JPH05343263A - Manufacture of electric double layered capacitor - Google Patents
Manufacture of electric double layered capacitorInfo
- Publication number
- JPH05343263A JPH05343263A JP14702292A JP14702292A JPH05343263A JP H05343263 A JPH05343263 A JP H05343263A JP 14702292 A JP14702292 A JP 14702292A JP 14702292 A JP14702292 A JP 14702292A JP H05343263 A JPH05343263 A JP H05343263A
- Authority
- JP
- Japan
- Prior art keywords
- electric double
- double layer
- electrolyte
- layer capacitor
- container
- 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.)
- Granted
Links
Classifications
-
- 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
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の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electric double layer capacitor.
【０００２】[0002]
【従来の技術】電気二重層コンデンサはメモリーバック
アップ用部品として広く用いられている。電池または商
用交流電源を直流に変換した電源と並列に電気二重層コ
ンデンサを接続し、電源の瞬断時に電気二重層コンデン
サに蓄積された電荷により種々の部品のバックアップす
るという形で使用されている。近年、１０Ｆ以上の大容
量をもつ電気二重層コンデンサが開発されるに至った。
例えば、Ｐｒｏｃｅｅｄｉｎｇ ｏｆ ｔｈｅ ４１ｓ
ｔ Ｅｌｅｃｔｒｏｎｉｃ Ｃｏｍｐｏｎｅｎｔｓ ａ
ｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｎｆｅｒｅｎｃｅ
ｐ５３１−５３６（１９９１）には２．３Ｖ−５００Ｆ
の電気二重層コンデンサが、Ｅｘｔｅｎｄｅｄ Ａｂｓ
ｔｒａｃｔ ｏｆ ｔｈｅ １８０ｔｈ Ｅｌｅｃｔｒ
ｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ Ｍｅｅｔｉｎ
ｇ，Ｐｈｏｅｎｉｘ ＡＺ，Ａｂｓｔｒａｃｔ Ｎｏ．
８０（１９９１）には５．５Ｖ−１０００Ｆの電気二重
層コンデンサがそれぞれ紹介されている。これらの電気
二重層コンデンサは、大容量でかつ等価直列抵抗が低い
ことを生かして、モータ制御装置のブレーキ動作を回生
状態、すなわちモータが発電機として作用する回生エネ
ルギーの蓄積素子としてその用途が期待されている。2. Description of the Related Art Electric double layer capacitors are widely used as memory backup parts. It is used in the form of connecting an electric double layer capacitor in parallel with a battery or a power supply obtained by converting a commercial AC power supply into a direct current, and backing up various parts by the electric charge accumulated in the electric double layer capacitor when the power supply is interrupted .. In recent years, an electric double layer capacitor having a large capacity of 10 F or more has been developed.
For example, Proceeding of the 41s
t Electronic Components a
nd Technology Conference
2.3V-500F for p531-536 (1991)
Electric Double Layer Capacitors by Extended Abs
tract of the 180th ectr
electrical Society Meetin
g, Phoenix AZ, Abstract No.
80 (1991) introduces 5.5V-1000F electric double layer capacitors. These electric double layer capacitors are expected to be used as a storage element of regenerative energy in which the braking operation of the motor control device is in a regenerative state, that is, the motor acts as a generator, by taking advantage of its large capacity and low equivalent series resistance. Has been done.
【０００３】[0003]
【発明が解決しようとする課題】従来の電気二重層コン
デンサの静電容量は数Ｆ以下であったのに対し、数十Ｆ
以上の静電容量をもつ大容量電気二重層コンデンサは、
基本素子に充填される分極性電極の重量が１０倍以上に
なる。このため従来の電気二重層コンデンサでは問題に
ならなかった電解液の分極性電極への含浸不足によるガ
スの発生や電解液に溶解した酸素によるリーク電流が大
きくなるといった問題が顕在化してきた。While the electrostatic capacity of the conventional electric double layer capacitor was several F or less, it was several tens of F.
A large-capacity electric double layer capacitor with the above capacitance is
The weight of the polarizable electrode filled in the basic element is 10 times or more. For this reason, problems such as generation of gas due to insufficient impregnation of the polarizable electrode with the electrolytic solution and increase in leakage current due to oxygen dissolved in the electrolytic solution have become apparent, which have not been a problem in conventional electric double layer capacitors.
