JP2009088274A - Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor - Google Patents
Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor Download PDFInfo
- Publication number
- JP2009088274A JP2009088274A JP2007256429A JP2007256429A JP2009088274A JP 2009088274 A JP2009088274 A JP 2009088274A JP 2007256429 A JP2007256429 A JP 2007256429A JP 2007256429 A JP2007256429 A JP 2007256429A JP 2009088274 A JP2009088274 A JP 2009088274A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- electric double
- layer capacitor
- agent
- double layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000004816 latex Substances 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000003273 ketjen black Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 13
- 230000004913 activation Effects 0.000 description 7
- -1 for example Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 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
- 229920003026 Acene Polymers 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NZHNWXPAAJHNNW-UHFFFAOYSA-J C1(OCC(C)O1)=O.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 Chemical compound C1(OCC(C)O1)=O.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 NZHNWXPAAJHNNW-UHFFFAOYSA-J 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011333 coal pitch coke Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011334 petroleum pitch coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
本発明は、電気二重層キャパシタ用電極およびその製造方法並びに電気二重層キャパシタに係り、特に内部抵抗が低く容量の高い電極を得る技術に関する。 The present invention relates to an electrode for an electric double layer capacitor, a manufacturing method thereof, and an electric double layer capacitor, and more particularly to a technique for obtaining an electrode having a low internal resistance and a high capacity.
近年、地球の環境問題などから、エンジン駆動であるガソリン車やディーゼル車に代わり、電気自動車やハイブリッド車への期待が高まっている。これらの電気自動車やハイブリッド車では、モーターを駆動させるための電源としては、高エネルギー密度かつ高出力密度特性を有する電気化学素子が用いられる。このような電気化学素子としては、電気二重層キャパシタがある。 In recent years, due to environmental problems on the earth, there are increasing expectations for electric vehicles and hybrid vehicles in place of engine-driven gasoline vehicles and diesel vehicles. In these electric vehicles and hybrid vehicles, an electrochemical element having high energy density and high output density characteristics is used as a power source for driving the motor. As such an electrochemical element, there is an electric double layer capacitor.
このような電気二重層キャパシタ、特に巻回型の電気二重層キャパシタにおける、電気自動車やハイブリッドカーのモーター駆動用電源、またはブレーキ時の回生エネルギー蓄電などのパワー用途では、電極の厚みを薄くすることによって、パワー密度の向上を図っている。そして、そのためには、電極をシート状にしてこれを集電体に接着するより、スラリー状の電極を集電体にコーティングする方法のほうが薄膜化が図れる。このようなコーティング電極には、成膜性の良好なポリフッ化ビニリデン‐Ｎメチルピロリドン溶液が用いられている（特許文献１）。
しかしながら、この方法では、内部抵抗が高く、パワー密度が満足できるものではないという課題があった。 However, this method has a problem that the internal resistance is high and the power density is not satisfactory.
本発明は、以上のような従来の技術的課題を背景になされたものであり、コーティングが可能で、内部抵抗の低い電気二重層キャパシタ用電極およびその製造方法並びに電気二重層キャパシタを提供することを目的とする。 The present invention has been made against the background of the conventional technical problems as described above, and provides an electrode for an electric double layer capacitor that can be coated and has a low internal resistance, a method for manufacturing the same, and an electric double layer capacitor. With the goal.
