JP3085392B2 - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JP3085392B2 JP3085392B2 JP18721090A JP18721090A JP3085392B2 JP 3085392 B2 JP3085392 B2 JP 3085392B2 JP 18721090 A JP18721090 A JP 18721090A JP 18721090 A JP18721090 A JP 18721090A JP 3085392 B2 JP3085392 B2 JP 3085392B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- separator
- double layer
- layer capacitor
- electric double
- 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.)
- Expired - Fee Related
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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は電気二重層コンデンサに関するものである。The present invention relates to an electric double layer capacitor.
［従来の技術］ 電気二重層コンデンサに用いる電解液としては従来、
過塩素酸、６フッ化リン酸、４フッ化ホウ酸またはトリ
フルオロメタンスルホン酸などのアルカリ金属塩、アン
モニウム塩またはテトラアルキルアンモニウム塩など電
気化学的に安定な電解質を、プロピレンカーボネート、
γ−ブチロラクトン、アセトニトリル、ジメチルホルム
アミドなどの極性有機溶媒に溶解したものが知られてい
る（特開昭48−50255号、同49−68254号、同59−232409
号、特公昭52−40025号などの公報）。[Prior art] As an electrolytic solution used for an electric double layer capacitor,
Electrochemically stable electrolytes such as perchloric acid, hexafluorophosphoric acid, alkali metal salts such as tetrafluoroboric acid or trifluoromethanesulfonic acid, ammonium salts or tetraalkylammonium salts, propylene carbonate,
Those dissolved in polar organic solvents such as γ-butyrolactone, acetonitrile, dimethylformamide and the like are known (JP-A-48-50255, JP-A-49-68254, JP-A-59-232409).
No., Japanese Patent Publication No. 52-4025).
これらの電解液はポリオレフィン、ポリアクリロニト
リルなどの合成繊維又はガラス繊維からなる不織布やマ
ニラ麻、パルプからなる天然紙などの多孔性セパレータ
中に含浸されて用いられている。These electrolytes are used by being impregnated in a porous separator such as a nonwoven fabric made of synthetic fibers such as polyolefin and polyacrylonitrile or glass fiber, and a natural paper made of manila hemp and pulp.
［発明が解決しようとする課題］ このような電解液を用いた従来の電気二重層コンデン
サにおいては、一般にユニットセルの耐電圧は2.8V前後
であり、主な用途であるメモリバックアップ電源として
用いる際には5.5Vの耐電圧が必要とされるので２セルを
直列に積層した状態で製品化されていた。しかし、5.5V
の電圧を長期間印加し続けると電解液の耐電圧に余裕が
ないため、２セル間の分配電圧に不均衡が生ずる場合が
あり、高電圧が印加されたセル中で電解液の溶媒の分解
が起こるためコンデンサの容量が低下したり、ガスの発
生によってセルケースが膨張するために内部抵抗が増大
したり、さらには電解液がセルから漏れたりすることが
あり、特に高温下での使用に際し、このような劣化現象
が顕著にあらわれるという問題点があった。[Problems to be Solved by the Invention] In a conventional electric double layer capacitor using such an electrolytic solution, the withstand voltage of a unit cell is generally about 2.8 V, and it is often used as a memory backup power supply, which is a main application. Requires a withstand voltage of 5.5 V, and thus has been commercialized in a state where two cells are stacked in series. But 5.5V
If the voltage is continuously applied for a long period of time, the withstand voltage of the electrolyte does not have a margin, so that the distribution voltage between the two cells may become unbalanced, and the decomposition of the solvent of the electrolyte in the cell to which the high voltage is applied This may cause a decrease in the capacity of the capacitor, an expansion of the cell case due to the generation of gas, and an increase in internal resistance.Also, electrolyte may leak from the cell, especially when used at high temperatures. However, there is a problem that such a deterioration phenomenon appears remarkably.
また、従来の電気二重層コンデンサは、リチウム電池
やニッケル／カドミニウム電池に比べて自己放電が大き
いため、負荷電流を流さない開路状態にて長期間放置す
るだけでもコンデンサ残存電圧がかなり低下してしまう
ので、長期間微少電流で放電するようなバックアップ用
途には不適当であった。この主原因は、電極中の電荷を
帯びた活性炭微粒子が電極から脱離し、電気泳動によっ
てセパレータ中を貫通して対極に接触し、電荷を失うた
めと考えられている。In addition, the conventional electric double layer capacitor has a large self-discharge as compared with a lithium battery or a nickel / cadmium battery, so that even if the capacitor is left for a long time in an open state where no load current flows, the capacitor residual voltage is considerably reduced. Therefore, it is unsuitable for backup use in which discharge is carried out with a very small current for a long time. It is considered that the main cause is that the charged activated carbon fine particles in the electrode are detached from the electrode, penetrate through the separator by electrophoresis and come into contact with the counter electrode, and lose the charge.
