of such an electrodeposition method, since the metal oxide is continuously deposited on the electrode, the obtained deposit becomes a lump and does not have a porous structure. It does not seem to give high specific capacity.
- the electrodeposition is discontinuously performed according to the potential to be scanned. Is almost the same lump as in the constant potential electrodeposition method and the constant current electrodeposition method.
- the discontinuity of electrodeposition increases as the potential scanning speed increases, and when the potential scanning speed exceeds a certain value, it is obtained depending on the type of metal, although it depends.
- the electrodeposits are likely to deposit from a lump to a granular, rod-like, or even stiff force to form a porous structure on the electrode surface. As a result, it is thought that the electrode material will have an extremely large specific capacity as compared with the conventional one.
- the specific capacity is further increased because the porous structure of the deposit by the potential scanning method at a high potential scanning rate further develops, and However, it is thought that it is easy to come into contact with the electrolyte because it is formed by a large number of continuous holes.
- a nanostructure having a size of 50 nm or less, which is made of a low-cost metal oxide, and a porous material of a conductive polymer comprising:
- a novel composite electrode material for redox capacitors having high energy density and high stability and a method for producing the same are provided.
- the properties of the electrode material of the redox capacitor obtained by the present invention are as follows: synergistic properties of a nanostructure composed of a metal oxide constituting a composite and a porous substance of a conductive polymer are obtained. Compared to electrode materials, it has the outstanding characteristics of high specific capacity, high power density, high energy density, and high stability, which are not achieved conventionally.
- the composite electrode material of the present invention has such excellent properties as described above.
- the characteristics of the electrode of the redox capacity cannot be attained with the electrode material consisting of a porous conductive polymer alone or the electrode consisting of a nanostructure consisting solely of a metal oxide.
- the specific capacity and energy density of the electrode are dramatically increased even if the amount of the nanostructure composed of the metal oxide in the composite electrode material is extremely small, and The specific capacity of the electrode increases as the thickness of the porous polymer porous material increases.
- Figure 11-1 is a scanning electron micrograph of manganese oxide deposits obtained at different potential scanning velocities during electrodeposition.
- Fig. 1-2 is a scanning electron micrograph (magnification: 100,000) of an electrodeposit of aluminum oxide.
- Fig. 2-1 shows cyclic voltammetry (CV) of the four manganese oxide deposits obtained in Example 1 at different potential scanning speeds during electrodeposition at a potential scanning speed of 100 mVZs. This shows the results of performing.
- Figure 2-2 shows the cyclic portane of the three cobalt-nickel composite oxide deposits obtained in Example 3 at different potential scanning speeds during electrodeposition at a potential scanning speed of 10 OmV / s. The result of the measurement (CV) is shown.
- Fig. 3-1 shows that the specific capacity of the redox capacitor was changed by changing the potential scanning speed at the time of CV curve measurement of the manganese oxide deposited at different potential scanning speeds at the time of electrodeposition in Example 1. Indicates a change.
- Fig. 3-2 shows the results obtained when the potential scanning speed at the time of CV curve measurement was changed for the cobalt-nickel composite oxide electrodeposit obtained in Example 3 at a potential scanning speed of 200 mV / s. This indicates that the specific capacity of the redox capacitor changes.
- Figure 4 shows the results of a cycle test when a manganese oxide electrodeposit was used as an electrode material for redox capacity.
- FIG. 5 shows scanning electron micrographs of a polyaniline electrodeposit and a polyaniline Z manganese oxide electrodeposit obtained on a stainless steel surface.
- FIG. 7 shows the change in the specific capacity of the redox capacity electrode of six kinds of polyaniline / manganese oxide deposits having different thicknesses of the polyaniline deposit.
- FIG. 8 shows the charge / discharge current for the electrode of polyaniline manganese oxide of the present invention (thickness of polyaniline electrodeposits: 4 mgZcm 2 , thickness of manganese oxide: 0.2 mg / cm 2 ). The change in specific capacity when the density is changed is shown.
