JP2007242994A5 - - Google Patents
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- JP2007242994A5 JP2007242994A5 JP2006065382A JP2006065382A JP2007242994A5 JP 2007242994 A5 JP2007242994 A5 JP 2007242994A5 JP 2006065382 A JP2006065382 A JP 2006065382A JP 2006065382 A JP2006065382 A JP 2006065382A JP 2007242994 A5 JP2007242994 A5 JP 2007242994A5
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- electric double
- current collector
- polarizable electrode
- double layer
- layer capacitor
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- 239000003990 capacitor Substances 0.000 claims description 39
- 239000008151 electrolyte solution Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 231100000078 corrosive Toxicity 0.000 claims description 16
- 231100001010 corrosive Toxicity 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 60
- 230000001629 suppression Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N Propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002822 niobium compounds Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 150000003482 tantalum compounds Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- AHJGWYVYYLJJFQ-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium;tetrafluoroborate Chemical compound F[B-](F)(F)F.CC=1N(C)C=C[N+]=1C AHJGWYVYYLJJFQ-UHFFFAOYSA-N 0.000 description 1
- FBPIPPWLOCMHGR-UHFFFAOYSA-N 1,3-dimethylimidazol-1-ium;tetrafluoroborate Chemical compound F[B-](F)(F)F.CN1C=C[N+](C)=C1 FBPIPPWLOCMHGR-UHFFFAOYSA-N 0.000 description 1
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
- KNIWGPCMWBGRBE-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium;tetrafluoroborate Chemical compound F[B-](F)(F)F.CCN1C=C[N+](C)=C1C KNIWGPCMWBGRBE-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K AlF3 Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- MHCAFGMQMCSRGH-UHFFFAOYSA-N aluminum;hydrate Chemical compound O.[Al] MHCAFGMQMCSRGH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XJRAKUDXACGCHA-UHFFFAOYSA-N tetraethylazanium;tetrafluoroborate Chemical compound F[B-](F)(F)F.CC[N+](CC)(CC)CC XJRAKUDXACGCHA-UHFFFAOYSA-N 0.000 description 1
- ODGCEQLVLXJUCC-UHFFFAOYSA-N tetrafluoroborate Chemical compound F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OHZMHURLSZDGTO-UHFFFAOYSA-N triethyl(methyl)azanium;tetrafluoroborate Chemical compound F[B-](F)(F)F.CC[N+](C)(CC)CC OHZMHURLSZDGTO-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Description
本発明は、各種電子機器に利用される電気二重層キャパシタに関し、特に低抵抗および長期信頼性に優れた電気二重層キャパシタに関するものである。 The present invention relates to an electric double layer capacitor used for various electronic devices, and more particularly to an electric double layer capacitor excellent in low resistance and long-term reliability.
従来の電気二重層キャパシタはアルミニウム箔などの集電体上の表面に活性炭を主成分とする分極性電極層を形成した分極性電極をセパレータを介して対向させることによりキャパシタ素子を構成し、このキャパシタ素子に電解液を含浸させることにより構成されているものである。 In the conventional electric double layer capacitor, a capacitor element is formed by facing a polarizable electrode having a polarizable electrode layer mainly composed of activated carbon on the surface of a current collector such as an aluminum foil via a separator. The capacitor element is made to be impregnated with an electrolytic solution.
上記電解液には低抵抗化のために電導度が高く、また電気分解による電解液の劣化を抑えるため、フッ素などのハロゲンを含む化合物を電解質として用いている。 The electrolyte solution has a high conductivity for reducing resistance, and a compound containing a halogen such as fluorine is used as an electrolyte in order to suppress deterioration of the electrolyte solution due to electrolysis.
また、上記分極性電極層には活性炭粉末とカーボンブラックとバインダーに加え、機械的強度向上のため低融点成分を含むものなどがある。 In addition to the activated carbon powder, carbon black and binder, the polarizable electrode layer includes a low melting point component for improving mechanical strength.
なお、この出願の発明に関連する先行技術文献としては、例えば、低抵抗化に関して特許文献１及び２、電極の強度アップに関して特許文献３が知られている。
上記特許文献１及び２では活性炭粉末とカーボンブラックとバインダーの組成や形状を制御することで分極性電極層の低抵抗化を図っており、上記特許文献３では分極性電極層にケイ酸塩やリン酸塩などの低融点成分を含むことで機械的強度向上を図っている。 In Patent Documents 1 and 2 described above, the resistance of the polarizable electrode layer is reduced by controlling the composition and shape of the activated carbon powder, carbon black, and binder. In Patent Document 3, silicate or By including low melting point components such as phosphate, mechanical strength is improved.