上記の課題を解決すべく、本発明の電気二重層キャパシタ用電極は、電極主剤と、導電性助剤と、前記電極主剤及び導電性助剤とを結合させる結合材と、主剤と導電性助剤とを主剤と導電助剤を水に分散させスラリー化させるために使用する分散材とから構成され、前記結合材は、ラテックスからなり、前記分散材は、カルボキシメチルセルロースナトリウム塩からなることを特徴とする。 In order to solve the above-mentioned problems, an electrode for an electric double layer capacitor of the present invention comprises an electrode main agent, a conductive auxiliary agent, a binder for bonding the electrode main agent and the conductive auxiliary agent, a main agent and a conductive auxiliary agent. And a dispersing agent used to disperse the main agent and the conductive additive in water to form a slurry, wherein the binder is made of latex, and the dispersing agent is made of carboxymethylcellulose sodium salt. And
また、本発明の電気二重層キャパシタ用電極の製造方法は、分散材としてカルボキシメチルセルロースナトリウム塩と、溶剤としての水を混合し、攪拌し、主剤として活性炭を、導電助剤としてケッチェンブラックを加え、バインダーとしてラテックスを加え、これらを混合してスラリーを作製し、作製したスラリーをアルミニウムエッチング箔にコーティングして電極を得ることを特徴とする。 The method for producing an electrode for an electric double layer capacitor according to the present invention comprises mixing carboxymethylcellulose sodium salt as a dispersing agent and water as a solvent, stirring, adding activated carbon as a main agent, and adding ketjen black as a conductive aid. A latex is added as a binder, these are mixed to prepare a slurry, and the prepared slurry is coated on an aluminum etching foil to obtain an electrode.
以上のような本発明によれば、内部抵抗が低く容量の高い電気二重層キャパシタ用電極を得ることができる。すなわち、溶剤系のスラリーに対して、水系のラテックスと分散材を組み合わせたスラリーを用いることにより、接着性が向上して、抵抗を低減させることができる。 According to the present invention as described above, an electrode for an electric double layer capacitor having a low internal resistance and a high capacity can be obtained. That is, by using a slurry in which an aqueous latex and a dispersion material are combined with a solvent-based slurry, adhesion can be improved and resistance can be reduced.
また、本発明において、結合材であるラテックスは、アクリル系エラストマーであることを特徴とする。 In the present invention, the latex as the binder is an acrylic elastomer.
さらに、本発明では、上記の電気二重層キャパシタ用電極を集電体に塗布してなる電気二重層キャパシタを得ることもできる。 Furthermore, in the present invention, an electric double layer capacitor obtained by applying the above electrode for an electric double layer capacitor to a current collector can also be obtained.
以上のように、本発明によれば、コーティングが可能で、内部抵抗の低い電気二重層キャパシタ用電極およびその製造方法並びに電気二重層キャパシタを提供することができる。 As described above, according to the present invention, an electrode for an electric double layer capacitor that can be coated and has a low internal resistance, a manufacturing method thereof, and an electric double layer capacitor can be provided.
次に、本発明を実施するための最良の実施形態（以下「本実施形態」と呼ぶ）について以下に説明する。 Next, the best mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described below.
［１．電極の構成］
まず、本実施形態の電気二重層キャパシタ用電極の材料について以下に説明する。本実施形態の電気二重層キャパシタ用電極は、電極材料（主剤）と、導電性助剤と、主剤及び導電性助剤とを結合させる結合材（バインダー）と、さらに主剤と導電性助剤とを主剤と導電助剤を水に分散させスラリー化させるために使用する分散材とから構成される。
[1. Electrode configuration]
First, materials for the electric double layer capacitor electrode of the present embodiment will be described below. The electrode for the electric double layer capacitor of the present embodiment includes an electrode material (main agent), a conductive auxiliary, a binder (binder) that combines the main agent and the conductive auxiliary, and further, the main agent and the conductive auxiliary. And a dispersing agent used to disperse the main agent and the conductive additive in water to form a slurry.
（１）電極材料（主剤）
正極・負極として用いる電極材料としては、活性炭やポリアセン等が挙げられる。活性炭としては、例えば、フェノール樹脂等の樹脂系炭素、椰子殻などの植物系炭素、石炭／石油系ピッチコークス、メソカーボンマイクロビーズ（ＭＣＭＢ）等を賦活して用いている。また、上記活性炭の賦活方法としては、水蒸気賦活・アルカリ賦活・塩化亜鉛賦活・電界賦活・リン酸賦活等を用いることができ、これらの賦活方法を適宜組み合わせても良い。
(1) Electrode material (main agent)
Examples of the electrode material used as the positive electrode and the negative electrode include activated carbon and polyacene. As the activated carbon, for example, resin-based carbon such as phenol resin, plant-based carbon such as coconut shell, coal / petroleum pitch coke, mesocarbon microbeads (MCMB) and the like are activated and used. Moreover, as activation method of the said activated carbon, steam activation, alkali activation, zinc chloride activation, electric field activation, phosphoric acid activation, etc. can be used, and these activation methods may be combined suitably.
