TW434604B - Supercapacitor structure and method of making same - Google Patents
Supercapacitor structure and method of making same Download PDFInfo
- Publication number
- TW434604B TW434604B TW088116384A TW88116384A TW434604B TW 434604 B TW434604 B TW 434604B TW 088116384 A TW088116384 A TW 088116384A TW 88116384 A TW88116384 A TW 88116384A TW 434604 B TW434604 B TW 434604B
- Authority
- TW
- Taiwan
- Prior art keywords
- electrode
- supercapacitor
- film
- patent application
- ultracapacitor
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 27
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- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- 239000011530 conductive current collector Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 5
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- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
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- 238000010438 heat treatment Methods 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
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- 210000003813 thumb Anatomy 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- NITMACBPVVUGOJ-UHFFFAOYSA-N 2,2,2-trifluoroethanimidamide Chemical compound NC(=N)C(F)(F)F NITMACBPVVUGOJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZBJBRUSGEJORQL-UHFFFAOYSA-N diphenan Chemical compound C1=CC(OC(=O)N)=CC=C1CC1=CC=CC=C1 ZBJBRUSGEJORQL-UHFFFAOYSA-N 0.000 description 1
- 229950002048 diphenan Drugs 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000011256 inorganic filler Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
- H01G11/72—Current collectors specially adapted for integration in multiple or stacked hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
- H01M10/4264—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing with capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M16/00—Structural combinations of different types of electrochemical generators
