JP6967688B2 - ハイブリッドキャパシタ - Google Patents
ハイブリッドキャパシタ Download PDFInfo
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- JP6967688B2 JP6967688B2 JP2021527695A JP2021527695A JP6967688B2 JP 6967688 B2 JP6967688 B2 JP 6967688B2 JP 2021527695 A JP2021527695 A JP 2021527695A JP 2021527695 A JP2021527695 A JP 2021527695A JP 6967688 B2 JP6967688 B2 JP 6967688B2
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- 239000003990 capacitor Substances 0.000 title claims description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 148
- 229910052782 aluminium Inorganic materials 0.000 claims description 77
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 229910002804 graphite Inorganic materials 0.000 claims description 48
- 239000010439 graphite Substances 0.000 claims description 48
- 238000007747 plating Methods 0.000 claims description 32
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910021385 hard carbon Inorganic materials 0.000 claims description 7
- 229910021384 soft carbon Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000011888 foil Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 15
- 239000008151 electrolyte solution Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- OGLIVJFAKNJZRE-UHFFFAOYSA-N 1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1 OGLIVJFAKNJZRE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- RDKKQZIFDSEMNU-UHFFFAOYSA-N 2-ethylsulfonylpropane Chemical compound CCS(=O)(=O)C(C)C RDKKQZIFDSEMNU-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- UPOHIXYDQZCJLR-UHFFFAOYSA-J tetraethylazanium tetrafluoride Chemical compound C(C)[N+](CC)(CC)CC.[F-].[F-].[F-].[F-].C(C)[N+](CC)(CC)CC.C(C)[N+](CC)(CC)CC.C(C)[N+](CC)(CC)CC UPOHIXYDQZCJLR-UHFFFAOYSA-J 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
本願は、2019年6月24日に、日本に出願された特願2019−116704号に基づき優先権を主張し、その内容をここに援用する。
ここで、電気二重層キャパシタに蓄積されるエネルギー(E)は、キャパシタの静電容量(C)と印加電圧(V)を用いてE=1/2×C×V2と表され、エネルギーは静電容量と印加電圧の二乗とに比例する。従って、電気二重層キャパシタのエネルギー密度を改善するために、電気二重層キャパシタの静電容量や印加電圧を向上する技術が提案されている。
有機電解液は使用できる電圧範囲が広いため、印加電圧を高めることができ、エネルギー密度を向上することができる。
負極活物質層は主に、負極活物質、バインダー、および、必要に応じた量の導電材を含むペースト状の負極材料を、負極側の集電体上に塗布し、乾燥して、形成することができる。
アルゴングローブボックス中で、LiClとKClを重量パーセント濃度(wt%)50:50の比率で含む溶液に対して、CaC2を5mol%加え、500℃で溶解させたものを溶融塩浴とした。陽極にはアルミニウム箔(厚さ50μm)を用い、陰極にはグラッシーカーボンを用いた。3mA/cm2の定電流で25分間電解を行い、純度99.99%のアルミニウム箔(厚さ50μm)上に炭素をめっきし、本実施例の正極側の集電体を得た。
SEMで集電体の断面を観察して炭素めっき膜の厚み(膜厚)を測定したところ、3μmであった。また、sp2構造の比率sp2/(sp2+sp3)を、軟X線XANES(X線吸収端近傍構造)を用いて測定したところ、83%であった。
負極側の集電体として実施例1の正極側の集電体と同様に、炭素めっき膜で被覆されたアルミニウム箔を用いたこと以外は、実施例1と同様の2032型コインセルを作製した。
正極活物質として大阪ガスケミカル株式会社製人造黒鉛(商品名:MCMB6−10)を用いたこと以外は、実施例1と同様の2032型コインセルを作製した。
負極活物質としてチタン酸リチウムLi4Ti5O12を用い、電解質に1Mの四フッ化ホウ酸リチウムLiBF4、溶媒にプロピレンカーボネート(PC)を用いた電解液を用いたこと以外は、実施例1と同様の2032型コインセルを作製した。
実施例1の炭素めっきと同じ手順において、定電流での電解の時間を変化させ、炭素めっき膜の厚みが異なる複数の集電体を作製した。具体的には、厚みが0nm、50nm、100nm、300nm、1000nm、2000nm、3000nm、5000nm、7000nm、10000nmのものを作製した。いずれも、定電流での電解の時間を変えたこと以外は、実施例1と同様の2032型コインセルを作製した。
実施例1で負極活物質として用いた関西熱化学株式会社製活性炭(商品名:MSP−20)を、正極活物質としても用いたこと以外は、実施例1と同様の2032型コインセルを作製した。
正極側の集電体としてDLCコーティングしたアルミニウム箔(以下、「DLCコートアルミニウム箔」ということがある)を用いたこと以外は、実施例1と同様の2032型コインセルを作製した。DLCコートアルミニウム箔は、非晶質炭素被膜で被覆されたアルミニウム材に相当する。DLCコートアルミニウム箔の製造法としては、純度99.99%のアルミニウム箔(厚さ50μm)に対して、アルゴンスパッタリングでアルミニウム箔表面の自然酸化膜を除去した後、そのアルミニウム表面近傍にメタン、アセチレンおよび窒素の混合ガス中で放電プラズマを発生させ、アルミニウム材に負のバイアス電圧を印加することによりDLC膜を生成させた。ここで、DLCをコーティング(被覆)したアルミニウム箔上のDLC膜の厚みを、ブルカー(BRUKER)社製触針式表面形状測定器DektakXTを用いて計測したところ、135nmであった。
Claims (7)
- ハイブリッドキャパシタであって、
正極は正極活物質として黒鉛を含み、
正極側の集電体はアルミニウム材であり、
前記アルミニウム材は、sp2構造の含有比率sp2/(sp2+sp3)が80%以上であり、かつsp 2 構造とsp 3 構造の両方を含有する炭素めっき膜で被覆されている
ことを特徴とするハイブリッドキャパシタ。 - 前記炭素めっき膜のビッカーズ硬度は、3HV〜80HVである
請求項1に記載のハイブリッドキャパシタ。 - 前記炭素めっき膜の厚みは、100nm以上、5000nm以下である
請求項1または2のいずれかに記載のハイブリッドキャパシタ。 - 負極側の集電体は、炭素めっき膜で被覆されたアルミニウム材、非晶質炭素被膜と負極活物質との間に導電性炭素層が形成されているアルミニウム材、非晶質炭素被膜で被覆されたアルミニウム材、エッチドアルミニウム、および、アルミニウム材からなる群から選択されたものである
請求項1〜3のいずれか一項に記載のハイブリッドキャパシタ。 - 前記黒鉛は、菱面体晶を含む
請求項1〜4のいずれか一項に記載のハイブリッドキャパシタ。 - 負極は、負極活物質として活性炭、黒鉛、ハードカーボン、および、ソフトカーボンからなる群から選択された炭素質材料、あるいはチタン酸リチウムの少なくとも1つを含む
請求項1〜5のいずれか一項に記載のハイブリッドキャパシタ。 - 前記炭素めっき膜は、溶融塩を原料とするめっき膜である
請求項1〜6のいずれか一項に記載のハイブリッドキャパシタ。
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