【０００４】[0004]
【課題を解決するための手段】本発明は電気二重層コン
デンサの製造工程において電解液を含浸した後に充電を
行い、再び電解液を含浸し封止を行うことを特徴とす
る。また基本素子を封止する時に電槽内の空間に不活性
ガスを封入することを特徴とする。The present invention is characterized in that, in the process of manufacturing an electric double layer capacitor, charging is performed after impregnating with an electrolytic solution, and then impregnated with the electrolytic solution again and sealing is performed. In addition, when the basic element is sealed, an inert gas is filled in the space inside the battery case.
【０００５】[0005]
【実施例】以下、実施例をもとに本発明を説明する。EXAMPLES The present invention will be described below based on examples.
【０００６】フェノール系活性炭粉末と粉末フェノール
樹脂の重量比が７０／３０になるように秤量し、ボール
ミルにて乾式混合を行った。この混合粉末１０ｇを１５
０℃、１００ｋｇ／ｃｍ2 の圧力で１０分間、金型成型
し５０×３５ｍｍ2 、厚さ６ｍｍの活性炭含有フェノー
ル樹脂板を得た。これを電気炉中、Ｎ2 雰囲気下で９０
０℃で２時間熱処理を行った。昇降温度速度は１０℃／
ｈとした。得られた活性炭／カーボン複合体の寸法は４
７×３３×６ｍｍ3 の直方体であり、図１の分極性電極
１となる。カーボン製集電極２は角柱状で上部が円筒形
であり、円筒部の上部にはネジ穴が設けてある。カーボ
ン系導電性接着剤カーボン製集電体２の角柱部に塗布
し、分極性電極１と接着し、１５０℃で３０分間熱硬化
した。[0006] Phenol-based activated carbon powder and powdered phenol resin were weighed so that the weight ratio was 70/30, and dry-blended with a ball mill. 10 g of this mixed powder
Molding was carried out at 0 ° C. and a pressure of 100 kg / cm 2 for 10 minutes to obtain an activated carbon-containing phenol resin plate of 50 × 35 mm 2 and a thickness of 6 mm. 90 in an N 2 atmosphere in an electric furnace
Heat treatment was performed at 0 ° C. for 2 hours. Temperature rise / fall rate is 10 ℃ /
It was set to h. The size of the resulting activated carbon / carbon composite is 4
It is a rectangular parallelepiped of 7 × 33 × 6 mm 3 and becomes the polarizable electrode 1 in FIG. The carbon collector electrode 2 has a prismatic shape and a cylindrical upper portion, and a screw hole is provided in the upper portion of the cylindrical portion. Carbon-based conductive adhesive was applied to the prismatic portion of the carbon current collector 2, adhered to the polarizable electrode 1, and thermally cured at 150 ° C. for 30 minutes.
【０００７】次に作製した電気二重層コンデンサの構造
を図１（ａ）、（ｂ）、（ｃ）を用いて次に説明する。
上述した集電体を一体化した分極性電極を片側電極とし
て同じ構成の片方の側電極をもう一つ用意し、厚さ２５
μｍのポリプロピレン製セパレータ３を狭んで向かい合
わせた。これらをアクリロニトリブタジエンスチレン
（以下ＡＢＳと略す）製容器４に挿入し、エポキシ樹脂
でＡＢＳ製蓋４’を接着した。蓋４’には電解液導入用
に７ｍｍφの穴が設けてある。集電体２と蓋４’の間を
エポキシ樹脂をシーリング剤にして接着封止した。分極
性電極１に電解液を含浸させるために、容器全体を真空
にした後、容器４に電解液を注入した。電解液として
は、３０ｗｔ％の硫酸水溶液を用いた。外部と通じる７
ｍｍφの穴が開いた状態で外部から１Ｖで２４時間定電
圧充電を行い、再び容器全体を真空にし分極性電極１に
電解液を含浸させ、全体を空気リークし電解液注入装置
から取りだした。この後、安全弁を兼ねたフィルム状の
栓６と蓋４’をエポキシ樹脂を用いて封止した。封止し
た容器４の蓋４’の外側からネジが切ってあるステンレ
ス製端子５を接続した。このようにして本発明の電気二
重層コンデンサを試作した。Next, the structure of the produced electric double layer capacitor will be described with reference to FIGS. 1 (a), 1 (b) and 1 (c).