-
- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
434604 A7 五、發明說明(1〉 發明背景 本發明有關能夠在數秒至數分鐘之範圍之相對長時期下 呈現高能量電容及高電流密度放電之電容器。此種,,超電 容’’特別可用於在比單獨之電池系統所需更短許多之時間 内遞送高量之電流至利用裝置。本發明特別針對超電容結 構,及其製法,其將基本電容器元件摻併成整體式、可撓 性結構,其可如所欲形成與利用裝置最相容之各種尺寸與 形狀,同時提供有利的高能量容量與電流密度。本發明進 一步利用可獲得之聚合物充電式電池技術,以便提供能夠 保有功率及使新穎之超電容結構多樣尺寸之混合超電容系 統。 可獲得之超電容大部分為具有雙層形式者,其中以包含 均勻分散電解質成分之微孔性、電絕緣、離子傳導之片材 兀件將一對電極(典型上包含活性碳微粒)隔開。典型之超 電容結構進一步包含與各自電極緊密接觸之導電性電流集 極元件。此種先前超電容之結構變異中通常者為手段,例 如壓縮配置,其維持元件間基本之密切實體接觸,以便確 保低内部電阻。此形式之電容器實例可見逑於美國專利第 3,536,936號’其中降低碳顆粒電極組合物以及電極/集極介 面之内部電阻至可使用程度所需之可觀之壓密壓力,在電 容器槽製造中產生嚴重困難。 已嘗試藉由直接施加物理壓力以外之方式以降低超電容 電極之内部電阻,著明者為經由統一碳微粒電極組合物與 導電性集極之若干方式。一種元素高溫燒結以達成此目的 -4- 本纸張尺度適用中關家標準(CNS)A4規& (21Q χ297公爱)" --I---I------* 裝 i — f請先閱讀背面之注意事項再填窝本頁) 11: -線 經濟部智慧財產局員工消費合作社印製 434604 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(2 ) 之方法見述於美國專利第5,115,378號’然而,如顯然可知 者,廣泛之處理步驟及高能量消耗導致此方法在經濟上不 爲所欲。進一步限制該方法普遍被接受者爲難駕馭所得之 固體及強硬之預成形f容器體,其無法輕易形成能夠符合 種種利用裝置空間需求之形狀。 將超電容結構之内部電阻最小化之其他手段嘗試了例如 將熱解之氣凝膠、碳發泡體電極與高溫焊接之導電性集極 兀件组合,如美國專利第5,26〇 855號中所述者。然而,此 種方法因爲除了缺少所得裝置之操作性之外,尚需要多方 面處理及消耗尚能量與時間,所以實行成功有限。 本發明特別提供在經濟之周圍條件下輕易製備可撓性、 低阻超電谷結構之手段,而克服先前超電容結構及製造 步驟之限制。此種簡單之製造步驟使得可將此等裝置擴大 使用於廣泛之種種構形與應用,包括與可相容之組合物及 結構之積體充電式電池能源組合。 發明概述 本發明之超電容結構與製造步驟大部份使用已成功製備 聚合物充電式電池之材料與技術,可注意到美國專利第 5,296,318 - 5,418,091 ^ 5,456,000 > 5,571,634 ' 5,587,253 中所不之Li離子電池,將其詳細敘述併入本文以供參考。 因此’可藉由將電極與自包含法性碳與離子導電性電解 質(聚合物組合物所製得之隔板薄膜層合,而方便製造具 有低内部電阻及能夠在可觀之時間期間產生高能量與高電 流密度之超電容裝置。 _____ -5- 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公餐) -- lllllll! — — — 11 · — — III — — < —-------I. V C請先閲讀背面之注意事項再填寫本頁) 4346 〇4 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(3 ) 根據本發明之超電容槽電極與隔板元件可使用任何廣泛 疋種種聚合物材料’如:聚(亞乙缔基氟-共-六氟丙烯KVdF :HFP)及聚(亞乙烯基氟-共-氣代三氟乙晞)(vdF : CTFE) 共聚物。此種元件較佳包含VdF : HFP共聚物基體與20至70 ' 重量%之可相容之使均質組合物維持可撓、自我支撑之薄 膜形式之有機塑化劑之组合。共聚物較佳包含约75至92重 量%之亞乙晞基氟(VdF)與2至25重量。/。之六氟丙烯(HFP), 在孩範圍中,後者之共單體將最後之共聚物之結晶性限制 至確保良好之膜強度同時保留約4〇至6〇0/〇之電解質鹽用之 較佳溶劑之程度。