しかし上記従来の構成においては、電解液中のフッ素イオンなどの腐食性イオンが集電体であるアルミニウムなどの金属箔と反応して、集電体と分極性電極層との間にフッ化アルミニウムなどの高抵抗の腐食生成物を形成してしまうという問題点を有していた。この腐食生成物により集電体と分極性電極層との界面抵抗が増大し、電気二重層キャパシタとしての抵抗も増大してしまうものであった。 However, in the above conventional configuration, corrosive ions such as fluorine ions in the electrolytic solution react with a metal foil such as aluminum which is a current collector, and aluminum fluoride is interposed between the current collector and the polarizable electrode layer. As a result, there is a problem that a high-resistance corrosion product is formed. This corrosion product increases the interface resistance between the current collector and the polarizable electrode layer and increases the resistance as an electric double layer capacitor.
そこで本発明はこのような従来の課題を解決し、低抵抗で特性劣化が少なく、長期信頼性に優れた電気二重層キャパシタを提供することを目的とするものである。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve such a conventional problem, and to provide an electric double layer capacitor having low resistance, little characteristic deterioration, and excellent long-term reliability.
上記目的を達成するために本発明は、金属箔からなる集電体に活性炭粉末とカーボンブラックとバインダーとからなる分極性電極層を形成した分極性電極を、電解液を含浸させたセパレータを介して前記分極性電極を対向させて陽極および陰極とし、これらをケースに収納してなる電気二重層キャパシタにおいて、前記集電体と前記分極性電極層との間に電解液中の電解質である腐食性イオンから集電体を保護する導電性のバリア層を設けたことを特徴とする電気二重層キャパシタとした。 In order to achieve the above object, the present invention provides a polarizable electrode in which a polarizable electrode layer made of activated carbon powder, carbon black, and a binder is formed on a current collector made of a metal foil via a separator impregnated with an electrolytic solution. In an electric double layer capacitor in which the polarizable electrodes are opposed to each other as an anode and a cathode, and these are housed in a case, corrosion that is an electrolyte in an electrolytic solution between the current collector and the polarizable electrode layer An electric double layer capacitor provided with a conductive barrier layer for protecting the current collector from reactive ions.
本発明の電気二重層キャパシタは、上記集電体と分極性電極層との間に電解液中の電解
質である腐食性イオンから集電体を保護する導電性のバリア層を設けることにより、集電体の表面を電解液中の電解質である腐食性イオンなどから保護し、容量を低下させることなく集電体と電解液との間での化学反応を抑制することができる。したがって、抵抗を低くすることができ、特性劣化の少ない長期信頼性に優れた電気二重層キャパシタを提供することができるものである。
In the electric double layer capacitor of the present invention, a conductive barrier layer that protects the current collector from corrosive ions that are electrolytes in the electrolyte is provided between the current collector and the polarizable electrode layer. The surface of the electric body can be protected from corrosive ions, which are electrolytes in the electrolytic solution, and the chemical reaction between the current collector and the electrolytic solution can be suppressed without reducing the capacity. Accordingly, it is possible to provide an electric double layer capacitor that can have low resistance and excellent long-term reliability with little characteristic deterioration.
本発明の請求項１に記載の発明においては、金属箔からなる集電体に活性炭粉末とカーボンブラックとバインダーとからなる分極性電極層を形成した分極性電極を、電解液を含浸させたセパレータを介して前記分極性電極を対向させて陽極および陰極とし、これらをケースに収納してなる電気二重層キャパシタにおいて、前記集電体と前記分極性電極層との間に電解液中の電解質である腐食性イオンから集電体を保護する導電性のバリア層を設けた構成を有する。 In the first aspect of the present invention, a separator in which a polarizable electrode in which a polarizable electrode layer made of activated carbon powder, carbon black and a binder is formed on a current collector made of a metal foil is impregnated with an electrolytic solution In an electric double layer capacitor in which the polarizable electrode is opposed to each other through an anode and a cathode, and these are housed in a case, an electrolyte in an electrolytic solution is interposed between the current collector and the polarizable electrode layer. A conductive barrier layer that protects the current collector from certain corrosive ions is provided.
