JPH07122467A - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JPH07122467A JPH07122467A JP5291444A JP29144493A JPH07122467A JP H07122467 A JPH07122467 A JP H07122467A JP 5291444 A JP5291444 A JP 5291444A JP 29144493 A JP29144493 A JP 29144493A JP H07122467 A JPH07122467 A JP H07122467A
- Authority
- JP
- Japan
- Prior art keywords
- tab terminal
- sealing body
- double layer
- electric double
- rubber sealing
- 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 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 47
- 238000007789 sealing Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 20
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 239000013043 chemical agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000004714 phosphonium salts Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 17
- 239000000945 filler Substances 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 abstract description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001741 Ammonium adipate Substances 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 235000019293 ammonium adipate Nutrition 0.000 abstract description 2
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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
【０００１】[0001]
【産業上の利用分野】本発明は電気二重層コンデンサに
関し、さらに詳しく言えば、巻回型電気二重層コンデン
サの封口部分の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor, and more particularly to an improvement of a sealing portion of a wound electric double layer capacitor.
【０００２】[0002]
【従来の技術】巻回型電気二重層コンデンサは、アルミ
ニウムエッチング箔などの集電体に活性炭およびカーボ
ンブラックなどを主体とする分極性電極を付着した電極
体の一対をセパレータ紙を介して巻回したコンデンサ素
子を有し、同コンデンサ素子に電解液を含浸させた後、
ゴム封口体とともにアルミニウム製外装ケース内に組み
込み、同外装ケースの開口部を封止することにより製造
される。2. Description of the Related Art A wound-type electric double layer capacitor is formed by winding a pair of electrode bodies in which a polarizable electrode mainly composed of activated carbon and carbon black is attached to a current collector such as an aluminum etching foil via separator paper. After having impregnated with the electrolytic solution,
It is manufactured by incorporating it into an aluminum outer case together with a rubber sealing body and sealing the opening of the outer case.
【０００３】この場合、図１に例示されているように、
陽極側および陰極側の各集電体１，２には、それぞれ引
出端子としてのタブ端子３がカシメやコールドウェルド
法などにて固着され、ゴム封口体４の透孔４ａを通して
外部に引き出されている。In this case, as illustrated in FIG.
Tab terminals 3 as lead-out terminals are fixed to the current collectors 1 and 2 on the anode side and the cathode side, respectively, by caulking or the cold weld method, and are drawn out through the through holes 4a of the rubber sealing body 4. There is.
【０００４】なお、タブ端子３はアルミニウムの丸棒部
３ａと、同丸棒部３ａの一部分を偏平に加工した平坦部
３ｂと、丸棒部３ａに溶接された引出線３ｃとからな
る。一般に、引出線３ｃにはＣＰ線（銅被覆鋼線）が用
いられるが、さらにその表面に半田メッキや錫メッキが
施されることもある。The tab terminal 3 comprises a round bar 3a made of aluminum, a flat part 3b obtained by flattening a part of the round bar 3a, and a lead wire 3c welded to the round bar 3a. Generally, a CP wire (copper-coated steel wire) is used as the lead wire 3c, but the surface thereof may be further plated with solder or tin.
【０００５】電解液について説明すると、近年において
はコンデンサの特性を向上させるために、高電導化のも
のや高温での使用下において安定性を有するものが使用
されている。[0005] Explaining the electrolytic solution, in recent years, in order to improve the characteristics of the capacitor, one having a high conductivity or one having stability under use at a high temperature is used.
【０００６】例えば、γ−ブチロラクトン、プロピレン
カーボネート、エチレンカーボネード、ジメトキシエタ
ン、アセトニトリルなどの単一もしくは混合溶媒中に第
４級アンモニウム塩もしくは第４級ホスホニウム塩を溶
質として溶解したものが電解液として使用されている。For example, a solution obtained by dissolving a quaternary ammonium salt or a quaternary phosphonium salt as a solute in a single or mixed solvent such as γ-butyrolactone, propylene carbonate, ethylene carbonate, dimethoxyethane and acetonitrile is used as an electrolytic solution. It is used.
【０００７】溶質例として、カチオン種は（Ｃ２Ｈ５）
４Ｐ＋、（Ｃ２Ｈ５）３ＣＨ３Ｐ＋、（Ｃ３Ｈ７）４Ｐ
＋、（Ｃ２Ｈ５）４Ｎ＋、（Ｃ２Ｈ５）３ＣＨ３Ｎ＋、
アニオン種はＢＦ４ −、ＰＦ４ −、ＣＦ３ＳＯ３ −、Ｃ
ｌＯ４ −などである。As an example of solute, the cationic species is (C 2 H 5 ).
4 P + , (C 2 H 5 ) 3 CH 3 P + , (C 3 H 7 ) 4 P
+, (C 2 H 5) 4 N +, (C 2 H 5) 3 CH 3 N +,
The anion species are BF 4 − , PF 4 − , CF 3 SO 3 − , C
lO 4 - and the like.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上述し
た第４級アンモニウム塩や第４級ホスホニウム塩を溶質
としたこの種の電解液は、低粘度で、かつ、活性である
ため、ゴム封口体とタブ端子の丸棒部との間の微小な隙
間からでも漏液してしまうという問題があった。However, this type of electrolytic solution containing the above-mentioned quaternary ammonium salt or quaternary phosphonium salt as a solute has a low viscosity and is active. There is a problem that liquid leaks even from a minute gap between the tab terminal and the round bar.
【０００９】特に、陰極側に固着されたタブ端子の近傍
においては、電場が印加されることにより、電解液のｐ
Ｈが強アルカリとなり、これによりタブ端子の丸棒部が
腐蝕され、また、ゴム封口体が膨潤され、高温での寿命
試験において漏液が発生するという不良が多発してい
た。In particular, in the vicinity of the tab terminal fixed on the cathode side, an electric field is applied, so that the p
H becomes a strong alkali, which corrodes the round bar portion of the tab terminal and causes the rubber sealing body to swell, which often causes a liquid leakage in a life test at high temperature.
【００１０】[0010]
【課題を解決するための手段】本発明は上記した課題を
解決するためになされたもので、その構成上の特徴は、
タブ端子が固着された集電体に活性炭およびカーボンブ
ラックなどを主体とする分極性電極を付着させてなる電
極体の一対をセパレータ紙を介して巻回したコンデンサ
素子を有し、同コンデンサ素子に第４級アンモニウム塩
または第４級ホスホニウム塩を溶質とした駆動用電解液
を含浸させ、ゴム封口体とともに外装ケース内に収納し
た電気二重層コンデンサにおいて、上記ゴム封口体がブ
チルゴムを樹脂加硫もしくはパーオキサイド加硫したも
のからなり、そのウォーレス硬度計による硬度が６０〜
９０、好ましくは６５〜８５としたことにある。The present invention has been made to solve the above-mentioned problems, and the structural features thereof are as follows.
It has a capacitor element in which a pair of electrode bodies, in which a polarizable electrode mainly composed of activated carbon and carbon black is attached to a current collector to which a tab terminal is fixed, is wound with separator paper between them. In an electric double layer capacitor which is impregnated with a driving electrolytic solution containing a quaternary ammonium salt or a quaternary phosphonium salt as a solute and is housed in an outer case together with a rubber sealing body, the rubber sealing body vulcanizes butyl rubber or It is made of peroxide vulcanizate and has a hardness of 60-
90, preferably 65-85.
【００１１】本発明においては、さらに少なくとも陰極
側の集電体に固着された上記タブ端子に、酸化性を有す
る化学的薬剤による化学的酸化または電解酸化により形
成される化成皮膜を設けることが好ましい。In the present invention, it is preferable that at least the tab terminal fixed to the current collector on the cathode side is provided with a chemical conversion film formed by chemical oxidation or electrolytic oxidation by an oxidizing chemical agent. .
【００１２】本発明に係るゴム封口体において、ゴムの
圧縮永久歪は５０％以下が好ましく、特に好ましくは２
５％以下のゴムが採用される。In the rubber sealing body according to the present invention, the compression set of rubber is preferably 50% or less, particularly preferably 2%.
Less than 5% rubber is used.
【００１３】圧縮永久歪の測定法を次に例示する。直径
１６ｍｍ、厚さ２．００ｍｍのゴム円板を５枚重ね、そ
の厚み（ｔ０）を測定する。５枚のゴム円板を金属板で
挟み、厚さ７．５ｍｍ（ｔ２）に圧縮し、１１５℃で７
０時間放置した後に金属板を除去し、開放後のゴム円板
の厚み（ｔ）を実測する。圧縮永久歪は（１）式によっ
て示される。A method for measuring compression set will be exemplified below. Five rubber discs having a diameter of 16 mm and a thickness of 2.00 mm are stacked, and the thickness (t 0 ) is measured. Five rubber discs are sandwiched between metal plates, compressed to a thickness of 7.5 mm (t 2 ), and heated at 115 ° C. for 7
After standing for 0 hour, the metal plate is removed, and the thickness (t) of the rubber disc after opening is measured. The compression set is expressed by equation (1).
【００１４】 圧縮永久歪（％）＝｛（ｔ０−ｔ）／（ｔ０−ｔ２）｝×１００…（１） ＝｛（１０．００−ｔ）／（１０．００−７．５０）｝×１００。Compression set (%) = {(t 0 −t) / (t 0 −t 2 )} × 100 ... (1) = {(10.00-t) / (10.00−7.50) )} × 100.
【００１５】本発明において、ゴムに配合するフィラー
としてカーボンの他に、ジルコニア、アルミナ、シリ
カ、シリカアルミナまたはそれらの焼成体などが耐アル
カリの見地から適宜用いられる。なお、ＺｎＯ、ＰｂＯ
などの重金属はアルカリに溶解し易いので好ましくな
い。In the present invention, in addition to carbon, zirconia, alumina, silica, silica-alumina or a fired body thereof is appropriately used as a filler to be mixed with rubber from the viewpoint of alkali resistance. Incidentally, ZnO, PbO
Heavy metals such as are easily dissolved in alkali and are not preferable.
【００１６】タブ端子を化学的酸化で化成処理するため
の化成液としては、酸化性を有する化学的薬剤のうち一
種以上を混合した水溶液、もしくはアルコール溶液を使
用することが好ましい。さらに好ましくは、酸化性を有
する化学的薬剤のうち一種以上と、リンを含有した化合
物類を一種以上混合した水溶液、もしくはアルコール溶
液を使用するのが良いが、これに限定されるものではな
い。As a chemical conversion liquid for chemical conversion treatment of tab terminals, it is preferable to use an aqueous solution or an alcohol solution in which one or more chemical agents having an oxidizing property are mixed. More preferably, an aqueous solution or an alcohol solution in which one or more oxidizing chemical agents and one or more phosphorus-containing compounds are mixed is used, but the invention is not limited thereto.
【００１７】タブ端子の電解酸化の場合には、タブ端子
をアジピン酸系水溶液や硼酸系水溶液などの電解液にて
陽極酸化処理を行なうのが好ましい。In the case of electrolytic oxidation of the tab terminal, it is preferable to subject the tab terminal to anodizing treatment with an electrolytic solution such as an adipic acid-based aqueous solution or a boric acid-based aqueous solution.
【００１８】本発明において、上記ゴム封口体と上記タ
ブ端子とを併用するのが好ましい。なお、化成皮膜はタ
ブ端子の少なくとも丸棒部に形成されれば良いが、場合
によっては、平坦部にも形成しても良い。In the present invention, it is preferable to use the rubber sealing body and the tab terminal together. The chemical conversion film may be formed on at least the round bar portion of the tab terminal, but may be formed on the flat portion in some cases.
【００１９】また、製品中の電解液中の水分量は５００
ｐｐｍ以下が好ましい。これは電圧印加により電解液の
水分が電気分解し水素が発生する。これにより、電解液
の耐圧が下がると同時に、内圧が上昇し製品の封止性を
損ねるとともに、電解液の蒸散が速められ、製品の寿命
が短くなるためである。The water content of the electrolytic solution in the product is 500.
ppm or less is preferable. This is because when a voltage is applied, the water content of the electrolytic solution is electrolyzed to generate hydrogen. As a result, the withstand pressure of the electrolytic solution is lowered, and at the same time, the internal pressure is increased to impair the sealing property of the product, and the evaporation of the electrolytic solution is accelerated, which shortens the life of the product.
【００２０】[0020]
【作用】ブチルゴムを樹脂加硫もしくはパーオキサイド
加硫することにより、電解液の透過飛散量が小さく気密
性に優れるとともに、耐アルカリ性も改善される。な
お、硬度を上記の範囲とすることにより、例えばパーツ
フィーダで搬送する際に静電気が帯びにくくなり、部品
の流れ工程がよりスムースとなり生産効率が向上する。
また、タブ端子に化成皮膜を形成することにより、耐ア
ルカリ性が良好となる。By vulcanizing butyl rubber with resin or peroxide, the amount of permeation and scattering of the electrolytic solution is small and the airtightness is excellent, and the alkali resistance is also improved. By setting the hardness within the above range, for example, static electricity is less likely to be generated when it is conveyed by a parts feeder, and the flow process of parts becomes smoother and the production efficiency is improved.
Further, by forming the chemical conversion film on the tab terminal, the alkali resistance is improved.
【００２１】[0021]
【実施例】エッチング処理した厚さ４０μｍ、幅１３ｍ
ｍ、長さ６０ｍｍのアルミニウム箔（集電体）の表面
に、活性炭を主体とし、アセチレンブラックとバインダ
ー（ＰＴＦＥ；ポリテトラフルオロエチレン）とを６：
３：１の割合で混練した炭素膜（分極性電極）を厚さ１
００μｍとして付着させて炭素電極とし、この炭素電極
の一対を厚さ６０μｍのセパレータ紙を挟んで巻回して
コンデンサ素子を形成し、同コンデンサ素子にＥｔ４Ｎ
ＢＦ４（テトラエチルアンモニウムテトラフルオロボレ
ート）／ＰＣ（プロピレンカーボネイト）が１ｍｏｌ／
ｌ（リットル）からなる電解液を含浸させて、定格２．
５Ｖ１．０Ｆ、直径８ｍｍ、軸長２０ｍｍの巻回型電気
二重層コンデンサを作製するにあたり、ゴム封口体と、
タブ端子として以下のものを用いた。[Example] 40 μm thick and 13 m wide after etching
Activated carbon was mainly used, and acetylene black and a binder (PTFE; polytetrafluoroethylene) were used on the surface of an aluminum foil (current collector) having a length of 60 m and a length of 6:
A carbon film (polarizable electrode) kneaded at a ratio of 3: 1 with a thickness of 1
A carbon electrode was formed by adhering it to a thickness of 00 μm, and a pair of the carbon electrodes were wound with a separator paper having a thickness of 60 μm being wound therebetween to form a capacitor element. Et 4 N was formed on the capacitor element.
BF 4 (tetraethylammonium tetrafluoroborate) / PC (propylene carbonate) is 1 mol /
1 (liter) is impregnated with an electrolytic solution to give a rating of 2.
In manufacturing a wound type electric double layer capacitor having a voltage of 5V1.0F, a diameter of 8 mm and an axial length of 20 mm, a rubber sealing body and
The following were used as tab terminals.
【００２２】なお、寸法について説明すると、ゴム封口
体の直径７．４ｍｍ、厚さ４．０ｍｍ、透孔（端子挿通
孔）１．２ｍｍとし、また、タブ端子としては図１のよ
うな形状で、丸棒部の直径１．３ｍｍ、同長さ２．４ｍ
ｍ、平坦部の幅１．５ｍｍ、同厚さ０．２５ｍｍ、同長
さ１０ｍｍとした。Explaining the dimensions, the rubber sealing body has a diameter of 7.4 mm, a thickness of 4.0 mm, a through hole (terminal insertion hole) of 1.2 mm, and the tab terminal has a shape as shown in FIG. , Round bar diameter 1.3mm, same length 2.4m
m, the width of the flat portion was 1.5 mm, the thickness was 0.25 mm, and the length was 10 mm.
【００２３】《実施例１》ゴム封口体として、カーボン
とシリカアルミナの焼結微粉末をフィラーとしたブチル
ゴムをパーオキサイド加硫したウォーレス硬度が７５の
ものを用いた。タブ端子は未化成とした。Example 1 As a rubber sealing member, a material having a Wallace hardness of 75, which was obtained by peroxide vulcanizing butyl rubber containing a sintered fine powder of carbon and silica-alumina as a filler, was used. The tab terminal is unformed.
【００２４】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、定格電圧
２．５Ｖを印加し、７０℃、２０００時間の高温負荷試
験を行なったところ、重量変化は−２．４ｍｇ（平均
値）、液漏れ数は０個であった。When a rated voltage of 2.5 V was applied to the 200 electric double layer capacitors to which the rubber sealing body and tab terminals were applied and a high temperature load test was performed at 70 ° C. for 2000 hours, a weight change was −2. 0.4 mg (average value), and the number of liquid leaks was 0.
【００２５】次に、ここで使用したブチルゴムと同ロッ
トのゴムを２ｍｍ厚のシート状に成型し、直径１６ｍｍ
に打ち抜き、５枚重ねたものを２５％（７．５０ｍｍ）
圧縮変形し、１１５℃で７０時間保持した後に開放し、
圧縮永久歪を測定したところ、１０％であった。Next, a rubber of the same lot as the butyl rubber used here was molded into a sheet having a thickness of 2 mm and a diameter of 16 mm.
25% (7.50 mm) of punched 5 sheets
Compressed and deformed, held at 115 ° C for 70 hours and then opened,
The compression set was measured and found to be 10%.
【００２６】なお、高温負荷試験前の電気二重層コンデ
ンサを解体し、電解液中の水分をカールフィッシャー法
で測定したところ、１８０ｐｐｍであった。The electric double layer capacitor before the high temperature load test was disassembled, and the water content in the electrolytic solution was measured by the Karl Fischer method to be 180 ppm.
【００２７】《実施例２》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムをパーオキサイ
ド加硫したウォーレス硬度が８０のものを用いた。そし
て、タブ端子には次のようにして化学的に化成皮膜を形
成した。Example 2 As a rubber sealing body, Example 1 was used.
A butyl rubber containing the same filler as in 1. was peroxide-vulcanized and had a Wallace hardness of 80. Then, a chemical conversion film was chemically formed on the tab terminal as follows.
【００２８】すなわち、リン酸０．５重量％およびクロ
ム酸カリウム０．５重量％からなる水溶液を沸騰させた
ものを反応浴とし、この反応浴中にタブ端子を浸漬して
１０分間化成処理し、丸棒部と平坦部に化成皮膜を形成
した。That is, a reaction solution was prepared by boiling an aqueous solution containing 0.5% by weight of phosphoric acid and 0.5% by weight of potassium chromate, and the tab terminals were immersed in this reaction bath and subjected to chemical conversion treatment for 10 minutes. A chemical conversion coating was formed on the round bar portion and the flat portion.
【００２９】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
１．５ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which the rubber sealing body and the tab terminal are applied,
When the same high temperature load test was conducted, the weight change was −
The amount of liquid leakage was 1.5 mg (average value) and 0.
【００３０】《実施例３》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムをパーオキサイ
ド加硫したウォーレス硬度が８２のものを用いた。そし
て、タブ端子には次のようにして電気化学的に化成皮膜
を形成した。Example 3 As a rubber sealing body, Example 1
A butyl rubber containing the same filler as in 1. was peroxide-vulcanized and had a Wallace hardness of 82. Then, a chemical conversion film was electrochemically formed on the tab terminal as follows.
【００３１】アジピン酸アンモニウム５重量％の水溶液
を液温５０℃に維持し、この化成浴中にタブ端子の平坦
部と丸棒部とを浸漬し、引出線を陽極とし、化成浴中に
対極を配置して電流密度１０ｍＡ／ｃｍ２、電圧１５０
Ｖを２時間印加し、陽極酸化処理した。An aqueous solution of 5% by weight of ammonium adipate was maintained at a liquid temperature of 50 ° C., the flat portion of the tab terminal and the round bar portion were immersed in this formation bath, and the leader wire was used as an anode, and the counter electrode was formed in the formation bath. Current density of 10 mA / cm 2 and voltage of 150
V was applied for 2 hours to perform anodizing treatment.
【００３２】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
１．８ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which this rubber sealing body and tab terminals were applied, Example 1
When the same high temperature load test was conducted, the weight change was −
1.8 mg (average value) and the number of liquid leaks was 0.
【００３３】《実施例４》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が７８のものを用いた。タブ端子は未化
成とした。Example 4 As a rubber sealing body, Example 1 was used.
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 78. The tab terminal is unformed.
【００３４】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
２．５ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which this rubber sealing body and tab terminal were applied, Example 1
When the same high temperature load test was conducted, the weight change was −
The number of liquid leaks was 2.5 mg (average value) and 0.
【００３５】《実施例５》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が７６のものを用いた。そして、タブ端
子には実施例２と同様にして化学的に化成皮膜を形成し
た。Example 5 As a rubber sealing body, Example 1
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 76. Then, a chemical conversion film was chemically formed on the tab terminal in the same manner as in Example 2.
【００３６】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
１．６ｍｇ（平均値）、液漏れ数は０個であった。Example 1 was carried out on 200 electric double layer capacitors to which the rubber sealing body and tab terminals were applied.
When the same high temperature load test was conducted, the weight change was −
The number of leaks was 1.6 mg (average value) and 0.
【００３７】《実施例６》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が７５のものを用いた。そして、タブ端
子には実施例３と同様にして電気化学的に化成皮膜を形
成した。Example 6 As a rubber sealing body, Example 1
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 75. Then, a chemical conversion film was electrochemically formed on the tab terminal in the same manner as in Example 3.
【００３８】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
１．８ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which the rubber sealing body and the tab terminal are applied,
When the same high temperature load test was conducted, the weight change was −
1.8 mg (average value) and the number of liquid leaks was 0.
【００３９】《実施例７》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が６０のものを用いた。そして、タブ端
子には実施例２と同様にして化学的に化成皮膜を形成し
た。Example 7 As a rubber sealing body, Example 1 was used.
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 60. Then, a chemical conversion film was chemically formed on the tab terminal in the same manner as in Example 2.
【００４０】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
２．２ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which this rubber sealing body and tab terminal were applied, Example 1
When the same high temperature load test was conducted, the weight change was −
The amount of liquid leakage was 2.2 mg (average value) and 0.
【００４１】《実施例８》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が８９のものを用いた。そして、タブ端
子には実施例２と同様にして化学的に化成皮膜を形成し
た。Example 8 As a rubber sealing body, Example 1 was used.
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 89. Then, a chemical conversion film was chemically formed on the tab terminal in the same manner as in Example 2.
【００４２】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
２．１ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which this rubber sealing body and tab terminal were applied, Example 1
When the same high temperature load test was conducted, the weight change was −
The number of liquid leaks was 2.1 mg (average value) and 0.
【００４３】《実施例９》ゴム封口体として、実施例１
と同様のフィラーを含有するブチルゴムを樹脂加硫した
ウォーレス硬度が６８のものを用いた。そして、タブ端
子には実施例２と同様にして化学的に化成皮膜を形成し
た。Example 9 As a rubber sealing body, Example 1
A butyl rubber containing the same filler as in 1. was vulcanized with a resin and had a Wallace hardness of 68. Then, a chemical conversion film was chemically formed on the tab terminal in the same manner as in Example 2.
【００４４】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
２．３ｍｇ（平均値）、液漏れ数は０個であった。Example 1 of 200 electric double layer capacitors to which this rubber sealing body and tab terminals were applied
When the same high temperature load test was conducted, the weight change was −
The amount of liquid leakage was 2.3 mg (average value) and 0.
【００４５】《実施例１０》ゴム封口体として、実施例
１と同様のフィラーを含有するブチルゴムを樹脂加硫し
たウォーレス硬度が７２のものを用いた。そして、タブ
端子には実施例３と同様にして電気化学的に化成皮膜を
形成した。Example 10 As the rubber sealing body, a butyl rubber containing the same filler as in Example 1 and vulcanized with resin and having a Wallace hardness of 72 was used. Then, a chemical conversion film was electrochemically formed on the tab terminal in the same manner as in Example 3.
【００４６】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
２．４ｍｇ（平均値）、液漏れ数は０個であった。About 200 of the above electric double layer capacitors to which this rubber sealing body and tab terminal were applied, Example 1
When the same high temperature load test was conducted, the weight change was −
The amount of liquid leakage was 2.4 mg (average value) and 0.
【００４７】〈従来例１〉ゴム封口体として、カーボ
ン、酸化亜鉛およびシリカ粉末をフィラーとしたブチル
ゴムをイオウ加硫したウォーレス硬度が７０のものを用
いた。タブ端子は未化成とした。<Prior Art Example 1> As a rubber sealing body, a butyl rubber containing carbon, zinc oxide and silica powder as a filler and sulfur-vulcanized and having a Wallace hardness of 70 was used. The tab terminal is unformed.
【００４８】このゴム封口体およびタブ端子を適用した
上記電気二重層コンデンサ２００個について、実施例１
と同様の高温負荷試験を行なったところ、重量変化は−
６．２ｍｇ（平均値）、液漏れ数は３個であった。次
に、実施例１と同じ方法でゴムの圧縮永久歪を測定した
ところ、９０％であった。About 200 of the above electric double layer capacitors to which the rubber sealing body and the tab terminal are applied,
When the same high temperature load test was conducted, the weight change was −
The amount of liquid leakage was 6.2 mg (average value) and three. Next, when the compression set of the rubber was measured by the same method as in Example 1, it was 90%.
【００４９】比較を容易にするため、上記実施例１〜１
０および従来例１の試験結果を表１に示すが、本発明に
よれば電解液の液漏れ量が大幅に減り、それに伴って液
漏れ不良をほぼ「０」にすることができた。In order to facilitate comparison, Examples 1 to 1 above
The test results of No. 0 and Conventional Example 1 are shown in Table 1. According to the present invention, the amount of electrolyte leakage was significantly reduced, and accordingly, the liquid leakage failure could be made almost “0”.
【００５０】[0050]
【表１】 [Table 1]
【００５１】[0051]
【発明の効果】以上説明したように、本発明によれば、
ゴム封口体としてブチルゴムを樹脂加硫もしくはパーオ
キサイド加硫したものからなり、その硬度を６０〜９０
（ウォーレス硬度計による）の範囲としたことにより、
さらにはタブ端子に酸化性を有する化学的薬剤による化
学的酸化または電解酸化により形成される化成皮膜を設
けることにより、第４級アンモニウム塩や第４級ホスホ
ニウム塩を溶質とした電解液を用いた巻回型電気二重層
コンデンサにおいて、漏液の発生を防止することができ
る。As described above, according to the present invention,
The rubber sealing body is made of butyl rubber resin-vulcanized or peroxide-vulcanized, and has a hardness of 60 to 90.
By setting the range (according to the Wallace hardness tester),
Furthermore, an electrolytic solution using a quaternary ammonium salt or a quaternary phosphonium salt as a solute was used by providing a chemical conversion film formed by chemical oxidation or electrolytic oxidation with a chemical agent having an oxidizing property on the tab terminal. In the wound electric double layer capacitor, it is possible to prevent the occurrence of liquid leakage.
【図１】ゴム封口体とタブ端子とを示した模式図。FIG. 1 is a schematic diagram showing a rubber sealing body and a tab terminal.
１，２ 集電体 ３ タブ端子 ３ａ 丸棒部 ３ｂ 平坦部 ４ ゴム封口体 ４ａ 透孔 1, 2 Current collector 3 Tab terminal 3a Round bar part 3b Flat part 4 Rubber sealing body 4a Through hole
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ (72)発明者 数原 学 神奈川県藤沢市辻堂新町２丁目２番１号 エルナー株式会社内Continuation of front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location C (72) Inventor Manabu Kazuhara 2-2-1 Tsujido Shinmachi, Fujisawa City, Kanagawa Elner Co., Ltd.
Claims (3)
よびカーボンブラックなどを主体とする分極性電極を付
着させてなる電極体の一対をセパレータ紙を介して巻回
したコンデンサ素子を有し、同コンデンサ素子に第４級
アンモニウム塩または第４級ホスホニウム塩を溶質とし
た電解液を含浸させ、ゴム封口体とともに外装ケース内
に収納した電気二重層コンデンサにおいて、上記ゴム封
口体はブチルゴムを樹脂加硫もしくはパーオキサイド加
硫したものからなり、その硬度は６０〜９０（ウォーレ
ス硬度計による）の範囲であることを特徴とする電気二
重層コンデンサ。1. A capacitor element in which a pair of electrode bodies each having a polarizable electrode mainly composed of activated carbon and carbon black attached to a current collector to which a tab terminal is fixedly attached is wound around a separator paper. In the electric double layer capacitor in which the capacitor element is impregnated with an electrolytic solution containing a quaternary ammonium salt or a quaternary phosphonium salt as a solute and is housed in an outer case together with a rubber sealing body, the rubber sealing body is made of butyl rubber. An electric double layer capacitor, which is made of vulcanized or peroxide vulcanized material and has a hardness of 60 to 90 (according to a Wallace hardness meter).
上記タブ端子には、酸化性を有する化学的薬剤による化
学的酸化または電解酸化により形成される化成皮膜が設
けられていることを特徴とする請求項１に記載の電気二
重層コンデンサ。2. A chemical conversion film formed by chemical oxidation or electrolytic oxidation by a chemical agent having an oxidizing property is provided on at least the tab terminal fixed to the current collector on the cathode side. The electric double layer capacitor according to claim 1.
が混合されることを特徴とする請求項２に記載の電気二
重層コンデンサ。3. The electric double layer capacitor according to claim 2, wherein the chemical agent is mixed with a compound containing phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5291444A JPH07122467A (en) | 1993-10-27 | 1993-10-27 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5291444A JPH07122467A (en) | 1993-10-27 | 1993-10-27 | Electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07122467A true JPH07122467A (en) | 1995-05-12 |
Family
ID=17768951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5291444A Pending JPH07122467A (en) | 1993-10-27 | 1993-10-27 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07122467A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952594A2 (en) * | 1998-03-23 | 1999-10-27 | Matsushita Electric Industrial Co., Ltd. | Aluminium electrolytic capacitor |
| WO2005076300A1 (en) * | 2004-02-05 | 2005-08-18 | Matsushita Electric Industrial Co., Ltd. | Aluminum electrolytic capacitor and its manufacturing method |
| US7768770B2 (en) * | 2006-02-14 | 2010-08-03 | Ls Mtron Ltd. | Connecting structure between electrode and lead, electric double layer capacitor having the same, and method for manufacturing the capacitor |
| US8780528B2 (en) | 2011-06-27 | 2014-07-15 | Panasonic Corporation | Electrolyte and electric double-layer capacitor using same |
-
1993
- 1993-10-27 JP JP5291444A patent/JPH07122467A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0952594A2 (en) * | 1998-03-23 | 1999-10-27 | Matsushita Electric Industrial Co., Ltd. | Aluminium electrolytic capacitor |
| EP0952594A3 (en) * | 1998-03-23 | 2004-01-14 | Matsushita Electric Industrial Co., Ltd. | Aluminium electrolytic capacitor |
| WO2005076300A1 (en) * | 2004-02-05 | 2005-08-18 | Matsushita Electric Industrial Co., Ltd. | Aluminum electrolytic capacitor and its manufacturing method |
| US7400491B2 (en) | 2004-02-05 | 2008-07-15 | Matsushita Electric Industrial Co., Ltd. | Aluminum electrolytic capacitor and method of producing the same |
| US7768770B2 (en) * | 2006-02-14 | 2010-08-03 | Ls Mtron Ltd. | Connecting structure between electrode and lead, electric double layer capacitor having the same, and method for manufacturing the capacitor |
| US8780528B2 (en) | 2011-06-27 | 2014-07-15 | Panasonic Corporation | Electrolyte and electric double-layer capacitor using same |
| JP5655945B2 (en) * | 2011-06-27 | 2015-01-21 | パナソニックＩｐマネジメント株式会社 | Electric double layer capacitor |
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