在此溶劑含量之範園内,最後包含混合 性電解質膜之5至10%鹽係產生約]|〇-4至1(r3 s/cmi有效室 恤下之離子導電性,然而薄膜並不展現溶劑滲出之證據, 此等溶劑滲出係會導致槽漏洩或導電性之損失。 根據本發明藉由將以塗覆、擠壓、或其他方式而自包含 如上述之聚亞乙烯基氟(PVdF)共聚物之材料之聚合物基體 之组合物所個別製得之電極與隔板槽元件層合而建造超電 容槽。例如,建造此種超電容槽時,將電極膜或薄膜製備 成乾燥而形成薄膜之具有活性碳粉末分散於塑化共聚物基 體溶液中之组合物澆鑄層s自薄膜切出所欲尺寸部分及熱 層口至個別之導電性電流集極箔片,如:銅與鋁網狀柵極 以形成負與正電容器電極。類似的使用共聚物基體溶液 以製備隔板薄膜,其中取適當尺寸之部分插置於组合中之 電極對之間,然後在壓力下加熱藉以將槽元件層合成整體 式可撓性超電容結構。 -6- - - -------------------訂--------· ~ ' <諳先閒讀背面之注意事項再填寫本頁) J 保 f - M 公 / zy X lu tz 格 現 4 < / 4346 〇 4 A7 B7 經濟部智慧財產局員工消費合作杜印製 五、發明說明(4 ) 在此階段中,層合結構包含顯著量之均勻分佈之有機塑 化劑,然後藉由將槽層合物浸潰在共聚物惰性之溶劑(如 :乙醚或己烷)中,以選擇性萃取塑化劑而不顯著影響槽 7G件階層之共聚物基體,而將該有機塑化物實質上移除。 然後可簡單的將萃取溶劑蒸發,以產生乾燥、微孔性超電 容槽,其後藉由浸潰或其他接觸電解質溶液(如:1MLip^ 於2份碳酸伸乙酯及丨诊碳酸二甲酯中)而活化,電解質溶 液埃充結構之孔以確保基本之離子導電性^ 可使用相同之製造步驟以形成具有—對相似電極配置在 具有相對極性之共同電極之個別侧上之超電容結構。此配 置之結果爲具有較一對等效並排之單一裝置爲少之重量及 因此提供較大之比能量密度之雙槽超電容。包含以雙金屬 電流集極爲介面之一對相對極性單一槽結構之種種配置, 產生能夠在一整體式裝置中提供二倍於單一槽電壓之等效 直排超電容。 本發明之特別有用之實施具有在上述之層合之超電容與 可獲得之聚合物層合充電式電池槽之間之材料與結構之相 谷性之優點,及提供包含咼能量輿高功率之經濟與可信來 源1單一整體式裝置以符合現代電子系統所呈現之廣範圍 之要求。 圖式簡要説明 將參考附圖以敘述本發明: 第1圖爲本發明之層合單一超電容槽結構之截面圖示; 第2囷爲本發明之層合雙並排超電容槽結構之截面圖示; 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ------- I--I--1^.--------訂---------I V Γ4先閱讀背Φ之注意ί項再填寫本頁) 434604 A7 B7 五、發明說明(5 經濟部智慧財產局員工消費合作社印製 弟圖爲本發明之層合混合 截面圖示; 屯化于电池/超電容槽結構之 !5圖爲本發明之超電容之充電,放電特徵之圖示;及 弟6圖爲本發明之超電容之循環安定性之圖示。 發明敘述 第圖所描述之本發明之層合超電容結構包括包含電 流集極落片U之正電極部件,較佳爲開放筛目銘拇極之形 式’其係在熱與壓力下層合於—對包含活性碳粉末分散於 塑化之聚合物黏合劑基體中之電極薄膜13,13之間β負電極 4件類似的包含電流集極猪片ϊ5,較佳爲開放篩目銅栅極 I形式,其係層合於另—對活性碳電極薄膜13,13之間。包 含塑化共聚物組合物之薄膜之隔板部件係位於複合電極 邵件之間,及施加熱與壓力以敕化及黏合聚合物成分及使 電極與隔板部件層合。個別電流集極箔片之延伸12,16便利 的提供超電容裝置用之連接端。 隔板薄膜18較佳自包含前示之pvdF : HFP共聚物(可自 Atochem North America公司購得,品名爲 Kynar FLEX)及相 容之有機塑化劑之组合物所製得。此種共聚物组合物亦較 佳供電極薄膜元件之製備,因爲能確保後續之層合介面相 容性。塑化劑較佳爲高沸點聚合物溶劑,如:g太酸二丁醋 、备大酸二甲醋、g太酸二乙g旨、或鱗酸參丁戰乙酷。可使用 無機填料附加物,如,煙燻鋁氧或矽烷化之煙壎矽氧,以 加強隔板薄膜之物理強度與熔融黏度,及於若干組合物中 閲 讀 背 面 之 注 意 事 項 再 填, 寫k 貪 訂 線 -8 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 434604 A7 B7 五、發明說明(6 ) ’以增加後續之電解質溶液吸收程度。 ί靖先閱讀背面之注意事項再填寫本頁) 自包含較佳之其中分散著商業上於超電容製造中所使用 之類之活性碳粉末之共聚物材料之塑化組合物類似的製備 電極薄膜元件13, 13。