WO2006132444A1 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- WO2006132444A1 WO2006132444A1 PCT/JP2006/312084 JP2006312084W WO2006132444A1 WO 2006132444 A1 WO2006132444 A1 WO 2006132444A1 JP 2006312084 W JP2006312084 W JP 2006312084W WO 2006132444 A1 WO2006132444 A1 WO 2006132444A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electric double
- double layer
- electrolyte
- graphite
- electrode
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 69
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 150000003413 spiro compounds Chemical class 0.000 claims abstract description 19
- 125000006413 ring segment Chemical group 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 66
- 239000011229 interlayer Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002050 diffraction method Methods 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 22
- 230000004913 activation Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 16
- 239000013078 crystal Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- -1 compound salts Chemical class 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- NZSICTQUKULOSA-UHFFFAOYSA-N 5-azoniaspiro[4.4]nonane Chemical class C1CCC[N+]21CCCC2 NZSICTQUKULOSA-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 7
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ODJKHOBNYXJHRG-UHFFFAOYSA-N 1,3-dimethylimidazole Chemical compound CN1[CH]N(C)C=C1 ODJKHOBNYXJHRG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 241001061127 Thione Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical class CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 2
- ZOMPBXWFMAJRRU-UHFFFAOYSA-N 3-ethyloxiran-2-one Chemical compound CCC1OC1=O ZOMPBXWFMAJRRU-UHFFFAOYSA-N 0.000 description 1
- JLEIRAYWBMNMKU-UHFFFAOYSA-N 3-ethylpentan-3-amine Chemical compound CCC(N)(CC)CC JLEIRAYWBMNMKU-UHFFFAOYSA-N 0.000 description 1
- HOTNVZSJGHTWIU-UHFFFAOYSA-N 6-azoniaspiro[5.5]undecane Chemical compound C1CCCC[N+]21CCCCC2 HOTNVZSJGHTWIU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 101000788892 Homo sapiens Zinc finger protein 280C Proteins 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 102100037681 Protein FEV Human genes 0.000 description 1
- 101710198166 Protein FEV Proteins 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 102100025295 Zinc finger protein 280C Human genes 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 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
- 239000011295 pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film 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
- 238000010248 power generation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
-
- 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an electrode for electric double layer capacity and an electric double layer capacity.
- electric double-layer capacitors that can be charged and discharged with a large current are promising as storage devices with high charging and discharging frequency, such as auxiliary power sources for electric vehicles, auxiliary power sources for solar cells, and auxiliary power sources for wind power generation. For this reason, electric double layer capacities with high energy density, rapid charge / discharge, and excellent durability are desired.
- the electric double layer capacitor has a structure in which a pair of polarizable electrodes are opposed to each other via a separator to form a positive electrode and a negative electrode.
- Each polarizable electrode is impregnated with an aqueous electrolyte solution or a non-aqueous electrolyte solution, and each polarizable electrode is joined to a collector electrode.
- Aqueous electrolyte solution can increase the volume capacitance density and reduce the resistance value, but the working voltage must be lower than the voltage at which water electrolysis occurs.
- a non-aqueous electrolyte is used to increase the energy density.
- a polarizable electrode material used in an electric double layer capacitor a carbon material having microcrystalline carbon similar to graphite (hereinafter referred to as “graphite”) (Referred to as “similar carbon material”) (Japanese Laid-Open Patent Publication Nos. 1 1-3 1 7 3 3 3, 2 0 0 0-0 7 7 2 7 3, and — Publication No. 0 6 8 1 6 4, Japanese Unexamined Patent Publication No. 2 0 0 0 — 0 6 8 1 6 5 and Japanese Unexamined Patent Publication No. 0 6 6 8).
- an electrolyte for electric field activation type capacitors it is suitable for electric field activation type capacitors that apply a high voltage with a wide potential window.