［課題を解決する為の手段］ 本発明はこのような従来技術の問題点を解決して、耐
電圧が高く、電圧印加による性能劣化が少なくかつ自己
放電が少ない電気二重層コンデンサを提供することを目
的として種々研究、検討した結果なされたものであり、
イオン透過性のセパレータの両側に一対の分極性電極を
対面させ、該分極性電極と電解液の界面に形成される電
気二重層に電荷を蓄積することを利用する電気二重層コ
ンデンサにおいて、セパレータは、平均細孔径が0.02μ
ｍ以下の微孔性ポリオレフィン膜であり、電解液は、常
温で液体のポリエーテルを溶媒として電解質を溶解した
ものであり、該電解液がセパレータの微細孔中に含浸さ
れていることを特徴とする電気二重層コンデンサを提供
するものである。[Means for Solving the Problems] The present invention solves such problems of the prior art, and provides an electric double layer capacitor having high withstand voltage, little performance degradation due to voltage application, and little self-discharge. It was made as a result of various studies and examinations for the purpose of
In an electric double layer capacitor utilizing a pair of polarizable electrodes facing each other on both sides of an ion-permeable separator and accumulating electric charge in an electric double layer formed at an interface between the polarizable electrode and the electrolytic solution, the separator is , The average pore size is 0.02μ
m or less microporous polyolefin membrane, the electrolytic solution is a solution obtained by dissolving the electrolyte using polyether as a solvent at room temperature, characterized in that the electrolytic solution is impregnated in the micropores of the separator. To provide an electric double-layer capacitor.
本発明においては、電解液の溶質として、アルカリ金
属、アルカリ土類金属、第４級アンモニウム、第４級ホ
スホニウムの過塩素酸塩、４フッ化ホウ酸塩、トリフル
オロメタンスルホン酸塩、６フッ化リン酸塩などを用い
ることができるが、電気伝導度、耐電圧の面からアルカ
リ金属塩類、特にリチウム塩類が好適に用いられる。In the present invention, as a solute of the electrolytic solution, alkali metal, alkaline earth metal, quaternary ammonium, quaternary phosphonium perchlorate, tetrafluoroborate, trifluoromethanesulfonate, hexafluoride Phosphates and the like can be used, but alkali metal salts, particularly lithium salts, are preferably used in view of electric conductivity and withstand voltage.
電解液の溶媒としては、低分子量のポリエーテル化合
物、例えばポリエチレンオキサイド、ポリプロピレンオ
キサイドあるいはポリエチレンオキサイド−ポリプロピ
レンオキサイド共重合体であり、平均分子量が100〜50
0、好ましくは200〜400のものが好適である。As a solvent for the electrolytic solution, a low molecular weight polyether compound, for example, polyethylene oxide, polypropylene oxide or polyethylene oxide-polypropylene oxide copolymer, the average molecular weight is 100 to 50
A value of 0, preferably 200 to 400 is suitable.
本発明において用いられるセパレータは延伸処理など
によって多孔性を付与した微孔性のポリオレフィン膜で
あり、電解液の保持・固定化の面から平均細孔径が0.02
μｍ以下である。また、セパレータは、電気伝導度の面
から空隙率は50％以上、特に80％以上であることが好ま
しく、厚さは20μｍ以下、特に10μｍ以下であることが
好ましい。The separator used in the present invention is a microporous polyolefin membrane provided with porosity by stretching or the like, and has an average pore diameter of 0.02 from the viewpoint of holding and fixing the electrolyte.
μm or less. The porosity of the separator is preferably 50% or more, particularly preferably 80% or more, and the thickness is preferably 20 μm or less, particularly preferably 10 μm or less from the viewpoint of electric conductivity.
電解液はセパレータ中の微細孔内に含浸することによ
って固定化されるが、電解液中にセパレータを浸漬し、
密閉圧力容器中で加熱、加圧処理することにより、含浸
処理時間を短縮できる。The electrolyte is fixed by impregnating the pores in the separator, but the separator is immersed in the electrolyte,
By heating and pressurizing in a closed pressure vessel, the impregnation time can be reduced.