Another polarizable electrode having the same structure as the polarizable electrode integrated with the above-described current collector is prepared as one polar electrode, and the thickness of the polarizable electrode is 25
The polypropylene separators 3 having a size of μm were narrowed and faced each other. These were inserted into a container 4 made of acrylonitrile-butadiene-styrene (abbreviated as ABS hereinafter), and an ABS lid 4'was adhered with an epoxy resin. The lid 4 ′ is provided with a hole of 7 mmφ for introducing the electrolytic solution. The space between the current collector 2 and the lid 4'was adhesively sealed using an epoxy resin as a sealing agent. In order to impregnate the polarizable electrode 1 with the electrolytic solution, the entire container was evacuated and then the electrolytic solution was injected into the container 4. A 30 wt% sulfuric acid aqueous solution was used as the electrolytic solution. Communicate with the outside 7
With the hole of mmφ opened, constant voltage charging was performed from the outside for 24 hours at 1 V, the entire container was evacuated again, and the polarizable electrode 1 was impregnated with the electrolytic solution. After that, the film-shaped stopper 6 also serving as a safety valve and the lid 4 ′ were sealed with an epoxy resin. From the outside of the lid 4 ′ of the sealed container 4, a screwed stainless steel terminal 5 was connected. Thus, the electric double layer capacitor of the present invention was manufactured as a prototype.
【０００８】前例と同様に分極性電極１を作製し、集電
体２と接続した１対の分極性電極の間にセパレータ３を
入れ、これらを容器４に挿入し、蓋４’をエポキシ樹脂
で接着した。蓋４’には電解液導入用に７ｍｍφの穴が
設けてある。集電体２と蓋４’の間をエポキシ樹脂をシ
ーリング剤にして接着封止した。分極性電極１に電解液
を含浸させるために、容器全体を真空にした後、容器４
に電解液を注入した。電解液としては、３０ｗｔ％の硫
酸水溶液を用いた。外部と通じる７ｍｍφの穴が開いた
状態で外部から１Ｖで２４時間定電圧充電を行い、再び
容器全体を真空にし分極性電極１に電解液を含浸させ、
全体を窒素リークし電解液注入装置から取りだした。こ
の後、安全弁を兼ねた、フィルム状の栓６戸蓋４’をエ
ポキシ樹脂を用いて封止した。封止した容器４の蓋４’
の外側からネジが切ってあるステンレス製端子５を接続
した。このようにして本発明の電気二重層コンデンサを
試作した。A polarizable electrode 1 was prepared in the same manner as in the previous example, a separator 3 was placed between a pair of polarizable electrodes connected to a collector 2, these were inserted into a container 4, and a lid 4'was attached to an epoxy resin. I glued it in. The lid 4 ′ is provided with a 7 mmφ hole for introducing an electrolytic solution. A space between the current collector 2 and the lid 4'was adhesively sealed using an epoxy resin as a sealing agent. In order to impregnate the polarizable electrode 1 with the electrolytic solution, the entire container is evacuated and then the container 4
The electrolytic solution was injected into. A 30 wt% sulfuric acid aqueous solution was used as the electrolytic solution. With a 7 mmφ hole communicating with the outside open, constant voltage charging was performed from the outside for 24 hours at 1 V, the entire container was evacuated again, and the polarizable electrode 1 was impregnated with the electrolytic solution.
The whole was leaked with nitrogen and taken out from the electrolyte injection device. After that, the film-shaped stopper 6 door cover 4'also serving as a safety valve was sealed with an epoxy resin. The lid 4'of the sealed container 4
A stainless steel terminal 5 with a screw cut from the outside was connected. Thus, the electric double layer capacitor of the present invention was manufactured as a prototype.