製備本發明之薄膜材料時可使用供堯 鑄或形成聚合物組合物之膜或薄膜之任何_般步驟。當使 用流體組合物祕或塗覆(如,以米尺或刮刀裝置)時,組 合物之黏度將一般因添加易揮發之澆錡溶劑如:四氫呋喃 (THF)、丙酮、或類似物而降低一般使此種塗層於溫和 溫度下空氣乾燥,以產生均質、塑化之共聚物組合物之自 我支撑膜。亦可藉由使商業形式(即,珠或粉末)之共聚物 在適量之塑化剖中潤脹,及然後將潤脹之質塊在加熱(如 ’約130。〇板或輕之間壓製或擠壓該混合物,而形成薄膜 材料’特別是作爲隔板元件使用者。 經濟部智慧財產局員工消費合作社印製 —不像先前之超電容結構依賴高度壓縮之裝置配置以維持 电極部件與電性電流集極洛片元件個別《間之基本緊密 接觸,本發明之槽邵件之層合即能單獨確保此種緊密性及 導致低阻力之電連續性,及提供最後超電容槽積體性與可 撓性。在層合之前,可將集極元件予以預處理,如,以電 *相谷之聚β物材科預處理,例如藉由塗敷〇 %至2 之類似於電極基體之共聚物溶液,典型上爲卜奸與2至 25 /〇 HFP ’及於25〇。至45〇°C下加熱約5至50秒,以幫助確保 此種積體層合,以及低介面電阻。較重一些之共聚物層( 如:藉由在3%之預處理聚合物溶液中浸潰所獲得者)單獨 提供優越之黏著而不需後加熱操作。 -9- (210 x 297 公釐〉 本紙張尺錢肖巾國國家標準((:㈣如規士· 434604 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(7 ) 當使用薄膜成形操作時,可以通常使用之器具完成組合 之超電容槽結構之層合。可將預賦形或預定尺寸之组合在 加熱輥之間壓縮,或可僅在重量爲約3 X 104至5 X 104 Pa之金 屬板之間於溫度爲約12〇。至160。(:之烘箱中,或於提供類似 條件之加熱壓機中壓製片刻。使用薄膜部件之連續粗匹 (web)時,較佳使用熱砑光輥進行操作β 超電容槽製造方法之最後操作將槽活化,包含將共聚物 塑化劑以電解質替換,以獲得離子導電性。此種替換較佳 經由在藉由將層合之槽結構(如:第1圖中者)浸潰於對共 聚物基體材料具有極少顯著影響之塑化劑溶劑中而自結構 之共聚物組合物中萃取出塑化劑後施加電解質溶液而完成 。對於較佳之PVdF共聚物而言,此種溶劑可爲乙醚或甲醚 、甲醇、己競•、及類似物。藉由將萃取溶劑適度緩慢蒸發 所形成之微孔性基體結構提供整個基體豐富之部位以供超 電容中所通常使用之一或多種非水性電解質溶液之持留。 使用包含VdF : HFP共聚物之组合物製備許多層合之超電 谷槽如’諸圖^中所描述者’及試驗電與物理適用性。下列 實例説明此種製備與用途。 實例1 藉由將10 g具有高度表面積〇000 m2/g)t活性碳粉末懸 浮於20 g之具有约380 x 1〇3娜之-88 : 12 wf :聊共聚物 (Atochem Kynar FLEX 2801)與3〇 g 之酞酸二丁醋(DBp)於约 160 g之丙酮之溶液中’而製備電極塗料组合物。將混合 物於機械攪拌器中攪拌约10分鐘,以確保均質性,及然後 -10- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) -------------裝--------訂----^-----線 (請先閱讀背面之注意事項再填寫本頁) 434604 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(8 ) 以刮刀裝置澆鑄在防黏著劑聚對酞酸乙二酯表面上,及使 其於室溫下在空氣中乾燥約1小時。輕易將所得之具有約 0.125 mm厚度之乾燥、硬、可撓性薄膜自塗覆表面移除及 分割成約50 mm X 80 mm之樣品以供作爲超電容電極元件。 將約50 ju m厚之铭開孔篩目網柵(如:Delker公司所行銷 之MicroGrid精細擴大之箔片)切割形成約50 mm X 100 mm之 電流集極元件11(第1圖)。將一聚合物組合物薄膜樣品配 置成與集極11之各表面接觸,以形成電極元件13, 13,及提 供延伸之集極端點垂片12。使此裝配通過加熱至約125°C 歷·力爲每線性cm之輥接觸處約45N之輥之間,其中,薄膜 13, 13之聚合物電極组合物充分軟化而穿透柵極集極11之開 孔篩目,及建立相干黏合,將集極穩穩嵌入以形成整體式 正電極部件。 使用一對電極薄膜13, 13及具有端點垂片16之銅柵極集極 箔片15以類似方式形成負電極部件。 