（２）導電性助剤
導電性助剤としては、ケッチェンブラック、アセチレンブラック、天然／人造黒鉛等が用いられる。
(2) Conductive auxiliary agent As the conductive auxiliary agent, ketjen black, acetylene black, natural / artificial graphite, or the like is used.
（３）分散材
本実施形態において、分散材としては、カルボキシメチルセルロースナトリウム塩（ＣＭＣ−Ｎａ）を用いる。なお、これらの分散材はポリマーのため結着力は弱いが、結果としてバインダーとしての効果も生じるが、本実施形態において分散材を用いる主目的としては主剤と導電助剤を水に分散させスラリー化させるためのものであり、バインダーとしての効果は副次的なものである。
(3) Dispersant In this embodiment, carboxymethylcellulose sodium salt (CMC-Na) is used as the dispersant. Although these dispersion materials are polymers, their binding power is weak, but as a result, the effect as a binder also arises. However, in this embodiment, the main purpose of using the dispersion material is to disperse the main agent and the conductive additive in water to form a slurry. The effect as a binder is secondary.
（４）結合材（バインダー）
バインダーには取り扱い易い水系のバインダーを用いることが好ましい。バインダーの配合量が多いと分極性電極層２の電気抵抗が大きくなるので、少量の配合でも分極性電極材料の保持力が大きいものが望ましい。この条件を満たすバインダーとして、アクリル系エストラマーのラテックスを使用する。また、分極性電極材料と導電性助剤を攪拌するための溶剤としては水を用いる。
(4) Binder (binder)
It is preferable to use a water-based binder that is easy to handle as the binder. When the blending amount of the binder is large, the electric resistance of the
［２．電気二重層キャパシタ］
以上の電極と電解液を用いて電気二重層キャパシタを形成することができる。用いる電解液としては非水系、水系がある。非水系の場合、溶媒としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、スルホラン、アセトニトリル及びジメトキシエタンからなる群から選ばれる１種以上を含むことが好ましい。溶質としてリチウムイオンを有するリチウム塩、第４級アンモニウムカチオンまたは第４級ホスホニウムカチオンを有する第４級アンモニウム塩または第４級ホスホニウム塩を挙げることができる。リチウム塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣＦ３ＳＯ３、ＬｉＣ（ＳＯ２ＣＦ３）2、ＬｉＡｓＦ６及びＬｉＳｂＦ６等が挙げられる。また、第４級アンモニウム塩または第４級ホスホニウム塩としては、Ｒ１、Ｒ２、Ｒ３、Ｒ４Ｎ＋またはＲ１、Ｒ２、Ｒ３、Ｒ４Ｐ＋で表されるカチオン（ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４は炭素数１〜６のアルキル基）と、ＰＦ６ −、ＢＦ４ −、ＣｌＯ４ −、Ｎ（ＣＦ３ＳＯ２）２ −、ＣＦ３ＳＯ３ −、Ｃ（ＳＯ２ＣＦ３）３−、ＡｓＦ６ −またはＳｂＦ６ −からなるアニオンとからなる塩であることが好ましい。特にＰＦ６ −、ＢＦ４ −、ＣｌＯ４ −、Ｎ（ＣＦ３ＳＯ２）２ −をアニオンとすることが好ましい。
[2. Electric double layer capacitor]
An electric double layer capacitor can be formed using the above electrodes and electrolyte. There are non-aqueous and aqueous electrolytes. In the case of a non-aqueous system, the solvent preferably contains one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, acetonitrile, and dimethoxyethane. Examples of the solute include a lithium salt having lithium ions, a quaternary ammonium salt or a quaternary phosphonium salt having a quaternary ammonium cation or a quaternary phosphonium cation. The
水系としては、カチオンとしてナトリウム、カリウム等のアルカリ金属、またはプロトンを用いる。アニオンとしては硫酸、硝酸、塩酸、リン酸、テトラフルオロほう酸、六フッ化リン酸、六フッ化ケイ酸などの無機酸、飽和モノカルボン酸、脂肪族カルボン酸、オキシカルボン酸、ｐ―トルエンスルホン酸、ポリビニルスルホン酸、ラウリン酸などの有機酸をプロトンとともに形成するアニオンを挙げることができる。 In the aqueous system, alkali metals such as sodium and potassium, or protons are used as cations. As anions, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorosilicic acid, saturated monocarboxylic acid, aliphatic carboxylic acid, oxycarboxylic acid, p-toluenesulfone The anion which forms organic acids, such as an acid, polyvinylsulfonic acid, and lauric acid with a proton can be mentioned.