- Tetraethyl quaternary ammonium salt, tetraethyl ammonium salt, asymmetric A type of triethylmethylammonium salt or the like used as an electrolyte has been used (Japanese Patent Laid-Open No. 2 0 00-0 7 7 2 7 3).
- Japanese Patent Laid-Open No. 2 0 00-0 7 7 2 7 3 Japanese Patent Laid-Open No. 2 0 00-0 7 7 2 7 3
- these electrolytes are difficult to insert between 0.36 5 and 0.385 nm of a graphite-like carbon material, so that the capacitance, DC internal resistance, etc. In this respect, the electrode performance of graphite-like carbon material could not be fully exploited.
- an electric field activated capacitor unlike the conventional activated carbon type, the capacity of the electrolyte ion at the time of electric field activation, especially its structure, can be exhibited only after the pores are formed by the insertion of electrolyte ions. , Capacitance performance is greatly affected. Focusing on the structural aspects of such electrolyte ions, imidazolium has a planar molecular structure. It has been proposed to use a salt as an electrolyte for an electric field activation type capacitor (Japanese Patent Laid-Open No. 2000-028 930). Since such an electrolyte is easily inserted between the layers of microcrystalline carbon, the capacitance of the obtained capacitor and the initial value of the DC internal resistance can be improved.
- the proposed imidazolium salt electrolyte has a narrower potential window than the tetraalkyl quaternary ammonium salt, and the electrolyte itself decomposes when a high voltage is applied. Therefore, the electrode performance of graphite-like carbon materials can be fully exploited. Cannot be used at high rated voltage.
- the present invention is an electric field activated electric double layer key that can improve the volume capacitance density (energy density), the resistance value, and the withstand voltage at the same time by selecting an electrolyte, and thereby sufficiently bring out the electrode performance of the graphite-like carbon material.
- the purpose is to provide a happi evening.
- A represents a spiro atom having sp 3 hybrid orbital
- Z 1 and Z 2 each independently form a saturated or unsaturated ring having 4 or more ring atoms including A.
- X_ represents an anion.
- FIG. 1 is a schematic diagram showing a method for producing a capacitor cell used in the examples.
- An electric double layer capacitor according to the present invention comprises a polarizable electrode containing a carbon material having a microcrystalline carbon similar to graphite, and an electrolyte containing a spiro compound represented by the general formula (1). It is a characteristic.
- the first expanded layer is further expanded to be further expanded.
- the entire ion is relatively bulky and the first stage insertion is unlikely to occur.
- the second stage of interlayer expansion does not occur.
- the second stage of interlayer expansion increases the specific surface area and makes it easier for electrolyte ions to move. Therefore, a higher capacitance and lower DC internal resistance than conventional field-activated capacitors using an electrolyte are realized. it can.
- the electrolyte containing the spiro compound according to the present invention has a wide potential window and can be used at a high voltage comparable to that of a quaternary ammonium salt, so that the energy density proportional to the square of the electrostatic capacity and the voltage is obtained. This can be significantly increased compared to the conventional method.
- the electrolyte containing the spiro compound according to the present invention is represented by the following general formula (1).
- A represents a spiro atom having an sp 3 hybrid orbital, and is specifically selected from nitrogen (N) and carbon (C).
- the positive charge of the spiro compound molecule is preferably localized on the spiro atom so that the charge is shielded by surrounding structures so that the effect of solvation is reduced.
- the spiro atom is preferably nitrogen in that the atomic radius is relatively small.
- Z 1 and Z 2 each independently represent an atomic group forming a saturated or unsaturated ring having 4 or more ring atoms including A.
- the two cyclic structures represented by Z 1 and Z 2 are similar in type and / or number of ring atoms so that the ease of insertion of the graphite-like carbon material between the crystal layers is less affected by the orientation of the molecules. It is more preferable that the type and number of ring atoms are the same.
- the number of ring atoms is preferably 5 or more from the viewpoint of the synthesis of the spiro compound, and 5 or more is most preferable because the conductivity decreases when it is 6 or more.