【０００９】[0009]
【参考例】前記２つの実施例と同様に電気二重層コンデ
ンサを組立た。分極性電極１に電解液を含浸させるため
に容器全体を真空にした後、容器４に電解液を注入し、
空気リークし電解液注入装置から取りだした。電解液と
しては、実施例１、実施例２と同じ３０ｗｔ％の硫酸水
溶液を用いた。この後、安全弁を兼ねたフィルム状の栓
６と蓋４’をエポキシ樹脂を用いて封止した。封止した
容器４の蓋４’の外側からネジが切ってあるステンレス
製端子５を接続した。このようにして電気二重層コンデ
ンサを試作した。Reference Example An electric double layer capacitor was assembled in the same manner as the above two examples. After vacuuming the entire container to impregnate the polarizable electrode 1 with the electrolytic solution, the electrolytic solution is injected into the container 4,
Air leaked and was taken out from the electrolyte injection device. As the electrolytic solution, the same 30 wt% sulfuric acid aqueous solution as in Examples 1 and 2 was used. After that, the film-shaped stopper 6 also serving as a safety valve and the lid 4 ′ were sealed with an epoxy resin. From the outside of the lid 4 ′ of the sealed container 4, a screwed stainless steel terminal 5 was connected. In this way, an electric double layer capacitor was prototyped.
【００１０】実施例１、実施例２、参考例で作製した電
気二重層コンデンサを２４時間０．９Ｖ定電圧充電した
後のリーク電流およびＥＳＲを測定した。ＥＳＲの測定
は１０ｍＶの信号電圧で、１ｋＨｚの時のインピーダン
スの実数部とした。この後、１００ｍＡで定電流放電さ
せ、電気二重層コンデンサの両端の電圧が０．５４Ｖか
ら０．４５Ｖになるのに要した時間から静電容量を求め
た。測定結果を次の表１にまとめる。The electric double layer capacitors produced in Examples 1, 2 and Reference Example were measured for leak current and ESR after being charged with a constant voltage of 0.9 V for 24 hours. The ESR was measured with a signal voltage of 10 mV and the real part of the impedance at 1 kHz. After that, the capacitor was discharged at a constant current of 100 mA, and the electrostatic capacity was obtained from the time required for the voltage across the electric double layer capacitor to change from 0.54V to 0.45V. The measurement results are summarized in Table 1 below.
【００１１】[0011]
【表１】 [Table 1]
【００１２】表１から明かなように、実施れ１は参考例
に比べてリーク電流、ＥＳＲは小さく、静電容量が大き
いことがわかる。実施例１で作製した電気二重層コンデ
ンサのリーク電流が小さくなるのは、電解液に溶存して
いたか、または分極性電極に吸着していた酸素が充電に
より電気分解し外部に放出されたため、リーク電流担体
が減少したことによる。またＥＳＲが小さくなるのは、
分極性電極に吸着した酸素または分極性電極と反応して
生成したＣＯ2 ガスがセパレータ内に気泡として滞留す
ることが無くなったため、セパレータ部の電解液の抵抗
分が減少したことによる。同様に静電容量が大きくなっ
たのは酸素やＣＯ2 ガスが分極性電極内部に滞留するこ
とが無くなったため、電気二重層容量に寄与する表面積
が増大したことによるものと推測される。実施例２の効
果は充電より一度放出した溶存酸素が、電解液の真空含
浸後に空気リークすると再び酸素が電気二重層コンデン
サ内に導入されることを防ぐことによる。その機構は上
述した実施例１と同様であり、実施例２の効果は表１の
実施例１の結果と比較することにより明かである。As can be seen from Table 1, in Example 1, the leakage current and ESR are smaller and the capacitance is larger than in the reference example. The leak current of the electric double layer capacitor manufactured in Example 1 becomes small because the oxygen dissolved in the electrolytic solution or adsorbed to the polarizable electrode was electrolyzed by the charge and released to the outside. This is due to the decrease in current carriers. Also, the ESR becomes smaller because
This is because the oxygen adsorbed on the polarizable electrode or the CO 2 gas generated by the reaction with the polarizable electrode did not stay in the separator as bubbles, and the resistance of the electrolytic solution in the separator portion decreased. Similarly, it is speculated that the electrostatic capacitance increased because the surface area contributing to the electric double layer capacitance increased because oxygen and CO 2 gas did not stay inside the polarizable electrode. The effect of Example 2 is that the dissolved oxygen released once from charging is prevented from being introduced into the electric double layer capacitor again when air leaks after the vacuum impregnation of the electrolytic solution. The mechanism is the same as that of the above-mentioned Example 1, and the effect of Example 2 is clear by comparing with the result of Example 1 of Table 1.
【００１３】これらの結果から電解液をあらかじめ窒素
ガスなどでバブリングし溶存酸素を減少させてから、電
気二重層コンデンサに導入することも同様の効果がある
ことが容易に推測される。From these results, it is easily inferred that the same effect can be obtained by introducing the electrolytic solution into the electric double layer capacitor after bubbling the electrolytic solution with nitrogen gas or the like to reduce the dissolved oxygen.