そして電気二重層キャパシタは次のようにして作製することができる。電解液としては、前記の非水系、水系のすべてを用いることができる。そして、電極として本発明の電極を用いる。これらの電極を集電体に塗布して電気二重層キャパシタ用電極体を形成する。 The electric double layer capacitor can be manufactured as follows. As the electrolytic solution, any of the above non-aqueous and aqueous systems can be used. And the electrode of this invention is used as an electrode. These electrodes are applied to a current collector to form an electrode body for an electric double layer capacitor.
以下に実施例により本発明をさらに具体的に説明する。なお、実施例１及び２におけるスラリー作製工程の模式図を図１に示す。
［実施例１］
分散材としてのカルボキシメチルセルロースナトリウム塩（ＣＭＣ−Ｎａ）と、溶剤としての水を混合、攪拌する（図１（ａ））。ここで、ＣＭＣ−Ｎａは粉末のため、次の工程において扱いやすいように予め水に溶解させるものである（図１（ａ））。
The present invention will be described more specifically with reference to the following examples. In addition, the schematic diagram of the slurry preparation process in Example 1 and 2 is shown in FIG.
[Example 1]
Carboxymethylcellulose sodium salt (CMC-Na) as a dispersion material and water as a solvent are mixed and stirred (FIG. 1 (a)). Here, since CMC-Na is a powder, it is dissolved in water in advance so as to be easily handled in the next step (FIG. 1 (a)).
ここに、主剤として活性炭（ＡＣ）を、導電助剤としてケッチェンブラック（ＫＢ）を加え、高いせん断を与えて分散させる。さらにバインダーとしてラテックスを加え、これらを混合してスラリーを作製する。このときの目標粘度は、３０００〜７０００ｍＰａ・ｓである（図１（ｂ））。 Here, activated carbon (AC) is added as a main agent, and ketjen black (KB) is added as a conductive assistant, and dispersed by applying high shear. Further, latex is added as a binder, and these are mixed to prepare a slurry. The target viscosity at this time is 3000 to 7000 mPa · s (FIG. 1B).
作製したスラリーをコーティング機でアルミニウムエッチング箔にコーティングし、引出し端子を設けて電気二重層キャパシタ用電極体を作製する（図１（ｃ））。 The produced slurry is coated on an aluminum etching foil with a coating machine, and a lead terminal is provided to produce an electrode body for an electric double layer capacitor (FIG. 1 (c)).