- Ring atoms can contain nitrogen, sulfur, oxygen, etc. in addition to carbon.
- the ring atom of the spiro compound according to the present invention has a substituent. In this case, it is preferable that the substituent is small, and it is more preferable that the substituent does not contain any substituent.
- x_ represents an anion.
- an anion from the viewpoint of electrochemical stability and molecular ion diameter, BF 4 _, PF 6 —, A s F 6 one, C l 0 4 —, CF 3 S 0 3 one, (CF 3 SO 2) 2 N—, A 1 C 1 4 —, S b F 6 and the like are preferable, and BF 4 — is particularly preferable.
- specific examples of the electrolyte cation suitably used in the present invention will be listed.
- the electrolyte according to the present invention may be used as it is without being diluted when it is liquid at room temperature, but it is generally preferable to use it as an electrolyte dissolved in an organic solvent.
- an organic solvent By using an organic solvent, the viscosity of the electrolyte can be lowered, and an increase in the internal DC resistance of the electrode can be suppressed.
- the organic solvent is selected depending on the solubility of the electrolyte and the reactivity with the electrode, but propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), jetyl carbonate (DEC), dimethoxetane.
- the electrolyte is a 1,1'-spirobipyrrolidinium compound, it has a solubility three or more times that of tetraethylammonium salt in propylene carbonate. The degree can be secured.
- the organic solvent may be used alone or as a mixed solvent combining two or more. Since the electrolyte ions inserted between the crystal layers of the graphite-like carbon material at the time of electric field activation are considered to be solvated with the surrounding solvent, it is preferable to use a solvent having a small molecular volume.
- the specific surface area of this graphite-like carbon material is preferably not more than 800 m 2 / g, and more preferably not more than 600 m 2 Z g. When the specific surface area exceeds 800 m 2 / g, sufficient electrostatic capacity can be obtained without using electric field activation. In addition, the amount of functional groups present on the surface of the graphite-like carbon material increases, and the performance of the electric double layer capacitor significantly decreases due to the decomposition of these functional groups when a voltage is applied.
- the specific surface area is a value measured by the BET 1-point method using “MO SO SORB” manufactured by UASA Ionics Co., Ltd. (drying temperature: 180 ° C., drying time: 1 hour).
- the graphite-like carbon material can be a low-temperature-fired carbon material that has not been activated. Wood, coconut shells, pulp waste liquid, fossil fuel-based coal, heavy petroleum oil, and so on are used as heat. It can be produced using various materials such as decomposed coal, petroleum-based pitch, cox, synthetic resin such as phenol resin, furan resin, polyvinyl chloride resin, and polyvinylidene chloride resin.
- the carbon material is classified into graphitizable carbon and non-graphitizable carbon, it is preferable to use graphitizable carbon containing a large amount of graphite-like microcrystalline carbon from the viewpoint of capacitance. It is also difficult to graphitize to suppress electrode expansion during electric field activation.
- the electric double layer capacitor electrode includes a conductive auxiliary material for imparting conductivity to the graphite-like carbon material.
- a conductive auxiliary material carbon black such as Ketchen black or acetylene black, vapor grown carbon fiber, fullerene, carbon nanotube, nanocarbon such as carbon nanohorn, powdery or granular graphite, etc. can be used.
- the conductive auxiliary material is composed of graphite-like carbon material and a binder. The amount is preferably 1 to 40% by mass, more preferably 3 to 20% by mass, based on the total mass. When the added amount of this conductive auxiliary material is less than 1% by mass, the DC internal resistance of the electric double layer capacitor is increased. On the other hand, when the amount added exceeds 40% by mass, the energy density of the electrode decreases.
- the current collector described later is formed when the capacitor cell is formed.
- the body takes up more volume and the energy density is lower.
- the density of the electrode cannot be increased, so that the energy density is similarly reduced and the internal resistance of the electric double layer capacitor is also increased.