- the electrode material for a redox capacitor of the present invention is a nano-particle of an amorphous oxide of at least one specific metal selected from the group consisting of manganese, nickel, tin, indium, tungsten, molybdenum, vanadium, cobalt, titanium and iron. It is characterized by including structures. Nanostructures are generally structures of a size expressed at the 100 nm level. It has been reported that metal oxide nanostructures are conventionally manufactured by vapor phase growth, solution phase growth, sol-gel methods, etc. This is the first time that the present invention has been manufactured by the precipitation method. In addition, the present invention is the first to provide a nanostructure such as a granular material, a rod shape, or a whisker shape having a high specific capacity as an electrode material for a redox capacitor.
- the nanostructure of the amorphous oxide of the specific metal according to the present invention has a size of 5 Onm or less, and further has a size of 30 nm or less.
- the “size” refers to the average diameter when the nanostructure is spherical, the thickness when the rod-shaped object / isker-shaped object, and the size when the nanostructure is a flat object. Means minor axis.
- the form of the nanostructure varies depending on the type of metal, when the metal is indium-tin or the like, it has a granular shape or a rod shape with a thickness of 5 O nm or less, preferably 30 nm or less.
- the metal When the metal is manganese, nickel, or the like, it is a whisker having a thickness of 13 nm or less, preferably 10 nm or less, and a length of 10 O nm or less, preferably 5 O nm or less. If the size of the nanostructure is larger than 50 nm, a large specific capacity cannot be obtained, which is not preferable.
- the metal forming the nanostructure of the amorphous oxide is at least one metal selected from the group consisting of manganese, nickel, tin, indium, tungsten, molybdenum, vanadium, cobalt, titanium and iron. Metal is used.
- metals provide preferable nanostructures as electrode materials for redox capacitors to form metal oxides having various oxidation numbers.
- at least one metal selected from the group consisting of manganese, nickel, tin, indium and cobalt is preferred, and manganese or nickel is particularly preferred.
- the electrode material of the present invention exhibits excellent characteristics, particularly when it is composed of a combination of two or more metals.
- combinations of two or more metals are preferably combinations of manganese, nickel, and / or cobalt, especially combinations of cobalt and nickel, nickel and manganese, and cobalt and manganese.
- the content ratio of the constituent metals differs depending on the type of the combination.
- the ratio of AZB (Mass ratio) is preferably set to 2Z98 to 50/50, particularly preferably to 190 to 20/80.
- the metal oxide constituting the electrode material of the present invention is amorphous (crystalline), but in some cases, the metal oxide is preferably a hydrate.
- the preferred hydration number of the hydrate varies depending on the type of metal.
- the nanostructure of the amorphous oxide of one or more specific metals according to the present invention is obtained by using an aqueous solution of a compound containing these metals as an electrolytic solution, and using a potential scanning speed force S 7 O mV / s or more. It is manufactured by depositing a nanostructure of a metal amorphous oxide on the surface of an electrode by a potential scanning electrodeposition method in the above. Here, it is necessary to use the potential scanning electrodeposition method and to set the potential scanning speed in the potential scanning electrodeposition method to 70 mVZs or more.
- the potential difference velocity in the potential scanning electrodeposition method is preferably at least 10 OmVZs, particularly preferably at least 15 OmVs.
- the content is preferably 350 mV / s or less, more preferably 25 OmVZs or less.
- a water-soluble compound of each of the above-mentioned specific metals forming an amorphous oxide is preferably used.
- inorganic acids such as sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid, and pickling acid, and organic acid salts such as acetic acid, citric acid, formic acid, and malic acid are used.
- the water-soluble compounds of these metals are used as aqueous solutions having a concentration of preferably from 0.1 to 10 mol / p, particularly preferably from 0.1 to 5 mol.
- a water-soluble compound of each metal is used at a concentration corresponding to the content of the amorphous oxide of the metal to be formed.
- the electrode substrate on which the amorphous oxide is deposited on the surface by the electrophoretic deposition method a substance that is not easily oxidized, for example, a noble metal material such as platinum or carbon can be used.
- a noble metal material such as platinum or carbon
- inexpensive materials such as stainless steel, nickel, and titanium can be used.
- stainless steel can be advantageously used in the present invention in terms of characteristics and cost.