［作用］ 本発明においては、電気化学的酸化あるいは還元に対
して安定なポリエーテル系の電解液を用いることによ
り、コンデンサの耐電圧が高く、電圧印加による性能劣
化を低減すると同時に、従来用いられていたセパレータ
厚さの1/10以下である10μｍ程度の極薄膜中の細孔内に
電解液を封じ込めることにより、セパレータ間の電気抵
抗は従来品とほぼ同等であって、かつ電極から離脱した
帯電カーボン粒子の電気泳動が上記微孔性セパレータに
よって阻止されるため、コンデンサの自己放電を大幅に
低減させることができるものである。[Function] In the present invention, by using a polyether-based electrolyte solution that is stable against electrochemical oxidation or reduction, the withstand voltage of the capacitor is high, the performance deterioration due to voltage application is reduced, and at the same time the conventional capacitor is used. By sealing the electrolyte in the pores of the ultra-thin film of about 10 μm, which is 1/10 or less of the separator thickness, the electrical resistance between the separators was almost the same as the conventional product, and the separator was separated from the electrode Since the electrophoresis of the charged carbon particles is blocked by the microporous separator, self-discharge of the capacitor can be significantly reduced.
［実施例］ 次に、実施例および比較例を図面に基づいて具体的に
説明する。Example Next, an example and a comparative example will be specifically described with reference to the drawings.
本発明の実施例および比較例に共通のものとして第１
図に示すようなコイン型電気二重層コンデンサのユニッ
トセル（直径18.4mm、厚み2.0mm）を次のようにして作
製した。先ず、活性炭粉末（比表面積2000m2/g）に10重
量％のポリテトラフルオロエチレンを添加して湿式混練
した後シート化した。このようにして得られたシートを
円板状に打ち抜いて分極性電極１および２（直径12mm、
厚み0.7mm）とし、この分極性電極１、２をステンレス
鋼製のキャップ４およびステンレス鋼製の缶５からなる
外装容器中に導電性密着剤にて固定した後、真空加熱乾
燥により電極中の水分を除去した。The first embodiment is common to Examples and Comparative Examples of the present invention.
A unit cell (diameter 18.4 mm, thickness 2.0 mm) of a coin-type electric double layer capacitor as shown in the figure was produced as follows. First, 10% by weight of polytetrafluoroethylene was added to activated carbon powder (specific surface area: 2000 m 2 / g), wet-kneaded, and formed into a sheet. The sheet thus obtained was punched into a disc shape and the polarizable electrodes 1 and 2 (diameter 12 mm,
The polarizable electrodes 1 and 2 are fixed in an outer container made of a stainless steel cap 4 and a stainless steel can 5 with a conductive adhesive, and then dried under vacuum to dry the electrodes. Water was removed.
次に、ユニットセル中に所定の電解液を注入して分極
性電極１、２に電解液を十分に含浸させた後、同じ電解
液を含浸させた所定のセパレータ３を分極性電極１、２
の間に配置し、ポリプロピレン製パッキング６を介して
キャップ４および缶５の端部をかしめて封口し一体化し
た。Next, after a predetermined electrolytic solution is injected into the unit cell to sufficiently impregnate the polarizable electrodes 1 and 2 with the electrolytic solution, a predetermined separator 3 impregnated with the same electrolytic solution is placed in the polarizable electrodes 1 and 2.
The ends of the cap 4 and the can 5 were caulked via a polypropylene packing 6 to seal and integrate.
前述のようにして作製した電気二重層コンデンサのユ
ニットセルを使用し、第１表に示すような種々の電解液
を電極中に含浸させ、かつ第１表に示すような種々のセ
パレータを用いた各セルについて、2.8Vの電圧を印加し
たときの初期容量および内部抵抗を測定した後、引き続
いてこのセルに2.8Vの電圧を印加しながら70℃で1000時
間貯蔵した後の容量および内部抵抗を測定し、初期容量
からの容量劣化率（％）を算出した。これらの測定結果
を第１表に示す。Using the unit cell of the electric double layer capacitor produced as described above, various electrolytes as shown in Table 1 were impregnated in the electrodes, and various separators as shown in Table 1 were used. For each cell, after measuring the initial capacity and internal resistance when a voltage of 2.8 V was applied, the capacity and internal resistance after storage at 70 ° C. for 1000 hours while applying a voltage of 2.8 V to this cell were then measured. It measured and calculated the capacity deterioration rate (%) from the initial capacity. Table 1 shows the measurement results.