- the thickness of the electrode is a value measured using a dial thickness gauge “SM-5 28” manufactured by Teclock Co., Ltd. in a state where no load other than the main body spring load is applied.
- a pressure that resists the pressure (expansion pressure) generated by the expansion of the graphite-like carbon material may be applied to the electrode from the outside.
- the volume capacitance density can be increased by applying a pressure of 0.1 to 30 MPa to the electrode from the outside during charging.
- the expansion is about 5 to 100%. It is preferable to set the external pressure so that this occurs.
- the polarity of the positive and negative electrodes is reversed and the electrolytic activation is performed again.
- the size of the crystal layer of the graphite-like carbon material matches the cation (the ion diameter is larger than that of the anion).
- the specific surface area is increased and the electrolyte ions are easily moved, so that a higher capacitance and a lower DC internal resistance can be realized.
- Comparative Example 2 A capacitor was assembled in the same manner as in Example 1, except that a 1.5 mol / L 1,3-dimethylimidazole tetrafluoroporate propylene carbonate solution was used as the electrolyte.
- a capacitor was assembled in the same manner as in Example 1 except that a propylene carbonate solution of N, N-jetylpyrrolidinium tetrafluoropoorate was used as the electrolyte.
- Example 1 shows that even though the types and numbers of constituent atoms of the electrolyte are almost the same, the two annular structures are obtained from the high volumetric capacitance density and energy density of Example 1. It can be seen that electric field activation is promoted by bonding the body with spiro atoms.
- the volume capacitance of an electric field activated electric double layer capacitor is obtained. Density (energy density), resistance value, and withstand voltage are improved at the same time, and the electrode performance of graphite-like carbon materials can be further enhanced.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/916,602 US20090303658A1 (en) | 2005-06-10 | 2006-06-09 | Electrode for Electric Double Layer Capacitor and Electric Double Layer Capacitor |
EP06757373A EP1890307A4 (en) | 2005-06-10 | 2006-06-09 | ELECTRODE FOR AN ELECTRIC DOUBLE-LAYER CAPACITOR AND ELECTRIC DOUBLE-LAYER CAPACITOR |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-171537 | 2005-06-10 | ||
JP2005171537 | 2005-06-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006132444A1 true WO2006132444A1 (ja) | 2006-12-14 |
Family
ID=37498620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/312084 WO2006132444A1 (ja) | 2005-06-10 | 2006-06-09 | 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 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090303658A1 (ja) |
EP (1) | EP1890307A4 (ja) |
KR (1) | KR20080012952A (ja) |
CN (1) | CN101194328A (ja) |
TW (1) | TWI367511B (ja) |
WO (1) | WO2006132444A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016225397A (ja) * | 2015-05-28 | 2016-12-28 | パナソニックIpマネジメント株式会社 | 蓄電デバイス及びその製造方法 |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8760851B2 (en) | 2010-12-21 | 2014-06-24 | Fastcap Systems Corporation | Electrochemical double-layer capacitor for high temperature applications |