これにより、集電体を電解液中の電解質である腐食性イオンなどから保護し、容量を低下させることなく集電体と電解液との間での化学反応を抑制することができるため、抵抗を低くすることができ、特性劣化の少ない長期信頼性に優れた電気二重層キャパシタを提供することができる。 This protects the current collector from corrosive ions, which are electrolytes in the electrolyte, and can suppress the chemical reaction between the current collector and the electrolyte without reducing the capacity. Therefore, it is possible to provide an electric double layer capacitor that is less deteriorated in characteristics and excellent in long-term reliability.
本発明の請求項２に記載の発明においては、集電体を電解液中の腐食性イオンから、高耐食性のタンタル、ニオブ、珪素、チタン及びその化合物のいずれかからなる導電性のバリア層で保護することで、容量を低下させることなく集電体と電解液との間での化学反応を抑制することができる。これにより、容量を低下させることなく集電体と電解液との間での化学反応を抑制することができるため、抵抗を低くすることができ、特性劣化の少ない長期信頼性に優れた電気二重層キャパシタを提供することができる。 In the invention according to claim 2 of the present invention, the current collector is made of a conductive barrier layer made of corrosive ions in the electrolytic solution, high corrosion-resistant tantalum, niobium, silicon, titanium, or a compound thereof. By protecting, the chemical reaction between the current collector and the electrolytic solution can be suppressed without reducing the capacity. As a result, the chemical reaction between the current collector and the electrolyte solution can be suppressed without reducing the capacity, so that the resistance can be lowered and the electric power source with excellent long-term reliability with little characteristic deterioration can be obtained. A multilayer capacitor can be provided.
本発明の請求項３に記載の発明においては、陰イオンと反応しやすい陽極側の集電体の
みを電解液中の電解質である腐食性の陰イオンから導電性のバリア層で保護する構成である。腐食性イオンはアニオンとして存在しているために電圧印加時には陽極と反応することがより多く、容量を低下させることなく陽極側の集電体と電解液との間での化学反応を抑制することができるため、抵抗変化を抑えることができ、更に電気二重層キャパシタの構成としての部材数を削減し、製造コストを抑えることができるものである。
In the invention described in claim 3 of the present invention, only the anode-side current collector that easily reacts with the anion is protected by the conductive barrier layer from the corrosive anion that is the electrolyte in the electrolytic solution. is there. Since corrosive ions exist as anions, they are more likely to react with the anode when voltage is applied, and suppress the chemical reaction between the current collector on the anode side and the electrolyte without reducing the capacity. Therefore, the resistance change can be suppressed, the number of members as the structure of the electric double layer capacitor can be reduced, and the manufacturing cost can be suppressed.
本発明の請求項４に記載の発明においては、特に腐食性のイオンに弱いアルミニウム集電体を電解液中の電解質である腐食性イオンから導電性のバリア層で保護し、容量を低下させることなくアルミニウム集電体と電解液との間での化学反応を抑制し、アルミニウム水和物を含めた高抵抗のアルミニウム腐食生成物の生成を抑制できる。これにより、容量を低下させることなく集電体と電解液との間での化学反応を抑制することができるため、初期の抵抗を低減し、電圧印加時の抵抗変化も抑えることができ、抵抗の低い特性劣化の少ない長期信頼性に優れた電気二重層キャパシタを提供することができる。 In the invention according to claim 4 of the present invention, an aluminum current collector that is particularly sensitive to corrosive ions is protected from corrosive ions that are electrolytes in the electrolyte solution by a conductive barrier layer, and the capacity is reduced. In addition, the chemical reaction between the aluminum current collector and the electrolytic solution can be suppressed, and the formation of high-resistance aluminum corrosion products including aluminum hydrate can be suppressed. As a result, the chemical reaction between the current collector and the electrolyte solution can be suppressed without reducing the capacity, so that the initial resistance can be reduced and the resistance change during voltage application can also be suppressed. Thus, it is possible to provide an electric double layer capacitor having a low characteristic deterioration and excellent long-term reliability.
（実施の形態１）
図１は本実施の形態における電気二重層キャパシタの構成を示した一部切り欠き斜視図、図２は同電気二重層キャパシタに使用される分極性電極を示した断面図である。
(Embodiment 1)
FIG. 1 is a partially cutaway perspective view showing a configuration of an electric double layer capacitor in the present embodiment, and FIG. 2 is a cross-sectional view showing a polarizable electrode used in the electric double layer capacitor.
図１と図２において、１はキャパシタ素子を示し、このキャパシタ素子１はリード線２ａ、２ｂを接続した集電体３ａ、３ｂ上に活性炭粉末とカーボンブラックとバインダーとからなる分極性電極層４ａ、４ｂを形成し、その間に短絡防止用のセパレータ５ａ、５ｂを介在させて巻回することにより構成されているものである。 1 and 2, reference numeral 1 denotes a capacitor element. The capacitor element 1 has a polarizable electrode layer 4a made of activated carbon powder, carbon black, and a binder on current collectors 3a and 3b to which lead wires 2a and 2b are connected. 4b is formed, and a short-circuit preventing separator 5a, 5b is interposed therebetween and wound.
また、図２に示すごとく、銅などからなる集電体３ａ、３ｂの表面に蒸着、スパッタなどで導電性のタンタルまたはニオブ化合物を形成し、集電体３ａ、３ｂと分極性電極層４ａ、４ｂの間にタンタルまたはニオブ化合物からなる導電性のバリア層６ａ、６ｂを設ける。 Further, as shown in FIG. 2 , conductive tantalum or niobium compounds are formed on the surfaces of current collectors 3a and 3b made of copper or the like by vapor deposition or sputtering, and current collectors 3a and 3b and polarizable electrode layer 4a, Conductive barrier layers 6a and 6b made of tantalum or a niobium compound are provided between 4b.
なお、電気二重層キャパシタとしての陽極をリード線２ａと、集電体３ａと、分極性電極層４ａと、セパレータ５ａと、導電性のバリア層６ａとからなる構成とした場合には、電気二重層キャパシタとしての陰極は同じ構成で小文字ｂを付したものとなる。 When the anode as the electric double layer capacitor is composed of the lead wire 2a, the current collector 3a, the polarizable electrode layer 4a, the separator 5a, and the conductive barrier layer 6a, The cathode as the multi-layer capacitor has the same configuration and a lowercase letter b.
前記キャパシタ素子１を、腐食性イオンを電解質とする電解液（図示せず）に含浸させ、図１に示すごとく、キャパシタ素子１の上端部にリード線２ａ、２ｂが挿通する孔を設けたゴム製の封口部材７を嵌め込み、アルミニウムからなる有底円筒状のケース８に収納してケース８の開口部を絞り加工することにより、封口部材７を圧縮してケース８を封止するように構成されている。 Rubber the capacitor element 1 is impregnated into electrolyte solution corrosive ions and an electrolyte (not shown), as shown in FIG. 1, provided with holes which lead 2a in the upper portion of the capacitor element 1, 2b are inserted A sealing member 7 made of aluminum is fitted into a case 8 having a bottomed cylindrical shape made of aluminum, and the opening of the case 8 is drawn to compress the sealing member 7 so that the case 8 is sealed. Has been.
また、電解液には、電解質にテトラエチルアンモニウムテトラフルオロボレート／溶媒としてプロピレンカーボネート（ＴＥＡＢＦ４／ＰＣ）や、トリエチルメチルアンモニウムテトラフルオロボレート／プロピレンカーボネート（ＴＥＭＡＢＦ４／ＰＣ）、１−メチル−３−メチルイミダゾリウムテトラフルオロボレート／プロピレンカーボネート（ＥＭＩＢＦ４／ＰＣ）、１−エチル−２、３−ジメチルイミダゾリウムテトラフルオロボレート／プロピレンカーボネート（ＥＤＭＩＢＦ４／ＰＣ）、１、２、３−トリメチルイミダゾリウムテトラフルオロボレート／プロピレンカーボネート（ＴＭＩＢＦ４／ＰＣ）及び１、３−ジメチルイミダゾリウムテトラフルオロボレート／プロピレンカーボネート（ＤＭＩＢＦ４／ＰＣ）だけでなく、硫酸、水酸化カリウムなどの水溶液なども用いられる。In addition, in the electrolyte solution, propylene carbonate (TEABF4 / PC), triethylmethylammonium tetrafluoroborate / propylene carbonate (TEMABF4 / PC), 1-methyl-3-methylimidazolium as a tetraethylammonium tetrafluoroborate / solvent as an electrolyte. Tetrafluoroborate / propylene carbonate (EMIBF4 / PC), 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate / propylene carbonate (EDMIBF4 / PC), 1,2,3-trimethylimidazolium tetrafluoroborate / propylene carbonate (TMIBF4 / PC) and 1,3-dimethylimidazolium tetrafluoroborate / propylene carbonate (DMIBF4 / PC). , Sulfuric acid and an aqueous solution of potassium hydroxide may also be used.
前記電解液中の硫酸イオンやフッ素イオンなどの腐食性イオンに対して、銅からなる集電体３ａ、３ｂの表面にタンタルまたはニオブ化合物のバリア層６ａ、６ｂを設けることで腐食抑制効果を得られる。タンタルまたはニオブ金属及びその化合物は化学的に非常に安定で酸にも強いことから、このバリア層６ａ、６ｂを設けることにより、集電体３ａ、３ｂの表層部分において、電解液中にアニオンとして含まれているフッ素イオンと銅からなる集電体３ａ、３ｂとの化学反応で生ずる高抵抗の腐食生成物の形成を防止できる。By providing barrier layers 6a and 6b of tantalum or niobium compounds on the surfaces of current collectors 3a and 3b made of copper against corrosive ions such as sulfate ions and fluorine ions in the electrolytic solution, a corrosion suppressing effect is obtained. It is done. Since tantalum or niobium metal and its compounds are chemically very stable and resistant to acids, by providing these barrier layers 6a and 6b, as anions in the electrolyte in the surface layer portions of the current collectors 3a and 3b, It is possible to prevent formation of a high-resistance corrosion product caused by a chemical reaction between the contained fluorine ions and the current collectors 3a and 3b made of copper.
その結果として、集電体３ａ、３ｂと分極性電極層４ａ、４ｂとの間の界面抵抗をさらに低減することができるとともに、集電体３ａ、３ｂと電解液との化学反応性を抑制することで、特性劣化が少なく、長期信頼性に優れた電気二重層キャパシタとすることができるものである。As a result, the interface resistance between the current collectors 3a and 3b and the polarizable electrode layers 4a and 4b can be further reduced, and the chemical reactivity between the current collectors 3a and 3b and the electrolytic solution is suppressed. As a result, the electric double layer capacitor with little deterioration in characteristics and excellent long-term reliability can be obtained.
なお、電解液中の電解質である腐食性イオンから集電体３ａ、３ｂを保護する導電性のバリア層６ａ、６ｂには、タンタルまたはニオブ化合物だけでなく耐食性の良い珪素やチタン化合物などでも同様の効果が得られ、前記集電体３ａ、３ｂにはアルミニウムや銅だけでなく鉄などの比抵抗の低い金属を使用することが可能になる。The conductive barrier layers 6a and 6b that protect the current collectors 3a and 3b from the corrosive ions that are electrolytes in the electrolyte solution are not limited to tantalum or niobium compounds but also silicon or titanium compounds having good corrosion resistance. Thus, the current collectors 3a and 3b can be made of a metal having a low specific resistance such as iron as well as aluminum and copper.
また、このバリア層６ａは少なくとも電気二重層キャパシタの陽極にあればよく、これは電解液中のフッ素イオンなどの腐食性イオンはアニオンとして存在しているため、実使用に相当する電圧印加時には陽極と反応することがより多いので、これにより、電気二重層キャパシタの構成としての部材数を削減し、製造コストを抑えることができるものである。 Further, the barrier layer 6a may if the anode of at least the electric double layer capacitor, which is because the corrosive ions such as fluorine ions in the electrolyte solution is present as the anion, when a voltage is applied which corresponds to the actual use anode As a result, the number of members as the structure of the electric double layer capacitor can be reduced, and the manufacturing cost can be reduced.
なお、このバリア層６ａ、６ｂは好ましくは集電体３ａ、３ｂの全面に渡って設けられているものであるが、部分的にバリア層６ａ、６ｂが存在していたとしてもバリア層６ａ、６ｂが存在しない場合と比較すると、上記のフッ素と集電体３ａ、３ｂとの反応を阻むことができ、抵抗を低くし、抵抗変化を抑える効果を奏するものである。 The barrier layers 6a and 6b are preferably provided over the entire surfaces of the current collectors 3a and 3b. Even if the barrier layers 6a and 6b partially exist, the barrier layers 6a and 6b Compared with the case where 6b does not exist, the reaction between the fluorine and the current collectors 3a and 3b can be prevented, and the resistance can be lowered and the resistance change can be suppressed.
また、このバリア層６ａ、６ｂの存在はオージェ電子分光やＥＳＣＡ（またはＸＰＳ、Ｘ線光電子分光）などといった表面分析によってリン成分などが検出されることによって確認することもできるものである。 The presence of the barrier layers 6a and 6b can also be confirmed by detecting a phosphorus component or the like by surface analysis such as Auger electron spectroscopy or ESCA (or XPS or X-ray photoelectron spectroscopy).
本発明における実施の形態によれば、集電体３ａ、３ｂと分極性電極層４ａ、４ｂからリード線２ａ、２ｂを用いて電極を引き出す形としたが、この形に特定されるものではなく、集電体３ａ、３ｂから直接電極を引き出す形でもよく、腐食性イオンの電解質を含む
電解液による電気二重層キャパシタであれば同様の効果を奏するものである。
According to the embodiment of the present invention, the electrodes are drawn from the current collectors 3a, 3b and the polarizable electrode layers 4a, 4b using the lead wires 2a, 2b. However, the present invention is not limited to this shape. The electrode may be directly drawn out from the current collectors 3a and 3b, and the same effect can be obtained as long as the electric double layer capacitor is made of an electrolytic solution containing a corrosive ion electrolyte.
以上のように、本発明にかかる電気二重層キャパシタによれば、集電体と分極性電極層との間の抵抗の増加を防止することができ、電気二重層キャパシタの低抵抗化を図ることができる。 As described above, according to the electric double layer capacitor of the present invention, it is possible to prevent an increase in resistance between the current collector and the polarizable electrode layer, and to reduce the resistance of the electric double layer capacitor. Can do.
この結果、電気二重層キャパシタの信頼性向上が可能になり、大電流における高信頼性などが要求される自動車のシステムなどに有用である。 As a result, it is possible to improve the reliability of the electric double layer capacitor, which is useful for automobile systems and the like that require high reliability at a large current.
１ キャパシタ素子
２ａ，２ｂ リード線
３ａ，３ｂ 集電体
４ａ，４ｂ 分極性電極層
５ａ，５ｂ セパレータ
６ａ，６ｂ バリア層
７ 封口部材
８ ケース
DESCRIPTION OF SYMBOLS 1 Capacitor element 2a, 2b Lead wire 3a, 3b Current collector 4a, 4b Polarization electrode layer 5a, 5b Separator 6a, 6b Barrier layer 7 Sealing member 8 Case
Claims (4)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006065382A JP2007242994A (en) | 2006-03-10 | 2006-03-10 | Electric double layer capacitor |
| PCT/JP2007/052628 WO2007094366A1 (en) | 2006-02-16 | 2007-02-14 | Electric double layer capacitor |
| EP07714181.0A EP1962308B1 (en) | 2006-02-16 | 2007-02-14 | Electric double layer capacitor |
| CN200780005783.0A CN101385103B (en) | 2006-02-16 | 2007-02-14 | Electric double layer capacitor |
| US12/159,950 US7924548B2 (en) | 2006-02-16 | 2007-02-14 | Electric double layer capacitor |
| KR1020087014549A KR100994639B1 (en) | 2006-02-16 | 2007-02-14 | Electric double layer capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006065382A JP2007242994A (en) | 2006-03-10 | 2006-03-10 | Electric double layer capacitor |
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| Publication Number | Publication Date |
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| JP2007242994A JP2007242994A (en) | 2007-09-20 |
| JP2007242994A5 true JP2007242994A5 (en) | 2008-11-27 |
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| JP2006065382A Pending JP2007242994A (en) | 2006-02-16 | 2006-03-10 | Electric double layer capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61203616A (en) * | 1985-03-07 | 1986-09-09 | 松下電器産業株式会社 | Electric doule-layer capacitor |
| JP2006024727A (en) * | 2004-07-08 | 2006-01-26 | Tdk Corp | Electrochemical element |
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