WO2014017597A1 - 分極性電極材およびこれを用いた電気二重層キャパシタ - Google Patents
分極性電極材およびこれを用いた電気二重層キャパシタ Download PDFInfo
- Publication number
- WO2014017597A1 WO2014017597A1 PCT/JP2013/070214 JP2013070214W WO2014017597A1 WO 2014017597 A1 WO2014017597 A1 WO 2014017597A1 JP 2013070214 W JP2013070214 W JP 2013070214W WO 2014017597 A1 WO2014017597 A1 WO 2014017597A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode material
- electric double
- double layer
- tungsten oxide
- layer capacitor
- Prior art date
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 87
- 239000003990 capacitor Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000002482 conductive additive Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 14
- 230000006866 deterioration Effects 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 87
- 238000000034 method Methods 0.000 description 22
- 239000008151 electrolyte solution Substances 0.000 description 19
- 238000000354 decomposition reaction Methods 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000011163 secondary particle Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 239000012752 auxiliary agent Substances 0.000 description 10
- 238000012423 maintenance Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002648 laminated material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical class O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000012093 Myrtus ugni Nutrition 0.000 description 1
- 244000234179 Myrtus ugni Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003621 hammer milling Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
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
-
- 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
- H01G11/24—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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
- H01G11/52—Separators
-
- 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
-
- 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 polarizable electrode material for an electric double layer capacitor with improved voltage resistance for the purpose of improving energy density and long-term reliability, and an electric double layer capacitor using the same.
- a polarizable electrode for an electric double layer capacitor of a high withstand voltage type that has a high energy density and little deterioration with time such as a decrease in capacitance with time or an increase in resistance with time, that is, excellent long-term reliability.
- the present invention relates to a material and an electric double layer capacitor using the same.
- An electric double layer capacitor is a power storage element that utilizes the capacitance of an electric double layer formed by adsorption / desorption of electrolyte ions at the interface between a pair of positive and negative polarizable electrodes and an electrolyte solution.
- Electric double layer capacitors can be used for small capacity types such as for memory backup, medium power types and large capacity types such as auxiliary power sources for electric vehicles, auxiliary power sources for solar cells, auxiliary power sources for wind power generation and instantaneous power failure compensation devices. Has been widely studied.
- the characteristics of the electric double layer capacitor include capacitance (C), operating voltage (V), energy density (E), internal resistance, and service life. Improvement of both characteristics is important, but recently, especially the improvement of energy density, which is a disadvantage of electric double layer capacitors, and further extension of the service life (improvement of long-term reliability) are the small capacity mentioned above. It has come to be demanded in applications from type to large capacity type.
- the electric double layer capacitor there are an aqueous electrolyte solution and a nonaqueous electrolyte solution.
- an aqueous electrolyte solution When an aqueous electrolyte solution is used, there is an advantage that a low resistance type electric double layer capacitor can be obtained.
- a non-aqueous electrolyte solution it can be used at a higher voltage. In a normal case, the operating voltage is about 2.5V, and when it is higher, it is used at about 2.7V.
- decomposition products coat the surface of the activated carbon or block the pores of the activated carbon, thereby reducing the surface area of the activated carbon and causing a decrease in capacitance. These decomposition products also cause an increase in resistance by closing the opening of the separator.
- the electric double layer capacitor As a method for reducing moisture in the electric double layer capacitor, for example, by improving the material of the separator and developing a separator that does not deteriorate even under high temperature and long time drying conditions, the electric double layer capacitor has a high withstand voltage. It has been reported that a long life is achieved (for example, see Patent Documents 1 and 2). By improving the separator, it is possible to increase the drying temperature condition.
- other components in the electric double layer capacitor such as organic components used in binders and adhesive layers, deteriorate, covering activated carbon or separators or blocking pores, causing a decrease in capacitance. There is a problem that the resistance increases as the electrode / current collector interface peels off. Further, in order to completely remove the moisture inside the activated carbon pores and the functional groups on the surface of the activated carbon, a heat treatment of several hundred degrees Celsius is required in vacuum or under an inert gas stream, which is not practical from the viewpoint of cost.
- the activated carbon fiber woven fabric after removal is stored in a completely dehumidified state, and if the electric double layer capacitor is not assembled, there is a problem that moisture re-adsorption and surface functional groups are re-introduced. Not practical.
- An object of the present invention is a polarizable electrode for an electric double layer capacitor of a high withstand voltage type that has a higher energy density and less deterioration with time of capacitance and resistance than before, that is, excellent long-term reliability. It is to provide a material and an electric double layer capacitor using the same.
- a polarizable electrode material that is used in an electric double layer capacitor and includes porous carbon particles, a conductive additive, tungsten oxide powder, and a binder As the surface area of the tungsten oxide per polarizable electrode material 1g is less than 0.2 m 2 or more ⁇ 6 m 2, wherein the tungsten oxide is dispersed in the polarizable electrode material, min A polar electrode material is provided.
- the electrode material according to (1) is provided, wherein the tungsten oxide has a primary particle diameter of 0.05 ⁇ m to 0.4 ⁇ m.
- (3) The electrode material according to (1) or (2), wherein the content of the tungsten oxide in the electrode material is less than 40% by mass.
- porous carbon particles according to any one of (1) to (3), wherein a ratio of mesopore volume to total pore volume is 30% to less than 85% An electrode material is provided.
- (6) The electrode material according to any one of (1) to (5), wherein the binder is polytetrafluoroethylene.
- An electric double layer capacitor is provided, wherein the electrode material according to any one of (1) to (6) is disposed at least on the negative electrode side through a separator.
- An electric double layer capacitor is provided, wherein a pair of positive and negative electrodes of the electrode material according to any one of (1) to (6) is disposed via a separator.
- a polarizable electrode material for an electric double layer capacitor having a high withstand voltage and an electric double layer capacitor using the same with the aim of improving energy density and long-term reliability are obtained. It is done. Specifically, a high withstand voltage type electrode for an electric double layer capacitor and an electric double layer capacitor having high energy density and little deterioration of capacitance and resistance with time, that is, excellent long-term reliability, can be obtained. .