- Metallic amorphous oxide is deposited on the anode surface by the potential scanning electrodeposition method, but in the case of indium, etc., the nanostructure is deposited on the cathode as a metal, which is then calcined to form a metal oxide. Good.
- a material with a metal amorphous oxide formed on the surface obtained by the potential scanning electrodeposition method is used as a redox capacitor electrode in the form of a current collector on an electrode substrate such as stainless steel. Can be used. It is preferable to select an inexpensive material for the electrode substrate on which the metal amorphous oxide is deposited by the potential scanning electrodeposition method in consideration of this point. However, instead of using the electrode on which the metal amorphous oxide was deposited on the surface as the redox capacity electrode, the electrodeposited metal amorphous oxide was peeled off from the electrode substrate, and this was separated into an appropriate medium. It can also be used as a redox capacitor electrode by forming a slurry using a binder and applying it to the current collector (electrode substrate) of the redox capacitor.
- Adhesion amount is preferably 0. 05 ⁇ lmgZcm 2, particularly preferably a 0. 1 ⁇ 0. 5 mgZcm 2.
- a feature of the present invention is that the electrode material of a redox capacitor comprising a nanostructure of a metal oxide of a metal obtained by potentiometric electrodeposition method, when its thickness is increased, the electrode material of the capacitor The specific capacity can be further increased.
- the electrode material of the nanostructure of the amorphous oxide of the metal of the present invention is, for example, a manganese oxide (FIG. 11) as demonstrated from FIG.
- the nanowhiskers are 7 to 8 nm thick and 30 to 50 nm long.
- indium oxide Fig. 12
- the electrode material of this nanowhisker has a square cyclic cyclic (CV) curve as shown in FIG. 2 of the embodiment described later, and has a target shape. It can be seen that is also excellent as a redox capacity electrode material in terms of reversibility and power density.
- CV square cyclic cyclic
- the electrode material of the amorphous nanostructure of the present invention has a high specific capacity as a redox capacity electrode material.
- the specific capacity in the case of manganese oxide is 428 FZg (in the case of cyclic portammetry scanning speed: 10 OmVZs), as evidenced by FIG.
- the specific capacity of the electrode material generally decreases significantly as the potential scanning speed in cyclic porttammetry increases.
- the potential scanning speed of the cyclic portane metrology was 1 OmVZs in the case of manganese oxide, as demonstrated in FIG.
- the specific capacity decreases only to about 55% when the voltage is increased to OmV / s, and this reduction rate remains almost the same regardless of the potential scanning speed during electrodeposition by the potential scanning method.
- the specific capacity when the electrode material is an amorphous oxide of two or more metals, and the specific capacity at a high potential scanning speed are excellent as shown in Figure 3-2. That is, in the case of cobalt nickel oxide, it reaches 695 F / g (when the potential scanning speed of cyclic voltammetry is 10 mV / s). Even when the potential scanning speed of cyclic voltammetry increases from 1 O mVZ s to 15 O mV / s, the specific capacity decreases to only about 65% and is kept extremely high.
- the electrode material of the amorphous oxide nanostructure of the present invention has high cycle durability. This is demonstrated from FIG. 4 in the examples described later, for example, in the case of manganese oxide, the potential scanning speed of cyclic portammetry: 100 1 111/3 was performed up to 100 cycles. However, a specific capacity reduction of about 8% was observed until the first 100 cycles, but after that there was almost no specific capacity reduction. This is significantly smaller than previously reported redox capacitors.
- the electrode material for redox capacity of the present invention can be used as a composite electrode material as a composite electrode further containing a conductive polymer porous material.
- the conductive polymer porous material may be in the form of particles, but is preferably in the form of a film having a thickness of preferably 10 to 200 m, particularly preferably 30 to 100 m.
- the conductive polymer is preferably selected from polyanilines, polypyrroles, and polythiophenes such as polythiophene, polytrimethylthiophene, and polyethylenedioxythiophene. Among them, polyanilines are preferred because of their ease of synthesis, high stability, low toxicity, and high conductivity.
- the metal oxide nanostructure exists on the surface of the conductive polymer porous material.