以先前之方式製備隔板薄膜塗料组合物,爲4g煙燻矽 氧於 6 g之 Kynar FLEX 2801 VdF : HFP共聚物及 10 g 之 DBP於 約40 g丙酮之溶液中之懸浮液。摻合之後,將混合物澆鑄 及乾燥成堅硬、可撓之薄膜,具有約0.075 mm之厚度,將 其分割成約50 mm X 80 mm之樣品。將一隔板薄膜樣品18配 置於先前製備之正與負電極部件乏間,及以個別電極部件 之方式將裝配層合,以形成可撓、整體式單一超電容結構 10 ° 其後將層合槽結構10浸潰於乙醚體中,其中,於溫和攪 -11 - _ .. ..Λ. 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公g ) ----- --------*-------訂·-------- (請先閱讀背面之注意事項再填寫本頁) -4 6 〇 4 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(θ) 摔約10分鐘4下’萃取電極與隔板薄膜组合物之DBP成分 。然後將結構10自萃取池中移出,及於室溫下予以空氣乾 燥。最後,藉由使槽浸潰於LipF6於碳酸伸乙酯(EC):碳酸 一甲酯(DMC)之2 : 1混合物中之1M之電解質溶液中約1〇分 鐘,而將槽於不含濕氣之大氣中活化,在此期間,槽將電 解質洛液吸入微孔性層合結構中以實質上替換原來之DBp 塑化劑。使用吸收材料溫和擦拭以移除表面電解質之後, 將活化超電容槽1〇(但除了延伸端點垂片12, 16之外)氣密式 把封於聚烯烴封套(未示)内,以維持不含濕氣之環境。 然後使呈埤約19.2 F之電容之超電容在〇至2 5V之範園内 重複2分鐘期間之充電/放電循環,及呈現第5圖中所示之 循環特徵。在擴充此種循環後之超電容之容量維持在約3 5 mAhr,如第6圖所示。 實例2 如第2圖中所描述製備能夠獲得顯著較大之比能量密度 之超電容雙槽20。如實例丨藉由將集極柵極21與碳電極薄 膜23層合而製造一對正電極部件。使用實例丨之電極組合 物製備具有實質上二倍厚度之頦外之電極薄膜2 7,2 7,及以 先則之方式與負銅柵極元件25層合,以形成單—負電極。 將此電極部件配置在二隔板薄膜28, 28及該對正電極之間, 作爲共同負電極,如第2圖所示,.及將裝配如前述層合以 形成雙槽超電容結構20。以此方式,消除_電流集極部件 之多餘重量,藉以減少槽之總質量。萃取所得之結構及使 用電解質溶液活化,如實例i中所述者,以產生能夠獲得 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----------------------訂 *-------- (請先閱讀背面之注意事項再填寫本頁) 434S0 4 A7 B7 五、發明說明(ι〇) 較大比能量密度之官能性超電容。 實例3 本發明之另—具體實施例描述於第3圖,及包含能夠提 供兩倍於以單槽超電容所獲得之電壓之雙極超電容結構。 製造此給構時,將各正銘集極栅極31與負銅集極拇極调 合於如實例1中所製備之碳電極薄膜33之間,以產生正與 負電極。此龢’藉由將實例2之雙倍厚度之碳電極薄膜”, 37層合至分別呈現鋁3Γ與銅35,表面之固體雙金屬箔片,而 製備單-雙極電極。然後將正、貞、及雙極電極層合及具 有隔板薄膜38, 38插置其間,以形成在萃取/活化後能夠提 供相當於单一結構之二槽系列之超電容。 實例4 本發明之超電容結構之方便性與多樣性於第4圖所示之 混合槽中特別明顯,其中將如第2圖之部分中所描述之單 一超電谷槽結構與聚合物Li離子電池槽層合,以產生能夠 提供如許多利用裝置所需之高能量密度與高功率二者之結 構。除了包含正集極21、正電極薄膜23,23、負電極薄膜27 、與隔板薄膜28之層合超電容結構(如實例2所述者)之外 ’混合結構包含具有層合正電池電極薄膜43, 43之正鋁柵極 電流集極41、隔板/電解質薄膜48 '負電池電極薄膜47、及 共同之超電容/f池負銅電流集極铉片45。 電池電極薄膜可包含上述文獻中所述之任何聚合物组合 物。對於本實例之目的而言,使用典型之正插入電極组合