- the present inventors have intensively studied. As a result, when tungsten oxide is added to the electrode material, the tungsten oxide is dispersed in the polarizable electrode material so that the surface area of the tungsten oxide per 1 g of the electrode material falls within a predetermined range.
- the energy density is further increased than before. It has been found that a high withstand voltage type electrode for an electric double layer capacitor and an electric double layer capacitor can be provided that are high in resistance and have little deterioration over time in capacitance and resistance, that is, excellent in long-term reliability.
- the polarizable electrode material according to the present invention is used in an electric double layer capacitor, and comprises porous carbon particles, a conductive additive, tungsten oxide powder, and a binder.
- the tungsten oxide contained in the polarizable electrode material of the present invention provides an electric double layer capacitor having a high energy density and little deterioration of capacitance and resistance with time, that is, excellent long-term reliability.
- the reason why high effect is recognized by including tungsten oxide is not clear, but it is thought to prevent clogging of porous carbon particles and separator pores by selectively decomposing moisture.
- the present invention in case of adding the tungsten oxide electrode material, such that the surface area of the tungsten oxide per electrode material 1g below 0.2 m 2 or more ⁇ 6 m 2, polarizable electrode material in the tungsten oxide It is characterized by being dispersed.
- the surface area of the tungsten oxide is based on the BET specific surface area of the tungsten oxide in a powder state before being mixed as an electrode material, and the BET specific surface area is determined by a nitrogen adsorption method. Measured. That is, the surface area of tungsten oxide per 1 g of electrode material is obtained by multiplying the tungsten oxide content of the electrode material by the BET specific surface area of tungsten oxide.
- the capacitance maintenance rate can be further increased and the internal resistance increase rate can be further decreased.
- the surface area of tungsten oxide is smaller than this range, the water decomposition action is not sufficient.
- the surface area of tungsten oxide is larger than this range, the ratio of the porous carbon particles is relatively lowered, so that the initial capacitance of the capacitor cell is lowered.
- the primary particle diameter of tungsten oxide may be 0.05 ⁇ m to 0.4 ⁇ m.
- the capacitance maintenance rate can be further increased and the internal resistance increase rate can be decreased as compared with the conventional case.
- the tungsten oxide particles generally exist as secondary particles in which a plurality of primary particles are aggregated, and the nominal particle size of commercially available tungsten particles indicates the secondary particle size.
- the decomposition action of moisture by tungsten oxide is proportional to the surface area of tungsten oxide. This surface area is correlated with the primary particle size rather than the secondary particle size. The surface area that substantially contributes to the reaction cannot be obtained from the secondary particle size, and in the particle size management based on the secondary particle size or nominal particle size, it is difficult to find a correlation with the action of water decomposition. It may be difficult to design the material.
- the present inventor has focused on the primary particle diameter, and found that there is a correlation between the surface area obtained from the primary particle diameter and the capacitance maintenance ratio, and by utilizing this correlation in the design of the electrode material, a better electrode material can be obtained.
- One aspect of the present invention to be provided has been completed.
- the primary particles are not necessarily spherical, and the BET specific surface area may not be accurately measured depending on the aggregation state.
- 200 or more arbitrary particle diameters are measured from an image with a magnification of 50,000 times or more based on observation with a scanning electron microscope (SEM) or transmission electron microscope (TEM).
- the primary particle diameter of tungsten oxide is 0.05 ⁇ m or more, more preferably 0.08 ⁇ m or more to 0.4 ⁇ m or less, and more preferably 0.28 ⁇ m or less.
- An electrode material capable of obtaining a moisture decomposition effect is provided. That is, it is possible to further increase the capacitance maintenance rate and lower the internal resistance increase rate than before.
- the tungsten oxide content in the electrode material may be less than 40% by mass.
- the content of the tungsten oxide powder in the polarizable electrode material is appropriately adjusted so that the surface area of tungsten oxide per 1 g of the electrode material falls within a predetermined range.
- 2% by mass or more and 40% by mass based on the total mass of the polarizable electrode material (the total mass is the dry mass after removing the molding aid used when blending the main components of the polarizable electrode material)
- the ratio is preferably less than%, more preferably 4% by mass or more and 30% by mass or less.
- moisture content is inadequate and an effect is not enough.
- the content of tungsten oxide exceeds 40% by mass, the ratio between the porous carbon particles and the conductive auxiliary agent is relatively decreased, and thus the initial resistance of the capacitor cell is increased. It is more preferable that the addition amount be 4% by mass or more and 30% by mass or less because the effect of decomposing moisture is remarkable and the initial resistance can be sufficiently lowered.
- the secondary particle diameter of the tungsten oxide powder any particle diameter can be used as long as it does not affect the thickness of the electrode layer when forming the electrode layer for an electric double layer capacitor.
- the tungsten oxide powder has a particle diameter of about 0.1 ⁇ m to 50 ⁇ m because it does not affect the thickness of the electrode layer and the pulverization / classification process does not cost much.
- the tungsten oxide powder is generally commercially available with a particle size of several tens of ⁇ m (nominal particle size, that is, secondary particle size).
- a process such as pulverization and classification is required, and as the secondary particle size is reduced, the pulverization time becomes longer and the yield also decreases. Cost increases. For this reason, about 0.1 ⁇ m is considered to be the minimum secondary particle diameter that can be used industrially.
- the electrode layer for an electric double capacitor usually has a thickness of about 0.01 to 1 mm.
- the maximum secondary particle diameter of the tungsten oxide powder is about 30 ⁇ m. It is considered the practical maximum secondary particle size.
- the tungsten oxide powder can be pulverized by various methods such as ball milling, jet milling, hammer milling, etc. as in the case of pulverizing activated carbon. If the target particle size (secondary particle size) cannot be adjusted by pulverization, the particle size (secondary particle size) may be adjusted by classification. Note that the primary particle size can also be changed by the steps of pulverization and classification.