ここで、活性炭、ケッチェンブラック及びカルボキシメチルセルロースナトリウム塩は粉末形状のものを用い、ラテックスは水系エマルジョン形状のものを用いた。また、それぞれの混合の割合は、主剤である活性炭を１０ｇとした場合、導電助剤のケッチェンブラックを０．５〜１．０ｇ、分散材としてのＣＭＣ−Ｎａを０．２ｇ、バインダーとしてのラテックスを０．２ｇとした。この実施例２の電気二重層キャパシタ用電極の材料構成を表１として示す。
［比較例１］
比較例１では、バインダーとして、ラテックスに代えてポリフッ化ビリニデンを用い、溶剤としてＮメチルピロリドンを用いた。また、カルボキシメチルセルロースナトリウム塩（実施例１）からなる分散材を用いずに、他の構成を上記実施例と同様にして、同様な方法にて電気二重層キャパシタ用電極体を作製した。
[Comparative Example 1]
In Comparative Example 1, polyvinylidene fluoride was used as the binder instead of latex, and N-methylpyrrolidone was used as the solvent. In addition, an electrode body for an electric double layer capacitor was produced in the same manner as in the above example, except that the dispersing material composed of carboxymethylcellulose sodium salt (Example 1) was not used.
［比較例２］
比較例２では、カルボキシメチルセルロースナトリウム塩（実施例１）は用いず、バインダーとしてポリテトラフルオロエチレン（ＰＴＦＥ）を用い、他の構成を実施例と同様にして同様な方法にて作成したスラリーを、圧延用ローラーを用いて、１５０μｍのシート状にした。そして、このシートをアルミニウムエッチング箔にカーボン系接着剤を用いて接着し、電気二重層キャパシタ用電極体を作製した。
[Comparative Example 2]
In Comparative Example 2, a carboxymethyl cellulose sodium salt (Example 1) was not used, and a slurry prepared in the same manner as in the Examples except that polytetrafluoroethylene (PTFE) was used as a binder. A 150 μm sheet was formed using a rolling roller. And this sheet | seat was adhere | attached on the aluminum etching foil using the carbon-type adhesive agent, and the electrode body for electric double layer capacitors was produced.
［比較結果］
上記のような実施例１、比較例１及び比較例２の電極を、各々２枚用いて正極、負極とし、１Ｍ四フッ化ホウ素テトラエチルアンモニウムプロピレンカーボネート溶液（１ＭＴＥＡＢＦ４／ＰＣ）に浸漬して、容量、内部抵抗を測定した。その結果を図２に示す。図２（ａ）は、ビーカーセル評価に基づいて得られた、実施例及び比較例の内部抵抗（Ω）を縦軸に表し容量（Ｆ／ｃｃ）を横軸に表すグラフであり、図２（ｂ）は実施例及び比較例の配合比を、図２（ｃ）はその配合比をグラム単位で示す表である。
[Comparison result]
The electrodes of Example 1, Comparative Example 1 and Comparative Example 2 as described above were each used as a positive electrode and a negative electrode, and immersed in a 1M boron tetrafluoride tetraethylammonium propylene carbonate solution (1MTEABF4 / PC). The internal resistance was measured. The result is shown in FIG. FIG. 2A is a graph obtained based on the beaker cell evaluation, in which the internal resistance (Ω) of Examples and Comparative Examples is represented on the vertical axis and the capacity (F / cc) is represented on the horizontal axis. (B) is a table | surface which shows the compounding ratio of an Example and a comparative example, and FIG.2 (c) is the table | surface which shows the compounding ratio in a gram unit.
図２（ａ）に示すように、実施例１は、比較例１より容量が高く、内部抵抗が低減している。また、シート電極である比較例２とは、内部抵抗に関しては差はなく、容量はより高くなっていることがわかる。 As shown in FIG. 2A, the capacity of Example 1 is higher than that of Comparative Example 1, and the internal resistance is reduced. Further, it can be seen that there is no difference in internal resistance and the capacity is higher than that of Comparative Example 2 which is a sheet electrode.
このように、本実施例では、比較例の溶剤系のスラリーに対して、水系のラテックスと分散材を組み合わせたスラリーを用いることにより、接着性が向上して、抵抗を低減させることができる。 As described above, in this example, by using a slurry in which an aqueous latex and a dispersion material are combined with respect to the solvent-based slurry of the comparative example, the adhesion can be improved and the resistance can be reduced.