- a conductive polymer porous material is present on the surface of a metal oxide nanostructure
- the metal oxide nanostructure and the conductive polymer porous material are uniformly contained, and a metal.
- Various modes such as a laminated structure of an oxide nanostructure and a conductive polymer porous material can be employed.
- the conductive polymer formed on the electrode shows particularly excellent conductivity, and when a specific metal oxide is further formed on the surface by electrodeposition, the conductive polymer becomes conductive. Since the polymer itself also acts as an electrode (current collector), electrodeposition of metal oxides is facilitated. For such a reason, an embodiment in which the metal oxide nanostructure is present on the surface of the conductive polymer porous material is preferable.
- the porous material of the conductive polymer is preferably formed as a porous film, and a metal oxide nanostructure having a size of 50 nm or less adheres to the surface of the porous film. Embodiments are preferred.
- the thickness of the film is preferably from 0.5 to 1 Omg / cm 2 , particularly preferably from 2 to 5 mg / cm 2 .
- the nanostructure of the metal oxide to be deposited is preferably from 0.01 to 1 mgZcm 2 , particularly preferably from 0.05 to 0.5 mg / cm 2 .
- the composite electrode material including the nanostructure made of the metal oxide of the present invention and the conductive polymer porous material is preferably produced as follows. That is, the nanostructure of the metal oxide is obtained by using an aqueous solution of a compound containing these metals as an electrolytic solution, and performing a potential scanning rate of 7 OmVZs or more by a potential scanning electrodeposition method. It is preferably produced by electrodepositing a substance on the electrode surface.
- the production of metal oxide nanostructures by such a potential scanning electrodeposition method uses the same apparatus as that for producing the above-described electrode material consisting of the metal oxide nanostructures alone, and the same water solubility of the same metal. It can be carried out using a compound electrolyte and under the same conditions.
- the porous material of the conductive polymer contained in the composite electrode in the present invention can be produced by various methods such as a chemical method and an electrochemical method.
- an electrochemical method by an electrodeposition method such as a constant potential electrodeposition method or a constant current electrodeposition method is preferable because the thickness of the porous material of the obtained conductive polymer can be easily controlled.
- the same potential scanning electrodeposition method as used in the production of the metal oxide nanostructure is particularly preferable because a more porous material can be obtained.
- a conductive polymer porous material having excellent characteristics can be produced by a potential scanning electrodeposition method at a high potential scanning speed of preferably 70 mV / s or more, particularly preferably 15 OmV / s or more.
- an aqueous solution of a monomer which forms a conductive polymer by electrolytic polymerization is preferably used as the electrolytic solution.
- the concentration of the monomer aqueous solution is preferably from 0.1 to 5 mol / L, particularly preferably from 0.2 to 2 mol / L.
- the electrolytic solution is preferably an acidic aqueous solution.
- an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid such as sulfonic acid, citric acid, formic acid, or malic acid is used.
- the concentration of the acid is preferably from 0.1 to 5 mol / l, particularly preferably from 0.2 to 2 mol / l.
- the potential scanning electrodeposition method for producing a conductive polymer porous material can be carried out in the same manner as the above-described potential scanning electrodeposition method for producing a metal oxide nanostructure.
- a metal oxide nanostructure in the case of producing a composite electrode material from the metal oxide nanostructure produced as described above and a conductive polymer porous material, for example, these may be referred to as a metal oxide nanostructure.
- a slurry can be formed using a binder, and the slurry can be applied simultaneously or sequentially to a current collector of a redox capacitor to manufacture an electrode of a redox capacitor.
- it is possible to easily manufacture the composite electrode material of the present invention by manufacturing both the nanostructure of the specific metal oxide and the porous material of the conductive polymer by the potential scanning electrodeposition method. Can be.
- an aqueous solution containing a monomer of the conductive polymer is used as an electrolytic solution, and a step of electrodepositing a porous material of the conductive polymer by a potential scanning electrodeposition method at a potential scanning speed of 7 OmVZs or more, Using an aqueous solution of the metal-containing compound as an electrolytic solution, and depositing a nanostructure composed of the metal oxide by a potential scanning electrodeposition method at a potential scanning rate of 7 OmVZs or more. It is preferably produced by a production method.