- the primary particle shape tends to be more spherical and the aggregated state tends to be eliminated by processes such as pulverization and classification, so that the correlation between the BET specific surface area and the primary particle size is further increased. The accuracy of management is improved.
- tungsten oxide and porous carbon particles are in a solid state. It is also possible to use solid (solid) -solid (solid) mixing, or at least one of which is a slurry dispersion in which at least one is previously dispersed in a liquid such as water or an organic solvent. Furthermore, in order to improve dispersibility at the time of mixing these, it is also possible to mix using ultrasonic mixing or a water flow.
- the longer the mixing time the higher the degree of uniform dispersion, which is preferable.
- the mixing time may be 1 minute or longer, preferably 5 minutes or longer, and more preferably 15 minutes or longer. However, if the mixing time exceeds a certain time, the degree of uniform dispersion does not improve, so the upper limit of the mixing time may be 3 hours or less as a guide.
- the polarizable electrode material of the present invention contains porous carbon particles.
- the ratio of the mesopore volume to the total pore volume in the porous carbon particles may be 30% or more, more preferably 35% to less than 85%, more preferably 60% or less. .
- Porous carbon has pores, and the pores can be micropores (micropores, micropores, micropores), mesopores (mesopores, mesopores), macropores (macropores) depending on the size of the pores. Pores and macropores).
- a pore having a diameter of 2 nm or less is defined as a micropore
- a pore having a diameter of 2 to 50 nm is defined as a mesopore
- a pore having a diameter of 50 nm or more is defined as a macropore.
- the pore size distribution can be obtained by obtaining an adsorption / desorption isotherm of nitrogen and analyzing the adsorption isotherm by the BJH method. Based on the pore size distribution, the ratio of the mesopore volume to the total pore volume can be determined. Similarly, the ratio of micropores and macropores can be determined.
- the mesopore ratio and the micropore ratio have an inverse correlation (the micro increases as the meso decreases, the micro decreases as the meso increases).
- the ratio of the mesopore volume is less than 30%, the ratio of the micropore volume is relatively increased, and pore clogging is likely to occur. This is presumably because decomposition products and gases generated in the electrode material become clogging substances when tungsten oxide decomposes moisture.
- the generation of clogging substances tends to increase, which becomes a problem particularly when used at a high voltage of, for example, 2.7 V or higher.
- the ratio of the mesopore volume is 85% or more, the ratio of the micropore volume is relatively low, and the initial capacitance is reduced.
- the mesopore volume ratio of 30% or more, more preferably 35% or more to less than 85%, more preferably 60% or less, an electrode material that can be sufficiently used even at 3.0V exceeding 2.7V is provided. Is done.
- the capacitance retention rate can be further increased and the internal resistance increase rate can be decreased as compared with the conventional case.
- the mesopore ratio can be appropriately adjusted by the porous carbon activation treatment. Further, porous carbon having an appropriate mesopore ratio may be procured from commercially available products.
- various methods such as gas activation and chemical activation can be applied. Water, carbon dioxide, oxygen, chlorine, sulfur dioxide, sulfur vapor, etc. can be used as the gas used for gas activation.
- chemicals used for chemical activation zinc chloride, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, phosphoric acid, calcium chloride, potassium sulfide and the like can be used.
- the kind of porous carbon contained in the polarizable electrode material of the present invention is not particularly limited as long as it is a carbonaceous material capable of forming an electric double layer, and activated carbon or the like can be used.
- Activated carbon having a BET specific surface area of 500 m 2 / g or more, preferably 1000 m 2 / g or more, and 3000 m 2 / g or less, preferably 2500 m 2 / g or less can be used. There is no restriction
- the activated carbon can be pulverized by various methods such as a ball mill, a jet mill, and a hammer mill. If the target particle size cannot be adjusted by pulverization, the particle size may be adjusted by classification.
- the porous carbon may be graphite-like microcrystalline carbon produced by subjecting a carbon material to activation treatment.
- This microcrystalline carbon forms an electric double layer when ions or the like enter between crystal layers when a voltage is applied, and can be obtained, for example, according to the technique disclosed in JP-A-11-317333.
- Spherical aggregate carbon black acetylene black, ketjen black, other furnace blacks, channel black, thermal lamp black, etc.
- hydrocarbons such as methane, propane, acetylene, etc. are vapor-phase pyrolyzed on graphite as a substrate And pyrolytic graphite deposited in the form of a thin film.
- ketjen black and acetylene black are preferred because they have a relatively small particle size and relatively good conductivity.
- the blending amount of the conductive auxiliary agent is preferably 10 parts by mass or less, where the total mass of the porous carbon particles, the conductive auxiliary agent, and the binder, which are the main constituent elements of the polarizable electrode material, is 100 parts by mass.
- the said total mass is a dry mass after removing the shaping
- the conductive auxiliary agent is used to lower the contact resistance between the porous carbon particles, and the conventional polarizable electrode layer usually contains 10 parts by mass or more.
- the amount of the conductive auxiliary agent is increased, the workability of the polarizable electrode layer is deteriorated, and problems such as cracks, cracks, and deterioration of rolling property are generated.
- the size of the particles is smaller than that of the activated carbon, if the particles are not uniformly dispersed, the inter-particle voids of the polarizable electrode layer are filled, and there is a problem that the diffusion of the electrolyte solution is hindered.
- the binder contained in the polarizable electrode material of the present invention binds the porous carbon particles, the conductive auxiliary agent and the tungsten oxide powder.
- the binder polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), polypropylene (PP), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), or the like can be used.
- PTFE which does not easily cause oxidation-reduction is preferable because the binder is easily oxidatively decomposed and reductively decomposed at a working voltage of 2.7 V or more, thereby reducing the binding force of the particles.
- the blending amount of the binder is preferably 1 to 30 parts by mass, more preferably 3 parts, with 100 parts by mass as a total mass of the porous carbon particles, the conductive auxiliary agent, and the binder, which are main components of the polarizable electrode material. ⁇ 20 parts by mass.
- the said total mass is a dry mass after removing the shaping
- the blending amount of the binder is less than 1 part by mass, it becomes difficult to hold the porous carbon particles on the polarizable electrode material.