Claims (5)
前記結合材は、ラテックスからなり、
前記分散材は、カルボキシメチルセルロースナトリウム塩からなることを特徴とする電気二重層キャパシタ用電極。 Used to disperse the main agent and the conductive auxiliary agent into water and to make a slurry by combining the main electrode agent, the conductive auxiliary agent, the binder for bonding the electrode main agent and the conductive auxiliary agent, and the main agent and the conductive auxiliary agent. And a dispersing material that
The binder is made of latex,
The electrode for an electric double layer capacitor, wherein the dispersing material is made of sodium carboxymethylcellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007256429A JP2009088274A (en) | 2007-09-28 | 2007-09-28 | Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007256429A JP2009088274A (en) | 2007-09-28 | 2007-09-28 | Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009088274A true JP2009088274A (en) | 2009-04-23 |
Family
ID=40661297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007256429A Pending JP2009088274A (en) | 2007-09-28 | 2007-09-28 | Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2009088274A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011216751A (en) * | 2010-03-31 | 2011-10-27 | Nippon Chemicon Corp | Electric double layer capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004128145A (en) * | 2002-10-01 | 2004-04-22 | Power System:Kk | Electric double layer capacitor and manufacturing method therefor |
| WO2007072815A1 (en) * | 2005-12-20 | 2007-06-28 | Zeon Corporation | Electric double layer capacitor |
-
2007
- 2007-09-28 JP JP2007256429A patent/JP2009088274A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004128145A (en) * | 2002-10-01 | 2004-04-22 | Power System:Kk | Electric double layer capacitor and manufacturing method therefor |
| WO2007072815A1 (en) * | 2005-12-20 | 2007-06-28 | Zeon Corporation | Electric double layer capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011216751A (en) * | 2010-03-31 | 2011-10-27 | Nippon Chemicon Corp | Electric double layer capacitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5392355B2 (en) | Electric double layer capacitor | |
| JP5637858B2 (en) | Electric double layer capacitor | |
| US20110075323A1 (en) | Capacitor | |
| CN108292568A (en) | Electrochemical apparatus and its manufacturing method | |
| JP2019050183A (en) | Aqueous electrolyte including protonic ionic liquid, and battery using the same | |
| CN101409154B (en) | Organic mixed super capacitor | |
| CN105742076A (en) | Alkali metal ion capacitor taking lithium orthovanadate as negative electrode active material | |
| CN107204485B (en) | A kind of polynary electrolyte of battery capacitor low temperature | |
| JP2013097908A (en) | Electrolytic solution for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using the same | |
| JP2010109080A (en) | Method for manufacturing electrode for storage element, electrode for storage element, and nonaqueous lithium type electricity storage element | |
| CN106169375A (en) | The lithium-ion capacitor of lithium titanate system | |
| JP6925972B2 (en) | Lithium-ion secondary battery and its manufacturing method | |
| JP5760369B2 (en) | Current collector for electric double layer capacitor and electric double layer capacitor | |
| JP2008091134A (en) | Electrode for electrochemical element, its manufacturing method, and electrochemical element | |
| WO2012105307A1 (en) | Lithium ion capacitor | |
| JP5223282B2 (en) | Electrode for electric double layer capacitor, method for producing the same, and electric double layer capacitor | |
| CN108807012B (en) | Lithium ion capacitor electrolyte and lithium ion capacitor containing same | |
| JP5052145B2 (en) | Method for producing lithium ion secondary battery | |
| JP6156823B2 (en) | Binders, electrodes and electrochemical devices | |
| JP2009088274A (en) | Electrode for electric double-layer capacitor, its manufacturing method, and electric double-layer capacitor | |
| US20130130126A1 (en) | Electrochemical cell for high-voltage operation and electrode coatings for use in the same | |
| US20130070390A1 (en) | Electrode active material, method for preparing the same, and electrochemical capacitor including the same | |
| JP2008166342A (en) | Lithium ion capacitor | |
| JP5724875B2 (en) | Electric double layer capacitor | |
| JP2017108127A (en) | Nonaqueous electrolytic solution for electric double layer capacitor, and electric double layer capacitor by use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100924 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120621 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120626 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20121106 |