US9214709B2 (en) | 2010-12-21 | 2015-12-15 | CastCAP Systems Corporation | Battery-capacitor hybrid energy storage system for high temperature applications |
US9001495B2 (en) | 2011-02-23 | 2015-04-07 | Fastcap Systems Corporation | High power and high energy electrodes using carbon nanotubes |
JP2014525219A (ja) | 2011-05-24 | 2014-09-25 | ファーストキャップ・システムズ・コーポレイション | 再充電可能エネルギ貯蔵を伴う高温用途のためのパワーシステム |
AU2012267770A1 (en) | 2011-06-07 | 2014-01-23 | Fastcap Systems Corporation | Energy storage media for ultracapacitors |
US9558894B2 (en) | 2011-07-08 | 2017-01-31 | Fastcap Systems Corporation | Advanced electrolyte systems and their use in energy storage devices |
CN104221110B (zh) | 2011-07-08 | 2019-04-05 | 快帽系统公司 | 高温能量储存装置 |
CA2843137A1 (en) * | 2011-07-27 | 2013-01-31 | Fastcap Systems Corporation | Power supply for downhole instruments |
EP3783192A1 (en) | 2011-11-03 | 2021-02-24 | FastCAP SYSTEMS Corporation | Production logging instrument |
US9206672B2 (en) | 2013-03-15 | 2015-12-08 | Fastcap Systems Corporation | Inertial energy generator for supplying power to a downhole tool |
US10872737B2 (en) | 2013-10-09 | 2020-12-22 | Fastcap Systems Corporation | Advanced electrolytes for high temperature energy storage device |
WO2015095858A2 (en) | 2013-12-20 | 2015-06-25 | Fastcap Systems Corporation | Electromagnetic telemetry device |
US11270850B2 (en) | 2013-12-20 | 2022-03-08 | Fastcap Systems Corporation | Ultracapacitors with high frequency response |
EP3204955B1 (en) | 2014-10-09 | 2022-01-05 | Fastcap Systems Corporation | Nanostructured electrode for energy storage device |
KR101583525B1 (ko) | 2014-10-31 | 2016-01-11 | 주식회사 알파켐 | 슈퍼캐패시터용 전해액 및 이를 함유한 슈퍼캐패시터 |
KR102469677B1 (ko) | 2015-01-27 | 2022-11-22 | 패스트캡 시스템즈 코포레이션 | 넓은 온도 범위 울트라커패시터 |
KR20190003793A (ko) * | 2016-05-20 | 2019-01-09 | 에이브이엑스 코포레이션 | 울트라커패시터용 전극 구조 |
CN109155206A (zh) * | 2016-05-20 | 2019-01-04 | 阿维科斯公司 | 超级电容器用的非水电解质 |
CN115579248A (zh) | 2016-05-20 | 2023-01-06 | 京瓷Avx元器件公司 | 在高温下使用的超级电容器 |
WO2018062285A1 (ja) * | 2016-09-30 | 2018-04-05 | 積水化学工業株式会社 | 炭素材料、キャパシタ用電極シート及びキャパシタ |
CA3045460A1 (en) | 2016-12-02 | 2018-06-07 | Fastcap Systems Corporation | Composite electrode |
US11557765B2 (en) | 2019-07-05 | 2023-01-17 | Fastcap Systems Corporation | Electrodes for energy storage devices |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000077273A (ja) * | 1998-09-03 | 2000-03-14 | Ngk Insulators Ltd | 電気二重層コンデンサ及びその製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6310762B1 (en) * | 1998-03-03 | 2001-10-30 | Jeol Ltd. | Carbon material for electric double layer capacitor, method of producing same, electric double layer capacitor and method of fabricating same |
JP2004289130A (ja) * | 2003-03-04 | 2004-10-14 | Jeol Ltd | 電気二重層キャパシタ |
JP2005005357A (ja) * | 2003-06-10 | 2005-01-06 | Japan Carlit Co Ltd:The | 電解コンデンサ用電解液及び電解コンデンサ |
WO2005022571A1 (ja) * | 2003-08-29 | 2005-03-10 | Japan Carlit Co., Ltd. | 電気二重層キャパシタ用電解液及び電気二重層キャパシタ |
WO2005088658A1 (ja) * | 2004-03-10 | 2005-09-22 | Power Systems Co., Ltd. | 蓄電要素及び電気二重層キャパシタ |
JP3996588B2 (ja) * | 2004-03-30 | 2007-10-24 | 株式会社パワーシステム | 電気二重層キャパシタ |
WO2006068291A1 (ja) * | 2004-12-21 | 2006-06-29 | Teijin Limited | 電気二重層キャパシタ |
-
2006
- 2006-06-08 TW TW095120376A patent/TWI367511B/zh not_active IP Right Cessation
- 2006-06-09 EP EP06757373A patent/EP1890307A4/en not_active Withdrawn
- 2006-06-09 CN CNA2006800207000A patent/CN101194328A/zh active Pending