- the polarizable electrode material according to the present invention can be produced in a layered manner by a sheet production method, a coating method (coating method), or the like to form a polarizable electrode layer.
- the sheet manufacturing method is a method in which a sheet (electrode layer) of an electrode material is formed in advance and then adhered to an aluminum foil.
- the coating method (coating method) is a method in which an electrode material is applied onto an aluminum foil as a current collector ( Coating) to form an electrode layer. When the same activated carbon is used, the sheet manufacturing method can obtain a higher capacitance than the coating method.
- a sheet manufacturing method is more suitable than a coating method in order to uniformly disperse tungsten oxide having a specific gravity greatly different from that of a carbon material in an electrode. For this reason, in this invention, a sheet manufacturing method is preferable as a manufacturing method of an activated carbon electrode.
- the conductive auxiliary agent for example, after adjusting the particle size of the porous carbon particles obtained by the above-described method so that the average particle diameter D50 is about 5 to 200 ⁇ m, the conductive auxiliary agent, the tungsten oxide powder, It can be kneaded by adding a binder, and rolled to form a sheet.
- liquid auxiliaries such as water, ethanol and acetonitrile may be used alone or in combination as appropriate.
- the electric double layer capacitor has a structure in which a pair of polarizable electrode layers are opposed to each other via a separator to be a positive electrode and a negative electrode. Each polarizable electrode layer is joined to a current collector, and each polarizable electrode layer is impregnated with an aqueous electrolyte solution or a non-aqueous electrolyte solution.
- An electric double layer capacitor is a power storage element that utilizes the capacitance of an electric double layer formed by adsorption / desorption of electrolyte ions at the interface between a polarizable electrode layer and an electrolyte solution.
- an insulating material such as microporous paper, glass, or a plastic porous film such as polyethylene, polypropylene, polyimide, or polytetrafluoroethylene can be used.
- the thickness of the separator is generally about 10 to 100 ⁇ m.
- non-aqueous electrolyte solution By selecting a suitable non-aqueous electrolyte solution as the electrolyte solution, it is possible to operate at a voltage higher than the voltage at which water electrolysis occurs.
- non-aqueous electrolyte solution known ones conventionally used in electric double layer capacitors can be appropriately employed depending on the solubility of the electrolyte in a solvent and the reactivity with the electrode.
- Solvents for the non-aqueous electrolyte solution include carbonate esters such as propylene carbonate and butylene carbonate; lactones such as ⁇ -butyrolactone and ⁇ -butyrolactone; sulfolanes; amide solvents such as dimethylformamide; nitromethane; 1,2-dimethoxyethane; acetonitrile And so on.
- a solvent may be used independently and may be used as a mixed solvent which combined 2 or more types.
- a quaternary ammonium salt, a quaternary imidazolium salt, a quaternary pyridinium salt, a quaternary pyrrolidinium salt, a quaternary phosphonium salt, etc. which are conventionally used, are used alone or as a mixture of two or more.
- BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , ClO 4 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , AlCl 4 ⁇ , SbF 6 ⁇ Etc. can be exemplified.
- the concentration of the electrolyte in the electrolyte solution is preferably 0.5 mol / L or more, and more preferably 1.0 mol / L or more.
- the upper limit of the electrolyte concentration is the solubility determined by the combination of the individual specific electrolyte and solvent.
- the polarizable electrode material of the present invention is disposed at least on the negative electrode side via a separator. Even when the polarizable electrode material of the present invention is disposed only on the negative electrode side, an electric double layer capacitor having the effects of the present invention (high energy density and excellent long-term reliability) can be obtained. Since tungsten oxide is expensive, when it is used for only one electrode, the amount of tungsten oxide used is small and the cost merit is large.
- the polarizable electrode material of the present invention may be disposed in a pair of positive and negative via a separator.
- an electric double layer capacitor having the effects of the present invention high energy density and excellent long-term reliability
- Example 1 Evaluation of the surface area of tungsten oxide per gram of polarizable electrode material A polarizable electrode material was prepared by changing the surface area of tungsten oxide per gram of polarizable electrode material. The electric double layer capacitor using these various polarizable electrode materials was measured for electrical characteristics and evaluated.
- YP-80F manufactured by Kuraray Chemical Co., Ltd.
- acetylene black powder
- the obtained tape-like material is rolled and rolled three times to form a sheet, and further dried at 150 ° C. for 1 hour to remove ethanol to obtain a sheet of polarizable electrode material having a width of 100 mm and a thickness of 150 ⁇ m. It was.
- a conductive adhesive liquid (Bunny Height T-602 manufactured by Nippon Graphite Industry Co., Ltd.) is applied, and an electrode material sheet is stacked, and this is pressed through a compression roll, and the contact interfaces are bonded together. A laminated sheet was obtained. The laminated sheet was placed in an oven set at a temperature of 150 ° C. and held for 10 minutes, and the polarizable electrode was obtained by evaporating and removing the dispersion medium from the conductive adhesive liquid layer. As shown in FIG.
- the dimension of the portion where the polarizable electrode material sheet is laminated is 3 cm square, and the lead portion (the portion where the polarizable electrode is not laminated on the current collector) is 1
- a square-shaped polarizable electrode was punched out in a shape of ⁇ 5 cm.
- ⁇ Durability evaluation test> The produced electric double layer capacitor was operated at a voltage higher than 2.7 V and 3.0 V. At the start of operation and after 1000 hours of operation, capacitance and internal resistance were measured and compared to evaluate how much capacity was maintained and how much internal resistance increased.
- Capacitance density The electric double layer capacitor was connected to a 4ch charge / discharge tester manufactured by Power Systems Co., Ltd., charged for 1500 seconds under the conditions of 10 mA / cm 2 and 3.0 V, and discharged until 0 V was obtained under the condition of 10 mA / cm 2.
- the electric double layer at the time of charging in the 10th cycle is integrated by integrating the discharge curve from the start of the discharge in the 10th cycle to 0 V when this operation is performed as 10 cycles.