また、自己放電特性を評価するために、上記コインセ
ルを2.8V定電圧で１時間充電した後、開路状態で室温で
保存し、残存電圧の経時変化を調べた。10時間後の残存
電圧を第１表に示した。In addition, in order to evaluate the self-discharge characteristics, the coin cell was charged at a constant voltage of 2.8 V for 1 hour, then stored in an open circuit state at room temperature, and the change with time of the residual voltage was examined. The residual voltage after 10 hours is shown in Table 1.
［効果］ 以上説明したように、本発明の電気二重層コンデンサ
は、電圧印加による容量劣化が少なくまた内部抵抗の変
化も少なく信頼性に優れ、かつ自己放電が極めて小さく
バックアップ電源として優れた特性を有していることが
わかる。 [Effects] As described above, the electric double layer capacitor of the present invention has excellent characteristics as a backup power supply, with little capacity deterioration due to voltage application, little change in internal resistance, excellent reliability, and extremely small self-discharge. It turns out that it has.
第１図は本発明による電気二重層コンデンサの一実施態
様を示す部分断面図である。 １、２……分極性電極、 ３……セパレータ、 ４……キャップ、 ５……缶、 ６……パッキング。FIG. 1 is a partial sectional view showing an embodiment of the electric double layer capacitor according to the present invention. 1, 2 ... Polarizable electrode, 3 ... Separator, 4 ... Cap, 5 ... Can, 6 ... Packing.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−186752（ＪＰ，Ａ) 特開 昭59−24732（ＪＰ，Ａ) 特開 平２−39513（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/02 H01G 9/038 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-186752 (JP, A) JP-A-59-24732 (JP, A) JP-A-2-39513 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01G 9/02 H01G 9/038
Claims (3)
分極性電極を対面させ、該分極性電極と電解液の界面に
形成される電気二重層に電荷を蓄積することを利用する
電気二重層コンデンサにおいて、セパレータは、平均細
孔径が0.02μｍ以下の微孔性ポリオレフィン膜であり、
電解液は、常温で液体のポリエーテルを溶媒として電解
質を溶解したものであり、該電解液がセパレータの微細
孔中に含浸されていることを特徴とする電気二重層コン
デンサ。1. An electric double layer utilizing a pair of polarizable electrodes facing both sides of an ion-permeable separator and accumulating electric charge in an electric double layer formed at an interface between the polarizable electrode and an electrolytic solution. In the capacitor, the separator is a microporous polyolefin membrane having an average pore diameter of 0.02 μm or less,
An electric double layer capacitor characterized in that the electrolytic solution is obtained by dissolving an electrolyte using polyether which is liquid at ordinary temperature as a solvent, and the electrolytic solution is impregnated in micropores of a separator.
厚さが20μｍ以下である請求項１に記載の電気二重層コ
ンデンサ。2. The electric double layer capacitor according to claim 1, wherein the separator has a porosity of 50% or more and a thickness of 20 μm or less.
る請求項１又は２に記載の電気二重層コンデンサ。3. The electric double layer capacitor according to claim 1, wherein the polyether has an average molecular weight of 100 to 500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18721090A JP3085392B2 (en) | 1990-07-17 | 1990-07-17 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18721090A JP3085392B2 (en) | 1990-07-17 | 1990-07-17 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0474405A JPH0474405A (en) | 1992-03-09 |
| JP3085392B2 true JP3085392B2 (en) | 2000-09-04 |
Family
ID=16202013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18721090A Expired - Fee Related JP3085392B2 (en) | 1990-07-17 | 1990-07-17 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3085392B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383427B2 (en) | 1997-12-24 | 2002-05-07 | Asahi Glass Company, Ltd. | Process for producing an electric double layer capacitor electrode |
| JP3844171B2 (en) * | 1998-05-22 | 2006-11-08 | 日立マクセル株式会社 | Electric double layer capacitor |
| US6631074B2 (en) | 2000-05-12 | 2003-10-07 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US6813139B2 (en) | 2001-11-02 | 2004-11-02 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
-
1990
- 1990-07-17 JP JP18721090A patent/JP3085392B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0474405A (en) | 1992-03-09 |
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