- 2006-06-09 WO PCT/JP2006/312084 patent/WO2006132444A1/ja active Application Filing
- 2006-06-09 KR KR1020077028652A patent/KR20080012952A/ko not_active Application Discontinuation
- 2006-06-09 US US11/916,602 patent/US20090303658A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000077273A (ja) * | 1998-09-03 | 2000-03-14 | Ngk Insulators Ltd | 電気二重層コンデンサ及びその製造方法 |
Non-Patent Citations (3)
Title |
---|
CHIBA K. ET AL.: "Spiro-gata Ammonium En Denkaieki Oyobi Kore o Mochiita Denki Nijuso Capacitor no Tokusei Hyoka", THE ELECTROCHEMICAL SOCIETY OF JAPAN DAI 72 KAI TAIKAI KOEN YOSHISHU, no. 1H21, 1 April 2005 (2005-04-01), pages 242, XP003005300 * |
See also references of EP1890307A4 * |
UE M. ET AL.: "Electrochemical Properties of Organic Liquid Electrolytes Based on Quaternary Onium Salts for Electrical Double-Layer Capacitors", J. ELECTROCHEM. SOC., vol. 141, no. 11, November 1994 (1994-11-01), pages 2989 - 2996, XP000764051 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016225397A (ja) * | 2015-05-28 | 2016-12-28 | パナソニックIpマネジメント株式会社 | 蓄電デバイス及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TWI367511B (en) | 2012-07-01 |
US20090303658A1 (en) | 2009-12-10 |
TW200705488A (en) | 2007-02-01 |
KR20080012952A (ko) | 2008-02-12 |
EP1890307A1 (en) | 2008-02-20 |
CN101194328A (zh) | 2008-06-04 |
EP1890307A4 (en) | 2011-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006132444A1 (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 | |
KR100836524B1 (ko) | 고용량 전극 활물질, 그 제조방법, 이를 구비한 전극 및에너지 저장 장치 | |
Zhang et al. | Carbon-based materials as supercapacitor electrodes | |
JP4705566B2 (ja) | 電極材及びその製造方法 | |
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 | |
KR101289521B1 (ko) | 전기 이중층 캐패시터의 제조 방법 | |
JP4959259B2 (ja) | 電気二重層キャパシタ | |
JP5228531B2 (ja) | 蓄電デバイス | |
Oyedotun et al. | Advances in supercapacitor development: materials, processes, and applications | |
KR101833081B1 (ko) | 내전압성을 향상시킨 전기 이중층 캐패시터용의 분극성 전극재 및 이를 이용한 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 | |
Chen et al. | Graphene based integrated tandem supercapacitors fabricated directly on separators | |
JP2016534565A (ja) | 分子篩を含有する炭素系電極 | |
TW201526048A (zh) | 具有改善老化性能的超級電容器 | |
TW201522219A (zh) | 高電壓與高電容之活性碳以及碳爲主之電極 | |
Kowsari | High-performance supercapacitors based on ionic liquids and a graphene nanostructure | |
JP2002231585A (ja) | 電気二重層コンデンサ | |
WO2007037523A9 (ja) | 電気二重層キャパシタ用炭素材料および電気二重層キャパシタ | |
JP6049205B2 (ja) | ウルトラキャパシタのための電解質合成 | |
EP2879143B1 (en) | Polarizable electrode material and electric double layer capacitor using same | |
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 | |
WO2007077906A1 (ja) | 非水系キャパシタ及びその製造方法 | |
Rustamaji et al. | Design, Fabrication, and Testing of Supercapacitor Based on Nanocarbon Composite Material | |
WO2011155000A1 (ja) | キャパシタ | |
Liu et al. | Supercapacitors: History, Theory, Emerging Technologies, and Applications |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200680020700.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2006757373 Country of ref document: EP Ref document number: 1020077028652 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWP | Wipo information: published in national office |
Ref document number: 2006757373 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11916602 Country of ref document: US |