- the capacitance of the capacitor was obtained, and this was divided by the electrode volume to calculate the capacitance density.
- Capacitance maintenance rate For the electric double layer capacitor described above, one cycle of an operation of discharging at a temperature of 70 ° C. under conditions of 10 mA / cm 2 and 3.0 V for 100 hours and then discharging until reaching 0 V under the condition of 10 mA / cm 2 And this operation was repeated.
- the capacitance at the first cycle and the cycle at the time when a predetermined time (1000 hours) has elapsed is obtained by the method described above for the capacitance density, and the result is the static value at the time when the predetermined time has elapsed from the start of measurement (the first cycle).
- the capacitance retention rate was evaluated by the capacitance retention rate [100 ⁇ (capacitance of the cycle when a predetermined time elapses) / (capacitance at the first cycle)] (%).
- FIG. 3 shows a graph plotting the relationship between the tungsten oxide surface area per 1 g of the electrode and the capacitance retention ratio after the test.
- polarizable electrode materials were prepared using various activated carbons having different mesopore ratios (see Table 2).
- the used activated carbon is MSP20 (Maxsorb manufactured by MC Evatech Co., Ltd.), YP50F (manufactured by Kuraray Chemical Co., Ltd.), activated carbon A, B, C (produced by adjusting the activation time).
- tungsten oxide tungsten trioxide having the same kind and addition amount was used so that the surface area of the tungsten oxide per 1 g of the electrode material was 1 m 2 / g. Except for the above points, an electrode material was produced in the same manner as in Example 1.
- the manufacture of the current collector, the polarizable electrode, the manufacture of the electric double layer capacitor, and the durability performance evaluation of the electric double layer were also performed in the same manner as in Example 1.
- the capacitance density maintenance ratio is 86% or more, and the internal resistivity increase rate is 150 to 180%. It was kept low.
- the capacitance maintenance rate was as low as 30% and the internal resistance increase rate was as high as 700%. This is because the decomposition products are mesopores of activated carbon. This is thought to be due to the blockage.
- the ratio of the mesopore volume of the porous carbon particles is 85%, the initial capacitance density is as low as 7 F / cm 3 , which is considered to be because the micropores of the porous carbon particles are relatively lowered. It is done.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
(1)電気二重層キャパシタにおいて用いられ、多孔質炭素粒子、導電補助剤、酸化タングステン粉末、およびバインダーを含む分極性電極材であって、
該分極性電極材1gあたりの該酸化タングステンの表面積が0.2m2以上~6m2未満になるように、該酸化タングステンが該分極性電極材中に分散していることを特徴とする、分極性電極材が提供される。
(2)該酸化タングステンの1次粒子径が0.05μm以上~0.4μm以下であることを特徴とする、(1)に記載の電極材が提供される。
(3)該電極材中の該酸化タングステンの含有量が40質量%未満であることを特徴とする、(1)または(2)に記載の電極材が提供される。
(4)該多孔質炭素粒子において全細孔容積に対するメソ孔容積の比率が30%以上~85%未満であることを特徴とする、(1)~(3)のいずれか1項に記載の電極材が提供される。
(5)圧延処理によりシート状にされたものであることを特徴とする、(1)~(4)のいずれか1項に記載の電極材が提供される。
(6)前記バインダーがポリテトラフルオロエチレンであることを特徴とする、(1)~(5)のいずれか1項に記載の電極材が提供される。
(7)(1)~(6)のいずれか1項に記載の電極材を、セパレータを介して少なくとも負極側に配置してなることを特徴とする、電気二重層キャパシタが提供される。
(8)(1)~(6)のいずれか1項に記載の電極材の正負一対を、セパレータを介して配置してなることを特徴とする、電気二重層キャパシタが提供される。
分極性電極材中の酸化タングステン粉末の含有量は、電極材1gあたりの酸化タングステンの表面積が所定の範囲になるように、適宜調整される。概して、分極性電極材の合計質量(合計質量は、分極性電極材の主要構成要素を配合する際に用いた成形助剤を除去した後の乾燥質量)を基準として、2質量%以上40質量%未満の比率であることが好ましく、4質量%以上30質量%以下の比率であることがさらに好ましい。含有量が2質量%未満の場合は、水分の分解作用が不十分であり、効果が十分でない。一方、酸化タングステンの含有量が40質量%を超えると、相対的に多孔質炭素粒子、導電補助剤の比率が低下するため、キャパシタセルの初期抵抗が上昇する。添加量が4質量%以上30質量%以下であると、水分の分解効果が顕著であると同時に初期抵抗を十分に低くできるため、より好ましい。