- a step of electrodepositing a porous material of the conductive polymer is performed, and then a step of electrodepositing a nanostructure made of the metal oxide is performed.
- the method of forming a nanostructure made of the metal oxide on the surface of the conductive material is preferable because the obtained electrode material has excellent characteristics.
- an electrodeposit obtained by electrodeposition is particularly preferable because it can be used as it is as a composite electrode for redox capacity.
- an inexpensive material such as stainless steel, titanium, nickel, or the like can be used, which is particularly advantageous.
- the composite electrode material of the present invention is, for example, as shown in the scanning electron micrograph of FIG. 6 described below, for example, a polyaniline porous material electrodeposit (thickness S mg Z cm 2 ) has a structure in which nanoparticulates of manganese oxide are deposited on the surface.
- the manganese oxide nanostructures are in the form of particles with a diameter of 10 to 20 nm and are attached to form a very porous structure on the surface of the polyaniline porous material. 2 mg / cm 2).
- This composite electrode material shows a specific capacity as high as 7 15 FZ g, which indicates that it is extremely excellent as an electrode material for a redox capacitor compared to a polyaniline single electrode.
- the composite electrode material of the present invention has a large cycle durability. This is demonstrated by Figure 9 below, for example, in the case of a composite electrode of polyaniline Z manganese oxide, the specific capacity decreases only 3.5% after 500 cycles of charging and discharging. . This is extremely small compared to the decrease in specific capacity of about 35% reported for conventional polyaniline electrodeposits. Although it has excellent characteristics as described above as the electrode material of the redox capacity of the present invention, it also has an advantage that it can be applied to a redox capacitor using a neutral aqueous solution as an electrolyte.
- the capacity of a neutral aqueous electrolyte solution is superior to that of an alkaline aqueous solution, an acidic aqueous solution, or a non-aqueous solution as an electrolytic solution in terms of handling, safety, and cost.
- the neutral aqueous solution preferably, chloride, sulfate, hydrochloride, or the like such as potassium, sodium, and lithium can be used.
- chloride, sulfate, hydrochloride, or the like such as potassium, sodium, and lithium can be used.
- an alkaline aqueous solution, an acidic aqueous solution, or even a non-aqueous solution can be used as an electrolytic solution.
- the concentration of these electrolytes is preferably 0.1-5 mol Z liter, particularly preferably 0.3-1 mol Z liter.
- the method for producing a redox capacitor using the electrode material of the present invention can be performed by known means.
- the electrode material of the present invention can be used for one or both of a positive electrode and a negative electrode of a redox capacitor.
- an electrode made of a conductive polymer material or the like can be used as the other electrode.
- the electrode material of the present invention may be used alone, but if necessary, may be used in combination with a conductive material or the like as needed to improve the conductivity of the electrode.
- the conductive material include conductive carbon such as activated carbon, and conductive polymers such as polyaniline and polythiophene.
- a binder such as a fluoropolymer such as tetrafluoroethylene which binds the electrode material and the conductive material of the present invention can be used.
- H 2 S0 4, Mn S0 4 ⁇ 5H 2 0, ⁇ Pi Na 2 S0 4 are from Aldrich (USA), all aqueous solutions were prepared using double distilled water .
- the electrolysis cell was a four-electrode system including a working electrode, a reference electrode, and two counter electrodes, and the working electrode was set between two platinum counter electrodes.
- a saturated calomel electrode (SCE) was used as the reference electrode.
- a thickness of 0.5 2 mm City sales of A stainless steel (304 grade) foil (oxide deposition area: 1 cm 2 ) was sanded in advance with sandpaper, the abrasive particles were washed away, and the air-dried one was used. Electrodeposition was performed at various potential scanning speeds with a potential width of 0.5 to 1.5 V, and deposits were obtained on the surface of stainless steel foil. The electrodeposits on the stainless steel were directly washed with distilled water and dried at room temperature for about 12 hours.
- X-ray diffraction analysis confirmed that the obtained deposit on stainless steel was in an amorphous state.
- the electrodeposits were evaluated as electrode materials for redox capacity in a Na 2 SO solution having a concentration of 1 molar Z liter at various potential scanning speeds by a cyclic polarimeter (CV).