物’其包含 10.5 g 之 Ι^,05Μη2Ο4、實例 1 之 2.8 g 之 VdF : HFP -13 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公发) --------------裝'-- {請先閱讀背面之注意事項再壤寫本頁) ]· · -*1° ;線· 經濟部智慧財產局員工消费合作社印製 4346 04 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(11) 共聚物、4.3 g之DBP、1,2 g之Super-P導電性碳粉末 '及約 20 g之丙明之懸浮液。將負電池電極組合物製備成7〇g粉 碎(<60 μιη)之市售石油煤焦、2 〇 g之VdF :抑?共聚物、 3.12 g之DBP、〇·37 g之Super-P碳、及約12 g之丙酌之懸浮-液。將此等組合物繞轉以形成如前述實例之電極薄膜。以 實例1中所製得之隔板薄膜形成電池槽隔板4g。以實例1所 述之方式進行最後之層合、萃取、活化、及包裝操作a 可以使用作爲液體電解質溶液之任何許多組合物成功的 將本發明之超電容結構活化。顯然可在電解質溶液中使用 此種有機溶劑如:碳酸伸丙酯、二乙氧乙烷、碳酸二乙醋 、二甲氧乙烷、嘍吩烷、及碳酸二丙酯、及其混合物β又 ’在活化電解質溶液之配方中,可使用進一步有用之鋰與 其他鹽’包括 LiC104、LiN(CF3S02)2、LiBF4、LiCF3S03、 LiSbF6、NBu4 BF4、及Et4NBF4 ,以约0.5與2 M之間之溶液濃 度使用。特別利用中所除外者爲美國專利第5,192,629號中 所述之LiPF"6及與LiBh之混合物之碳酸伸乙醋/碳酸二甲醋 组合物》 雖然上述實例與許多有用之超電容結構之製備有大部份 關#’但將其他變異同樣包括在本發明之範w壽内,如所附 之申請專利範圍所示者。 -14- 本紙張尺度適用中國國家標準(CNS)A4規格(210^ 297公g ) ---I----i —--I --------訂--------- (.請先閱讀背面之注意事項再填寫本頁)
Claims (1)
- 4346 Ο 4 Α8 Β8 C8 D8 經濟部智慧財產局員工消費合作社印製 申請專利範圍 1. 一種超電容結構,包含鄰接 疋正包極邵件、負電極部 件、及放置在其間之隔板部件,特徵在於 a) 各該電極部件包含黏合著導電性電流集極元件之可撓 性、聚合物基體組合物膜, b) 該隔板部件包含可棱性、聚合物基體組合物膜,及 0各該部件於各自介面處黏合 麵秘。至一或多個鄰接部件,形 成整體式可撓性層合結構。 2. 根據中請專利範圍第1之超電容結構,其中該聚合物電 極膜組合物包含均句分伟於該基體中之活性碳粉末。 3. 根據申請專利範圍第】項之超電容結構,其中至少一個 該集極元件包含開孔篩目栅極β 4. 根據中請專利範圍第3項之超電容結構,其中該集極元 件撕極係以加熱方式黏合於—對該電極薄膜之間,藉 以使得該薄膜組合物穿過該柵極之開口以形成將該集 極埋在該電極部件體内之凝聚性黏合。 5. 根據申請專利範圍第丨項之超電容結構’特徵在於該聚 W基體組合物包含亞乙烯基氟與2至25重量%之六氟 丙烯共聚物’其中有2G至7〇重量%的與該共聚物相容之 有機塑化劑均勻分佈於其内^ 6 ·根據申請專利範圍第1項之超電容結構,特徵在於該聚 合物基體組合物包含亞乙烯基氟與2至25重量%之六氟 丙烯共聚物,該共聚物起初具有均勻分佈於其内的2〇 至70重量%的與該共聚物相容之有機塑化劑,且其中 15 ΜΛ張尺度適用中國國家標準(CNS)从见格(2ΐ〇χ297公董 I H - n I— II ϋ n r, i ------It _ T _ _______ i 1----r' (請先閲讀背面之注意事項再填寫本頁) 申請專利範圍 C8 D8 一· 該塑化劑係已萃取並以電解質溶液取代。 7.根據申請專利範圍第i項之超電容結構,包含至少一對 電極部件,其具有第一極性與各自之隔板部件配置在 具有相對極性之共同中間電極部件表面。 8 -根據申請專利範圍第丨項之超電容結構,包含至少—對 電接郅件,其具有相對極性與各自之隔板部件配置在 包含-對黏合至中間雙金屬集極元件表面之電椏薄膜 之中間雙極電極部件表面。 9 ·根據申請專利範圍第丨項之超電容結構,其中至少—個 該集極元件包含具有充電式電池結構之共同類極性集 極元件,該充電式電池結構包含鄰接黏合之包括集接 、_件之正電極郅件、包括集極元件之負電極部件、及 放置在其間之隔板部件,該電池結構部件與該超電容 結構部件黏合以形成整體式可撓性混合層合結構。 1M艮據申請專利範圍第”之超電容結構,其中該正電池 電極部件包含具有鐘插入化合物之塑化聚合物基體組 經濟部中央#準局舅工消費合作社印震 合物’及該負電池電極部件包含具有能夠插鋰離子之 材料之塑化聚合物组合物β U·—種製造超電容結構之方法,其包含將正電極部件、 負電極部件、及放置在其間之隔板部件鄭接配置,特 徵在於 a)將各該電極部件形成如黏合至導電性電流集極元件之 聚合物基體組合物之可撓性膜, 16- 本紙張尺^家揉準(2獻297公釐丁 ABCD 4346 0 4 •、申請專利範圍 - b) 將該隔板郅件形成如聚合物基體組合物之可撓性膜, 及 c) 將各該部件於各自介面處黏合至一或多個鄰接部件, 以形成整體式可撓性層合結構。 