酸化タングステン粉末の粉砕に関しては活性炭の粉砕と同様にボールミル、ジェットミル、ハンマーミル等種々の方法で行うことができる。粉砕により目標の粒度(2次粒子径)に整えることができなければ、分級により粒度(2次粒子径)を調整しても良い。
なお、粉砕・分級といった工程によって、1次粒子径も変化し得る。概して、粉砕・分級といった工程によって、1次粒子の形状はより球形に近づき、また凝集状態が解消される傾向にあるため、BET比表面積と1次粒子径の相関はより高まり、1次粒子径の管理の精度は向上する。
賦活法はガス賦活、薬品賦活等の種々の方法を適用できる。ガス賦活で用いるガスは水蒸気、二酸化炭素、酸素、塩素、二酸化硫黄、硫黄蒸気等が使用できる。薬品賦活で用いる薬品は塩化亜鉛、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、リン酸、塩化カルシウム、硫化カリウム等が使用できる。
活性炭のBET比表面積が、500m2/g以上、好ましくは1000m2/g以上であり、3000m2/g以下、好ましくは2500m2/g以下である活性炭を用いることが可能である。活性炭の原料について、特に制限はない。具体的に例示すると、植物系の木材、椰子殻、パルプ廃液、化石燃料系の石炭、石油重質油、それらを熱分解した石炭、石油系ピッチ、コークス、合成樹脂であるフェノール樹脂、フラン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニルビニリデン樹脂等の種々の材料を用いることができる。
2.7V以上の使用電圧ではバインダーの酸化分解、還元分解も起こり易く、それにより粒子の結着力が弱くなるので、酸化還元を起こし難いPTFEが好ましい。
分極性電極材1gあたりの酸化タングステン表面積を変化させて、分極性電極材を作製した。この種々の分極性電極材を用いた電気二重層キャパシタについて、電気的特性を測定し、評価を行った。
[分極性電極材]
多孔質炭素粒子としてBET法による比表面積が約2100m2/gの水蒸気賦活の椰子殻活性炭(クラレケミカル株式会社社製「YP-80F」)80質量部と、導電補助剤としてアセチレンブラック粉末(電気化学工業株式会社製「デンカブラック 粉状品」)10質量部と、バインダーとしてポリテトラフルオロエチレン粉末(三井デュポンフロロケミカル株式会社製「テフロン6J」)10質量部と、分極性電極材1gあたりの表面積が所定の量になるように種類、添加量を調整した種々の三酸化タングステン(表1参照)からなる混合物にエタノール30質量部を加えて混錬後、テープ状にペースト押出した。その後、得られたテープ状物にロール圧延を3回実施してシート化し、更に150℃で1時間乾燥させてエタノールを除去することにより幅100mm、厚さ150μmの分極性電極材のシートを得た。
幅150mm、厚さ50μmの高純度エッチドアルミニウム箔(KDK株式会社製「C512」)を集電体とした。
集電体の片面に、導電性接着剤液(日本黒鉛工業株式会社製バニーハイトT-602)を塗布して電極材シートを重ね、これを圧縮ロールに通して圧着し、接触界面同士を貼り合わせた積層シートを得た。この積層シートを、温度150℃に設定したオーブンに入れて10分間保持し、導電性接着剤液層から分散媒を蒸発除去することにより分極性電極を得た。この積層シートを、図1に示したように、分極性電極材シートが積層された部分の寸法が3cm角で、リード部(集電体上に分極性電極が積層されていない部分)が1×5cmの形状になるように打ち抜いて方形状の分極性電極とした。
二枚の分極性電極を正極、負極とし、その間にセパレータとして厚さ80μm、3.5cm角の親水化処理した多孔質PTFEシート(日本ゴア株式会社製「BSP0708070-2」)を1枚挿入して、5×10cmの二枚のアルミラミネート材(昭和電工パッケージング株式会社製「PET12/AL20/PET12/CPP30ドライラミネート品」)で電極およびセパレータ部を覆い、リード部を含む3辺を熱融着によりシールしてアルミパックセルを作成した。(図2に、アルミラミネート材を熱融着する前の電気二重層キャパシタを示す。)熱融着の際、リード部の一部をアルミパックセルの外部に導き出し、リード部とアルミパックセルとの接合部がリード部とアルミラミネート材の熱融着によりシールされるようにした。このアルミパックセルを150℃で24時間真空乾燥した後、アルゴン雰囲気で-60℃以下の露点を保ったグローブボックス内に持ち込み、開口部(シールされていない辺)を上に向けて1.5モル/Lのトリエチルメチルアンモニウムテトラフルオロボレートの炭酸プロピレン(TEMA/PC)溶液4mLを電解質溶液としてアルミパックに注入し、-0.05MPaの減圧下に10分間静置して、電極内部のガスを電解質溶液で置換した。最後にアルミパックの開口部を融着密封することにより、単積層型の電気二重層キャパシタを作製した。この電気二重層キャパシタを40℃において24時間保存し、電極内部まで電解質溶液をエージングした。その後キャパシタを5×5cm、厚さ5mmのSUS板で挟み、面方向から1MPaで加圧し、例1の電気二重層キャパシタを作製した。
作製した電気二重層キャパシタについて、2.7Vより高い電圧、3.0Vで運転を行った。運転開始時と、1000時間運転後に、静電容量および内部抵抗を測定し、それらを比較し、どの程度容量が維持されるか、および、どの程度内部抵抗が上昇するかを評価した。
[静電容量密度]
上記電気二重層キャパシタについて、株式会社パワーシステム社製4ch充放電試験機に接続し、10mA/cm2、3.0Vの条件で1500秒充電し、10mA/cm2の条件で0Vになるまで放電を行う操作を1サイクルとし、これを10サイクル連続して行った際の、10サイクル目の放電開始から0Vになるまでの放電曲線を積分して、該10サイクル目の充電時における電気二重層キャパシタの静電容量を求め、これを電極体積で除して静電容量密度として算出した。
放電開始から全放電時間の10%の範囲までの放電曲線を最小二乗法により直線近似し、放電開始時における放電開始電圧との電圧差ΔVを用いてR=ΔV/Iの式より求めた。
上記電気二重層キャパシタについて、70℃の温度下で、10mA/cm2、3.0Vの条件で、100時間フロート充電した後、10mA/cm2条件で0Vになるまで放電を行う操作を1サイクルとし、この操作を繰り返した。1サイクル目と所定時間(1000時間)経過時のサイクルでの静電容量を、静電容量密度について上記した方法で求め、結果は、測定スタート時(1サイクル目)に対する所定時間経過時の静電容量の維持率[100×(所定時間経過時のサイクルの静電容量)/(1サイクル目の静電容量)](%)で静電容量維持率を評価した。
上記静電容量維持率測定時に、直流内部抵抗も測定し、(所定時間経過時の内部抵抗)/(初期の内部抵抗)×100で内部抵抗上昇率を評価した。
多孔質炭素粒子において全細孔容積に対するメソ孔容積の比率を変化させて、分極性電極材を作製した。この分極性電極材を用いた電気二重層キャパシタについて、種々の電気的特性を測定し、評価を行った。
10 分極性電極
11 集電体
12 分極性電極層
13 導電性接着剤
15 セパレータ
16 アルミラミネート材
Claims (8)
- 電気二重層キャパシタにおいて用いられ、多孔質炭素粒子、導電補助剤、酸化タングステン粉末、およびバインダーを含む分極性電極材であって、
該分極性電極材1gあたりの該酸化タングステンの表面積が0.2m2以上~6m2未満になるように、該酸化タングステンが該分極性電極材中に分散していることを特徴とする、分極性電極材。 - 該酸化タングステンの1次粒子径が0.05μm以上~0.4μm以下であることを特徴とする、請求項1に記載の電極材。
- 該電極材中の該酸化タングステンの含有量が40質量%未満であることを特徴とする、請求項1または2に記載の電極材。
- 該多孔質炭素粒子において全細孔容積に対するメソ孔容積の比率が30%以上~85%未満であることを特徴とする、請求項1~3のいずれか1項に記載の電極材。
- 圧延処理によりシート状にされたものであることを特徴とする、請求項1~4のいずれか1項に記載の電極材。
- 前記バインダーがポリテトラフルオロエチレンであることを特徴とする、請求項1~5のいずれか1項に記載の電極材。
- 請求項1~6のいずれか1項に記載の電極材を、セパレータを介して少なくとも負極側に配置してなることを特徴とする、電気二重層キャパシタ。