- X-ray diffraction analysis of electrodeposited film W X-ray diffractometer manufactured by Rigaku Corporation RINT2100, using CuKa ray. Observation of the surface condition of the electrodeposit was conducted by JE ⁇ L. Type electron microscope: JSM-6304F was used.
- Fig. 11-1 shows scanning electron micrographs of manganese oxide deposits obtained at different potential scanning speeds during electrodeposition.
- Fig. 11 la shows the relatively low potential scanning speed. It is an electrodeposit of mV / s, and its form is a spherical mass.
- Fig. 1-1b shows an electrodeposit with a potential scanning rate of 10 OmV / s, which is an amorphous porous material.
- Figures 11c and 11d are deposits with a high potential scanning speed of 200 mVZs, with magnifications of 30,000 and 200,000, respectively. In this case, it can be seen that the deposit has a thickness of 7 to 8 nm and a length of 30 to 50 nm and has a nano-structure.
- Figure 2-1 shows the manganese oxide deposits at the potential scanning speed (l: 50 mV "s, 2: 100 mV / s, 3: 15 OmV / s, 4: 20 OmVZs) during electrodeposition.
- the results obtained when the electrode was used as an electrode material for Redox capacity at a thickness of 0.2 mg / cm 2 at a potential scanning rate of 10 OmVZs in cyclic portmetry are shown. Also in this case, since the obtained curve has a square shape and a target shape, it can be understood that the electrodeposit is excellent as an electrode material for redox capacity in terms of reversibility and output density.
- Fig. 3-1 shows the potential scanning of cyclic manganese oxide deposits at different potential scanning speeds (5 OmVZs, 10 OmV / s, 15 OmV / s, and 20 OmV / s) during electrodeposition. This shows that the specific capacity of the redox capacity changes when the speed is changed.
- the thickness of the electrodeposit was evaluated at 0.1 SmgZcm 2 .
- Deposits of 20 OmV / s, which have different potential scanning speeds at the time of electrodeposition within the scope of the present invention, can reach a specific capacity of 482 F / g (potential scanning speed of cyclic voltammetry: 10 mV / s). did.
- Figure 4 shows the results of a cycle test when a manganese oxide electrodeposit (potential scanning speed during electrodeposition was 20 OmVZs) was used as an electrode material for redox capacity.
- the cycle test was performed up to 1000 cycles at a potential scanning rate of cyclic portammetry of 10 OmVZs and a potential width of 100 OmV. A decrease in specific capacity of about 8% was observed until the first 100 cycles, but after that there was almost no decrease in specific capacity.
- Example 2 The same electrolytic cell as that used in Example 1 was used, and stainless steel (304 grade) was used as the working electrode.
- the potential of tin, nickel, and indium was the same at the same potential scanning speed of 20 OmV / s. Scanning electrodeposition was performed.
- an electrolytic solution a concentration of 100 mmol / l of N i C 1 2 - 6H 2 0 and concentration of 50 mM mixed solution of CoC 1 2 ⁇ 6H 2 0 and Z liter (pH 8. 0) was used as the electrolytic solution, the row potentials scanning electrodeposition at the potential scan rate 20 OmVZs ivy.
- the deposit on the stainless steel was 0.12 mgZcm 2 , and an X-ray diffraction analysis performed in the same manner as in Example 1 showed that a cobalt (20 wt%)-nickel (80 wt%) complex system was obtained. It was an oxide.
- KOH electrolyte of 1M Figure 2-2 shows the results obtained when the potential scanning speed in the liquid and in the cyclic polarimetry was 1:50 mV / s, 2: 200 mV / s, and 3: 500 mV / s.
- the obtained curve has a quadrangular shape and a target shape, and thus it can be seen that the electrodeposit is excellent as an electrode material family of Redox Capacitor in terms of reversibility and output density.
- Example 2 The same electrolytic cell as used in Example 1 was used, and stainless steel (304 grade) was used as the working electrode. As in Example 3, mixed aqueous solutions of various metal salts were used as the electrolyte. By performing potential scanning electrodeposition at a potential scanning speed of 20 OmV / s, various amorphous composite oxides shown in Table 2 were obtained on a stainless steel electrode.