12.根據申請專利範園第之方法,其中將該鄰接之電 極與隔板部件於壓力下加熱以使個別之聚合物基體組 合物軟化及進行該部件之間凝聚性之層合黏合。 I3·根據申請專利範圍第u項之方法,特徵在於 a) 各該部件之聚合物基體薄膜係由其中均勻分佈了如 至7〇重量%的可與該聚合物相纟之有機塑化劑之聚 合物組合物所形成, b) 使用對聚合物惰性之溶劑自該層合結構 卞·^出眘哲 上全部之塑化劑, n c) 使用電解質溶液取代由此萃取出之塑化劑。 - - I 1 —^n ^1.^1 I ^/aJ <#先閱讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作社印製 -17- 私紙張尺度通用中國國家標準(CNS ) A4洗格(210X297公釐)
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|---|---|---|---|
| US09/159,557 US6181545B1 (en) | 1998-09-24 | 1998-09-24 | Supercapacitor structure |
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| Publication Number | Publication Date |
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| TW434604B true TW434604B (en) | 2001-05-16 |
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|---|---|---|---|
| TW088116384A TW434604B (en) | 1998-09-24 | 1999-09-23 | Supercapacitor structure and method of making same |
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| Country | Link |
|---|---|
| US (2) | US6181545B1 (zh) |
| EP (1) | EP1116249A1 (zh) |
| JP (1) | JP2002525864A (zh) |
| KR (1) | KR100460570B1 (zh) |
| CA (1) | CA2342980A1 (zh) |
| MY (1) | MY115499A (zh) |
| TW (1) | TW434604B (zh) |
| WO (1) | WO2000017898A1 (zh) |
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|---|---|---|---|---|
| TWI386133B (zh) * | 2009-10-05 | 2013-02-11 | Taiwan Textile Res Inst | 組合式可撓性織物電容模組 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6187061B1 (en) | 2001-02-13 |
| CA2342980A1 (en) | 2000-03-30 |
| KR100460570B1 (ko) | 2004-12-08 |
| JP2002525864A (ja) | 2002-08-13 |
| MY115499A (en) | 2003-06-30 |
| US6181545B1 (en) | 2001-01-30 |
| WO2000017898A1 (en) | 2000-03-30 |
| EP1116249A1 (en) | 2001-07-18 |
| KR20020010563A (ko) | 2002-02-04 |
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