- 請求項1~6のいずれか1項に記載の電極材の正負一対を、セパレータを介して配置してなることを特徴とする、電気二重層キャパシタ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13823901.7A EP2879143B1 (en) | 2012-07-26 | 2013-07-25 | Polarizable electrode material and electric double layer capacitor using same |
KR1020157001353A KR102055033B1 (ko) | 2012-07-26 | 2013-07-25 | 분극성 전극재 및 이것을 사용한 전기 이중층 캐패시터 |
US14/413,321 US9552931B2 (en) | 2012-07-26 | 2013-07-25 | Polarizable electrode material and electric double layer capacitor using same |
CN201380039728.9A CN104508775B (zh) | 2012-07-26 | 2013-07-25 | 极化性电极材料及使用该材料的双电层电容器 |
JP2014527006A JP6150801B2 (ja) | 2012-07-26 | 2013-07-25 | 分極性電極材およびこれを用いた電気二重層キャパシタ |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012165800 | 2012-07-26 | ||
JP2012-165800 | 2012-07-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014017597A1 true WO2014017597A1 (ja) | 2014-01-30 |
Family
ID=49997404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/070214 WO2014017597A1 (ja) | 2012-07-26 | 2013-07-25 | 分極性電極材およびこれを用いた電気二重層キャパシタ |
Country Status (6)
Country | Link |
---|---|
US (1) | US9552931B2 (ja) |
EP (1) | EP2879143B1 (ja) |
JP (1) | JP6150801B2 (ja) |
KR (1) | KR102055033B1 (ja) |
CN (1) | CN104508775B (ja) |
WO (1) | WO2014017597A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015195645A (ja) * | 2014-03-31 | 2015-11-05 | デクセリアルズ株式会社 | ポリマー素子、電子機器、カメラモジュールおよび撮像装置 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3293745B1 (de) * | 2016-09-12 | 2019-08-14 | Heraeus Battery Technology GmbH | Additiv-material für eine elektrode einer elektrochemischen zelle, doppelschichtkondensator und herstellungsverfahren für eine elektrode desselben |
CN110534350B (zh) * | 2019-08-22 | 2022-03-22 | 江苏大学 | 一种功能化碳纳米片/wo3纳米棒复合材料及制备方法 |
KR102640902B1 (ko) | 2021-11-08 | 2024-02-27 | 한국생산기술연구원 | 테트라히드로퓨란-2,5-디카르복실산을 이용한 테트라히드로퓨란-2,5-디에스터의 제조 및 분리 정제 방법 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10106900A (ja) | 1996-09-27 | 1998-04-24 | Toyota Motor Corp | 電気二重層キャパシタ用電極 |
JPH11317333A (ja) | 1998-03-03 | 1999-11-16 | Jeol Ltd | 電気二重層コンデンサ用炭素材料、電気二重層コンデンサ用炭素材料の製造方法、電気二重層コンデンサ及び電気二重層コンデンサの製造方法 |
JP2003209029A (ja) | 2002-01-11 | 2003-07-25 | Meidensha Corp | 耐電圧を向上させた電気二重層キャパシタ |
JP2003282371A (ja) * | 2002-03-27 | 2003-10-03 | Matsushita Electric Ind Co Ltd | 電気化学蓄電デバイス用電極材料とこれを用いた電気化学蓄電デバイス、および電気化学蓄電デバイス用電極の製造方法 |
JP2007067155A (ja) | 2005-08-31 | 2007-03-15 | Mitsubishi Paper Mills Ltd | 電気化学素子用セパレータ |
JP2007073810A (ja) | 2005-09-08 | 2007-03-22 | Honda Motor Co Ltd | 電気二重層キャパシタ |
JP2008112827A (ja) | 2006-10-30 | 2008-05-15 | Mitsubishi Paper Mills Ltd | 電気二重層キャパシタ用セパレータ |
WO2008056536A1 (fr) * | 2006-11-08 | 2008-05-15 | Toyota Jidosha Kabushiki Kaisha | Dispositif de stockage d'électricité, utilisation et procédé de production de celui-ci |
JP2008252062A (ja) | 2007-03-08 | 2008-10-16 | Mitsubishi Electric Corp | 電気二重層キャパシタ用電極シートの製造方法及び電気二重層キャパシタ |
JP2008270807A (ja) * | 2007-04-16 | 2008-11-06 | Korea Inst Of Science & Technology | 超極細炭素繊維上に堆積された金属酸化物からなるスーパーキャパシタ用電極およびその製造方法 |
JP2011233845A (ja) | 2010-04-30 | 2011-11-17 | Nihon Gore Co Ltd | 耐電圧性を向上させた電気二重層キャパシタ用の分極性電極材およびこれを用いた電気二重層キャパシタ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0890963A3 (en) * | 1997-07-09 | 1999-11-17 | Mitsubishi Chemical Corporation | Electric double-layer capacitor |
CN100382214C (zh) * | 2003-07-03 | 2008-04-16 | 中国科学院电工研究所 | 一种用于超级电容器的复合碳基电极材料及其制备方法 |
JP4273215B2 (ja) * | 2004-08-27 | 2009-06-03 | 独立行政法人産業技術総合研究所 | 炭素で被覆された金属微粒子からなるレドックス型キャパシタの電極材料、このものからなるレドックス型キャパシタの電極および該電極を備えたレドックス型キャパシタ |
CN103370756B (zh) * | 2010-12-28 | 2018-05-11 | 巴斯福股份公司 | 包含增强的电化学特性的碳材料 |
-
2013
- 2013-07-25 EP EP13823901.7A patent/EP2879143B1/en active Active
- 2013-07-25 US US14/413,321 patent/US9552931B2/en active Active