- Example 5 was used in this example, H 2 S0 4, MnS0 4 - 5H 2 0, and N a 2 S_ ⁇ 4 is a Aldric Inc. (USA), all aqueous solutions were prepared using double distilled water .
- the electrolysis cell was a four-electrode cell having a working electrode, a reference electrode, and two counter electrodes, and the working electrode was set between two Pt counter electrodes.
- a saturated calomel electrode (SCE) was used as the reference electrode.
- SCE saturated calomel electrode
- As the working electrode commercially available 0.2 mm thick stainless steel (304 grade) yl (area: 1 cm 2 ) is polished with sandpaper in advance, the abrasive particles are washed away, air-dried, and the air is dried. Using.
- the electrostatic Analyte Poria diphosphorus manganese oxide, Na 2 S_ ⁇ 4 aqueous solution having a concentration 0.1 mol Z l and the electrolyte, the thickness 0 made Polypropylene Evaluation of electrode materials for redox capacity using 1 mm porous sheet as a separator was performed at various current densities by charge / discharge cycles.
- the X-ray diffraction analysis of the deposits was performed using CuKa rays with an X-ray diffractometer (RINT2100, manufactured by Rigaku Corporation). The observation of the surface state of the deposits was carried out by JEOL scanning type. Electron microscope: JSM-6340F was used.
- FIG. 5 shows a scanning electron micrograph of the polyaniline electrodeposit and the polyaniline Z manganese oxide electrodeposit obtained on the stainless steel surface in Example 1. It is understood that a of the above is an electrodeposit of polyaniline, and its surface morphology is a porous material composed of granular materials. “B” in FIG. 5 is an electrodeposit of polyaniline manganese oxide, and it can be seen that manganese oxide nano-particles are attached innumerably to the surface of the electrode to form porosity. Evaluation of electrodeposits as electrode materials for redox capacitors
- Analyte conductive type polyaniline Z manganese oxide is similar to the above, the Na 2 S 0 4 aqueous solution having a concentration 1 mole / liter as electrolyte, the current density 1 OmAZcm 2 As a result, it was found that the charge Z discharge cycle efficiency was extremely high in the range of 0.98 to 0.99.
- Fig. 7 shows the same redox electrodes as those used in Fig. 6 above, but with six different polyaniline Z manganese oxide deposits with different thicknesses of polyaniline deposits.
- the figure shows the change in specific capacity of the electrode. Evaluation of specific capacity, in the same manner as described above, the Na 2 S 0 4 aqueous solution having a concentration 0.1 mol l and the electrolyte, the line at the charge Z discharge cycles at a current density of 1 OmAZcm 2 ivy. For comparison, the specific capacity of each electrode of a polyelectrolyte electrodeposit having no manganese oxide electrodeposit on the surface was also evaluated.
- the specific capacity of the polyaniline / manganese oxide electrode of the present invention is much larger than that of the polyaniline electrode.
- the specific capacity of the polyaniline electrode increases linearly as the thickness of the polyaniline electrodeposit increases, while the specific capacity of the polyaniline / manganese oxide electrode increases with the thickness of the polyaniline electrodeposit. It can be seen that when reaches a predetermined thickness, it saturates there. This fact means that the deposition of manganese oxide is effective only on the surface layer of the polyaniline deposit.
- FIG. 8 shows the current density of the charging / discharging of the electrode of the polyaniline / manganese oxide of the present invention (thickness of the polyaniline electrodeposit: 4 mgZcm 2 , thickness of the manganese oxide: 0.2 mgZcm 2 ). Shows the change in specific capacity when. For comparison, the specific capacity of a polyaniline electrodeposit having no manganese oxide electrodeposit on the surface is also shown.
- the polyaniline / manganese oxide electrode has a high specific capacity of 690 FZg, which is based on the specific capacity of the polyaniline electrodeposit shown in FIG. 8 and the manganese reported in Patent Document 2 described above. It can be seen that the specific capacity is dramatically higher than the specific capacity of the oxide electrode.
- Example 5 the conductive polymer deposit shown in Table 3 (thickness: 4 mg Z cm 2 ) was used in place of the polyaniline deposit obtained on the surface of the stainless steel electrode, and The same electrolytic cell as in Example 5 was used, except that the metal oxides shown in Table 3 (attachment amount: 0.2 mg / cm 2 ) were deposited on the surface of the conductive polymer deposit. Then, a composite electrode material was manufactured in the same manner.
- the novel electrode material for redox capacity provided by the present invention has a specific capacity, a high power density, a high energy density, a high stability, and a low cost, so that the redox capacity using this is
- various types of electrical equipment continue to be miniaturized, it is widely used as a compact, lightweight, large-capacity, high-stability, and rapid charge / discharge power storage device for various types of electrical equipment, portable equipment, hybrid vehicles, and electric vehicles. It can be used.
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JP2004-028389 | 2004-02-04 | ||
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JP2004201098A JP2005252217A (ja) | 2004-01-21 | 2004-07-07 | レドックスキャパシタ用酸化物電極材料及びその製造方法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8609018B2 (en) | 2008-11-05 | 2013-12-17 | Korea Institute Of Science And Technology | Electrode for supercapacitor having manganese oxide-conductive metal oxide composite layer, fabrication method thereof, and supercapacitor comprising same |
US11948740B2 (en) * | 2017-09-25 | 2024-04-02 | National University Corporation Chiba University | Porous conductor having conductive nanostructure and electricity storage device using same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000068166A (ja) * | 1998-08-21 | 2000-03-03 | Nichicon Corp | 電気二重層コンデンサ |
JP2000124082A (ja) * | 1998-10-14 | 2000-04-28 | Fuji Electric Co Ltd | エネルギー貯蔵素子およびその製造方法 |
JP2001093512A (ja) * | 1999-09-16 | 2001-04-06 | Ness Co Ltd | スーパキャパシタ用金属酸化物電極及びその製造方法 |
JP2003045750A (ja) * | 2001-07-13 | 2003-02-14 | Ness Capacitor Co Ltd | 導電性高分子をコーティングした金属酸化物電気化学擬似キャパシタの電極及びその製造方法 |
JP2003512284A (ja) * | 1999-10-27 | 2003-04-02 | アイトゲネッシーシェ テヒニッシェ ホッホシューレ チューリッヒ | 遷移金属酸化物から成るナノチューブを製造するための方法 |
JP2004103669A (ja) * | 2002-09-05 | 2004-04-02 | National Institute Of Advanced Industrial & Technology | スーパーキャパシター |
-
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- 2005-01-21 WO PCT/JP2005/001157 patent/WO2005071702A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000068166A (ja) * | 1998-08-21 | 2000-03-03 | Nichicon Corp | 電気二重層コンデンサ |
JP2000124082A (ja) * | 1998-10-14 | 2000-04-28 | Fuji Electric Co Ltd | エネルギー貯蔵素子およびその製造方法 |
JP2001093512A (ja) * | 1999-09-16 | 2001-04-06 | Ness Co Ltd | スーパキャパシタ用金属酸化物電極及びその製造方法 |
JP2003512284A (ja) * | 1999-10-27 | 2003-04-02 | アイトゲネッシーシェ テヒニッシェ ホッホシューレ チューリッヒ | 遷移金属酸化物から成るナノチューブを製造するための方法 |
JP2003045750A (ja) * | 2001-07-13 | 2003-02-14 | Ness Capacitor Co Ltd | 導電性高分子をコーティングした金属酸化物電気化学擬似キャパシタの電極及びその製造方法 |
JP2004103669A (ja) * | 2002-09-05 | 2004-04-02 | National Institute Of Advanced Industrial & Technology | スーパーキャパシター |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8609018B2 (en) | 2008-11-05 | 2013-12-17 | Korea Institute Of Science And Technology | Electrode for supercapacitor having manganese oxide-conductive metal oxide composite layer, fabrication method thereof, and supercapacitor comprising same |
US11948740B2 (en) * | 2017-09-25 | 2024-04-02 | National University Corporation Chiba University | Porous conductor having conductive nanostructure and electricity storage device using same |
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