【００１４】[0014]
【発明の効果】以上の説明のように、本発明によれば電
気二重層コンデンサを封止する前に充電を行うか、電気
二重層コンデンサに窒素を封入することにより、電気二
重層コンデンサのリーク電流を低下させるとともにＥＳ
Ｒを低減させ、静電容量を大きくすることができる。As described above, according to the present invention, the electric double layer capacitor is charged before the electric double layer capacitor is sealed, or nitrogen is filled in the electric double layer capacitor, thereby leaking the electric double layer capacitor. The current is reduced and ES
It is possible to reduce R and increase the capacitance.
【図１】本発明で作製した電気二重層コンデンサの例を
表した図である。FIG. 1 is a diagram showing an example of an electric double layer capacitor manufactured according to the present invention.
１ 分極性電極 ２ カーボン集電体 ３ セパレータ ４ 容器 ４’ 蓋 ５ 端子 ６ 安全弁 1 Polarizing electrode 2 Carbon current collector 3 Separator 4 Container 4'Lid 5 Terminal 6 Safety valve
Claims (2)
電気二重層コンデンサを充電することを特徴とする電気
二重層コンデンサの製造方法。1. A method for manufacturing an electric double layer capacitor, which comprises charging the electric double layer capacitor before sealing the electric double layer capacitor.
記載の電気二重層コンデンサの製造方法。2. An inert gas is sealed in the battery case.
A method for manufacturing the electric double layer capacitor described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14702292A JP3099518B2 (en) | 1992-06-08 | 1992-06-08 | Manufacturing method of electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14702292A JP3099518B2 (en) | 1992-06-08 | 1992-06-08 | Manufacturing method of electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05343263A true JPH05343263A (en) | 1993-12-24 |
| JP3099518B2 JP3099518B2 (en) | 2000-10-16 |
Family
ID=15420780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14702292A Expired - Fee Related JP3099518B2 (en) | 1992-06-08 | 1992-06-08 | Manufacturing method of electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3099518B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016354A1 (en) * | 1998-09-14 | 2000-03-23 | Asahi Glass Company Ltd. | Method for manufacturing large-capacity electric double-layer capacitor |
| JP2002246277A (en) * | 2001-02-20 | 2002-08-30 | Kyocera Corp | Electric double layer capacitor and its producing method |
| US7414825B2 (en) | 2005-06-27 | 2008-08-19 | Sanyo Electric Co., Ltd. | Electrochemical device |
| JP2013048213A (en) * | 2011-07-26 | 2013-03-07 | Sato Komusho:Kk | Electric double layer capacitor |
| WO2016122070A1 (en) * | 2015-01-29 | 2016-08-04 | 한국전기연구원 | Method for modifying carbon material electrode surface by current carrying, surface-modified carbon material electrode, and electrochemical capacitor comprising surface-modified carbon material electrode |
-
1992
- 1992-06-08 JP JP14702292A patent/JP3099518B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016354A1 (en) * | 1998-09-14 | 2000-03-23 | Asahi Glass Company Ltd. | Method for manufacturing large-capacity electric double-layer capacitor |
| US6379402B1 (en) * | 1998-09-14 | 2002-04-30 | Asahi Glass Company, Limited | Method for manufacturing large-capacity electric double-layer capacitor |
| JP2002246277A (en) * | 2001-02-20 | 2002-08-30 | Kyocera Corp | Electric double layer capacitor and its producing method |
| JP4623840B2 (en) * | 2001-02-20 | 2011-02-02 | 京セラ株式会社 | Manufacturing method of electric double layer capacitor |
| US7414825B2 (en) | 2005-06-27 | 2008-08-19 | Sanyo Electric Co., Ltd. | Electrochemical device |
| JP2013048213A (en) * | 2011-07-26 | 2013-03-07 | Sato Komusho:Kk | Electric double layer capacitor |
| WO2016122070A1 (en) * | 2015-01-29 | 2016-08-04 | 한국전기연구원 | Method for modifying carbon material electrode surface by current carrying, surface-modified carbon material electrode, and electrochemical capacitor comprising surface-modified carbon material electrode |
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