- 2013-07-25 CN CN201380039728.9A patent/CN104508775B/zh active Active
- 2013-07-25 KR KR1020157001353A patent/KR102055033B1/ko active IP Right Grant
- 2013-07-25 WO PCT/JP2013/070214 patent/WO2014017597A1/ja active Application Filing
- 2013-07-25 JP JP2014527006A patent/JP6150801B2/ja active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10106900A (ja) | 1996-09-27 | 1998-04-24 | Toyota Motor Corp | 電気二重層キャパシタ用電極 |
JPH11317333A (ja) | 1998-03-03 | 1999-11-16 | Jeol Ltd | 電気二重層コンデンサ用炭素材料、電気二重層コンデンサ用炭素材料の製造方法、電気二重層コンデンサ及び電気二重層コンデンサの製造方法 |
JP2003209029A (ja) | 2002-01-11 | 2003-07-25 | Meidensha Corp | 耐電圧を向上させた電気二重層キャパシタ |
JP2003282371A (ja) * | 2002-03-27 | 2003-10-03 | Matsushita Electric Ind Co Ltd | 電気化学蓄電デバイス用電極材料とこれを用いた電気化学蓄電デバイス、および電気化学蓄電デバイス用電極の製造方法 |
JP2007067155A (ja) | 2005-08-31 | 2007-03-15 | Mitsubishi Paper Mills Ltd | 電気化学素子用セパレータ |
JP2007073810A (ja) | 2005-09-08 | 2007-03-22 | Honda Motor Co Ltd | 電気二重層キャパシタ |
JP2008112827A (ja) | 2006-10-30 | 2008-05-15 | Mitsubishi Paper Mills Ltd | 電気二重層キャパシタ用セパレータ |
WO2008056536A1 (fr) * | 2006-11-08 | 2008-05-15 | Toyota Jidosha Kabushiki Kaisha | Dispositif de stockage d'électricité, utilisation et procédé de production de celui-ci |
JP2008252062A (ja) | 2007-03-08 | 2008-10-16 | Mitsubishi Electric Corp | 電気二重層キャパシタ用電極シートの製造方法及び電気二重層キャパシタ |
JP2008270807A (ja) * | 2007-04-16 | 2008-11-06 | Korea Inst Of Science & Technology | 超極細炭素繊維上に堆積された金属酸化物からなるスーパーキャパシタ用電極およびその製造方法 |
JP2011233845A (ja) | 2010-04-30 | 2011-11-17 | Nihon Gore Co Ltd | 耐電圧性を向上させた電気二重層キャパシタ用の分極性電極材およびこれを用いた電気二重層キャパシタ |
Non-Patent Citations (1)
Title |
---|
FRONTIERS OF DEVELOPMENT OF NEXT-GENERATION CAPACITOR, 2009, pages 91,141 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015195645A (ja) * | 2014-03-31 | 2015-11-05 | デクセリアルズ株式会社 | ポリマー素子、電子機器、カメラモジュールおよび撮像装置 |
Also Published As
Publication number | Publication date |
---|---|
KR20150037844A (ko) | 2015-04-08 |
CN104508775B (zh) | 2018-03-02 |
EP2879143B1 (en) | 2019-11-27 |
JP6150801B2 (ja) | 2017-06-21 |
US9552931B2 (en) | 2017-01-24 |
JPWO2014017597A1 (ja) | 2016-07-11 |
EP2879143A4 (en) | 2016-03-02 |
CN104508775A (zh) | 2015-04-08 |
EP2879143A1 (en) | 2015-06-03 |
US20150138693A1 (en) | 2015-05-21 |
KR102055033B1 (ko) | 2019-12-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5578925B2 (ja) | 耐電圧性を向上させた電気二重層キャパシタ用の分極性電極材およびこれを用いた電気二重層キャパシタ | |
US9053871B2 (en) | High surface area and low structure carbon blacks for energy storage applications | |
JP4959259B2 (ja) | 電気二重層キャパシタ | |
JP4878881B2 (ja) | 電気二重層キャパシタ用電極および電気二重層キャパシタ | |
CN110582464B (zh) | 改质活性炭和其制造方法 | |
KR20080012952A (ko) | 전기 이중층 캐패시터용 전극 및 전기 이중층 캐패시터 | |
JP2013157603A (ja) | リチウムイオンキャパシタ用活性炭、これを活物質として含む電極、及び前記電極を用いるリチウムイオンキャパシタ | |
KR20070114214A (ko) | 전기 이중층 캐패시터의 제조 방법 | |
JP6150801B2 (ja) | 分極性電極材およびこれを用いた電気二重層キャパシタ | |
JP7462066B2 (ja) | 非水系アルカリ金属蓄電素子および正極塗工液 | |
Kim et al. | Ribbon-like activated carbon with a multi-structure for supercapacitors | |
EP3831772A1 (en) | Carbon material and method for producing same, electrode material for electrical storage device, and electrical storage device | |
JP2007019491A (ja) | 電気二重層キャパシタ用電極および電気二重層キャパシタ | |
Aalto et al. | Carbon nanotube supercellulose supercapacitor | |
JP2015198169A (ja) | Edlc用電極及びedlc | |
JP6179195B2 (ja) | 電気二重層キャパシタ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13823901 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014527006 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14413321 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013823901 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20157001353 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |