JP2001118546A - Electrochemical cell - Google Patents
Electrochemical cellInfo
- Publication number
- JP2001118546A JP2001118546A JP2000291062A JP2000291062A JP2001118546A JP 2001118546 A JP2001118546 A JP 2001118546A JP 2000291062 A JP2000291062 A JP 2000291062A JP 2000291062 A JP2000291062 A JP 2000291062A JP 2001118546 A JP2001118546 A JP 2001118546A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode case
- stainless steel
- case
- electrochemical cell
- 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.)
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Classifications
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、小型で大容量の電気化
学セルに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a small and large-capacity electrochemical cell.
【０００２】[0002]
【従来の技術】従来、湿式の電気化学セルの正極ケース
材料には、例えば特開昭６２−９４９０８号公報では、
前記ケース内面にアルミニウム層を設けたオーステナイ
ト・フェライト系ステンレス鋼（ＳＵＳ３２９Ｊ１）が
使用されている（以下Ａｌ−ＳＵＳクラッド材と略
記）。2. Description of the Related Art Conventionally, as a positive electrode case material for a wet electrochemical cell, for example, Japanese Patent Application Laid-Open No. Sho 62-94908 discloses:
Austenitic ferritic stainless steel (SUS329J1) having an aluminum layer on the inner surface of the case is used (hereinafter abbreviated as Al-SUS clad material).
【０００３】図５には、従来の電気化学セルとして電気
二重層キャパシタの一構成例を示す。図中、分極性電極
２、２’として、各々の片面にアルミニウムのプラズマ
溶射法による集電体層を形成した活性炭繊維布を用い、
さらに前記活性炭繊維を例えばレーザー溶接法などで正
極ケース１及び負極ケース６に溶接していた。前記電極
２、２’をセパレータ７を介して対向させ、有機電解液
を注入後、正極ケースの上部を内方にかしめて組立てい
た。また、電解液には、非プロトン性のγ−ブチルラク
トン、エチレンカーボネイト、プロピレンカーボネイト
等にテトラアルキルアンモニウム塩やテトラアルキルホ
スホニウム塩などを溶解した溶液を使用している。FIG. 5 shows a configuration example of an electric double layer capacitor as a conventional electrochemical cell. In the figure, as the polarizable electrodes 2 and 2 ′, an activated carbon fiber cloth having a current collector layer formed on one side of each by a plasma spraying method of aluminum was used.
Further, the activated carbon fiber is welded to the positive electrode case 1 and the negative electrode case 6 by, for example, a laser welding method. The electrodes 2, 2 'were opposed to each other with the separator 7 interposed therebetween, and after pouring the organic electrolyte, the upper part of the positive electrode case was crimped inward to assemble. Further, as the electrolytic solution, a solution in which a tetraalkylammonium salt, a tetraalkylphosphonium salt, or the like is dissolved in aprotic γ-butyl lactone, ethylene carbonate, propylene carbonate, or the like is used.
【０００４】[0004]
【発明が解決しようとする課題】上述した従来の電気化
学セルは、通常２〜２．８Ｖで使用されるが、正極ケー
スがステンレス鋼単体の時、前記ケース内面の陽極酸化
が起こり、金属が溶出し、そのためセルのインピーダン
スの上昇や静電容量の減少が観られるので、前記の金属
イオンの溶出を抑制するために、正極ケースの内面にア
ルミニウム層を設けているのである。The above-mentioned conventional electrochemical cell is usually used at a voltage of 2 to 2.8 V. However, when the positive electrode case is made of stainless steel alone, anodization of the inner surface of the case occurs and the metal becomes Since elution occurs, and therefore, an increase in cell impedance and a decrease in capacitance are observed, an aluminum layer is provided on the inner surface of the positive electrode case to suppress the elution of the metal ions.
【０００５】つまり、以上の理由により、ＪＩＳ規格品
ＳＵＳ３２９Ｊ１、ＳＵＳ４４７Ｊ１を単体として正極
ケースに使うことができないために、ステンレス鋼とア
ルミニウムの異種金属同士をラミネイトして正極ケース
としているが、アルミニウムを均一な層にすることが難
しく、またいくつかのラミネイト工程を必要とするの
で、ステンレス鋼単体の数倍のコスト高となっている。In other words, for the above reasons, it is not possible to use JIS standard products SUS329J1 and SUS447J1 as a single unit in the positive electrode case. Therefore, different types of metals such as stainless steel and aluminum are laminated to form the positive electrode case. Because it is difficult to form layers and requires several laminating steps, the cost is several times higher than that of stainless steel alone.
【０００６】さらには、正極を抜き絞り加工時に、正極
ケースの上の周縁部にアルミニウム層がかぶさってしま
う場合があり、前述したセル組立時、つまり正極ケース
１と負極ケース６を合体させ、正極ケースを内方にかし
めてセルを封口する際に正極ケースの内面のアルミニウ
ムが剥離し、その小片が負極ケース６と接触してショー
ト原因となっている。なお、正極ケースのアルミニウム
層がステンレス鋼側にかぶさらない場合にも、正極ケー
スと負極ケースの封口条件の若干のズレにより、前述し
たアルミニウムの小片によるショートが発生する。Further, when the positive electrode is pulled out and drawn, an aluminum layer may be covered on the periphery of the positive electrode case. At the time of the above-described cell assembly, that is, the positive electrode case 1 and the negative electrode case 6 are combined, When the case is crimped inward to seal the cell, aluminum on the inner surface of the positive electrode case peels off, and small pieces thereof come into contact with the negative electrode case 6 to cause a short circuit. In addition, even when the aluminum layer of the positive electrode case does not cover the stainless steel side, short-circuiting due to the small pieces of aluminum described above occurs due to a slight deviation in sealing conditions between the positive electrode case and the negative electrode case.
【０００７】本発明は、以上のように有機電解液を用い
る電気化学セルを２〜２．８Ｖの電圧で使用する時に、
正極ケースの内部にアルミニウム層を設けることなく陽
極酸化を抑制し、正極ケースの製造コストを低減し、さ
らにはセルの生産性向上を目的とする。According to the present invention, when an electrochemical cell using an organic electrolyte is used at a voltage of 2 to 2.8 V as described above,
An object of the present invention is to suppress anodic oxidation without providing an aluminum layer inside the positive electrode case, reduce the manufacturing cost of the positive electrode case, and further improve cell productivity.
【０００８】[0008]
【課題を解決するための手段】本発明は、正極ケースと
してＮｉオーステナイトステンレス鋼又は高耐食オース
テナイト・フェライト二相ステンレス鋼の鋼種の一部を
使用することで、上記の問題点を解決することを目的と
する。The present invention solves the above problems by using a part of Ni austenitic stainless steel or a high corrosion resistant austenitic / ferritic duplex stainless steel as a positive electrode case. Aim.
【０００９】[0009]
【作用】本発明は、上記手段により最高使用電圧２．８
Ｖを有し、生産ラインで組立が容易で安易な電気化学セ
ルを得ることができる。According to the present invention, the maximum working voltage is 2.8 by the above means.
It is possible to obtain an electrochemical cell having V and easy to assemble in a production line and easy.
【００１０】本発明で使用する高Ｎｉオーステナイトス
テンレス鋼は高Ｃｒ高Ｍｏオーステナイトステンレス鋼
で、一例としてＪＩＳ規格品ＳＵＳ３１７Ｊ４Ｌは苛酷
な環境下でも優れた耐食性を示す。表１に高クロム高モ
リブデンオーステナイトステンレス鋼ＳＵＳ３１７Ｊ４
Ｌの化学的成分表を示す。The high Ni austenitic stainless steel used in the present invention is a high Cr high Mo austenitic stainless steel. For example, JIS standard SUS317J4L exhibits excellent corrosion resistance even in a severe environment. Table 1 shows the high chromium and high molybdenum austenitic stainless steel SUS317J4.
2 shows a chemical composition table of L.
【００１１】[0011]
【表１】 [Table 1]
【００１２】また、２５Ｃｒ−６Ｎｉ−３．５Ｍｏで代
表されるオーステナイト・フェライト系の二相組織を有
するステンレス鋼の鋼種の一部であるＳＵＳ３２９Ｊ４
Ｌもまた前者のＳＵＳ３１７Ｊ４Ｌよりも若干劣るが、
同様に優れた耐食性を示す。この二相ステンレス鋼ＳＵ
Ｓ３２９Ｊ４Ｌの化学成分を表２に示す。SUS329J4 which is a part of stainless steel having an austenitic / ferritic dual phase structure represented by 25Cr-6Ni-3.5Mo.
L is also slightly inferior to the former SUS317J4L,
It also shows excellent corrosion resistance. This duplex stainless steel SU
Table 2 shows the chemical components of S329J4L.
【００１３】[0013]
【表２】 [Table 2]
【００１４】以上の二種類の材料で作製した各々の正極
ケースを用いた電気化学セルにおいて、その内面が有機
電解液や正極と直接触れても、高耐食性のため有機電解
液への溶解が抑制される。In an electrochemical cell using each of the positive electrode cases made of the above two types of materials, even if the inner surface is in direct contact with the organic electrolyte or the positive electrode, dissolution in the organic electrolyte is suppressed due to high corrosion resistance. Is done.
【００１５】[0015]
【実施例】以下に、本発明の実施例を図面を参照しなが
ら説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１６】（実施例１）まず、水溶液中での種々ステ
ンレス鋼の腐食テストを行った。塩化物を含む水溶液中
での、各種温度における孔食電位の測定したものを図２
に示した。図２中、ａおよびｂが本発明に用いるＳＵＳ
３１７Ｊ４ＬとＳＵＳ３２９Ｊ４Ｌであり、ｃがＳＵＳ
３２９Ｊ１がそれぞれの特性である。ａは温度を上げて
も孔食電位が変化せず、ｂは温度の上昇とともに電位は
下がってくるが、ａ、ｂともに耐孔食性に優れている。
ｃは温度の上昇とともに急激に電位が下がりはじめ、耐
孔食性に劣る。(Example 1) First, corrosion tests of various stainless steels in an aqueous solution were performed. Figure 2 shows the measured pitting potential at various temperatures in an aqueous solution containing chloride.
It was shown to. In FIG. 2, a and b are SUS used in the present invention.
317J4L and SUS329J4L, where c is SUS
329J1 is each characteristic. In the case of a, the pitting potential does not change even when the temperature is increased, and in the case of b, the potential decreases as the temperature rises. However, both a and b have excellent pitting resistance.
In the case of c, the potential starts to drop sharply as the temperature rises, and is inferior in pitting resistance.
【００１７】（実施例２）次に、有機電解液中で種々の
ステンレス鋼のアノード側及びカソード側のＣｉ／Ｃｉ
+ 参照電極に対する電圧／電流特性を測定した。なお、
電解液は四フッ化ホウ酸テトラエチルアンモニウム
（（Ｃ2 Ｈ5 ）4 ＮＢＦ4 ）をプロピレンカーボネイト
に溶解したものを用いた。(Example 2) Next, Ci / Ci on the anode side and the cathode side of various stainless steels in an organic electrolytic solution.
+ Voltage / current characteristics with respect to the reference electrode were measured. In addition,
The electrolyte used was a solution of tetraethylammonium tetrafluoroborate ((C 2 H 5 ) 4 NBF 4 ) dissolved in propylene carbonate.
【００１８】図３中、本発明ＡがＳＵＳ３１７Ｊ４Ｌ、
ＢがＳＵＳ３２９Ｊ４Ｌがステンレス鋼単体、従来の比
較例として、ＣがＳＵＳ３２９Ｊ１にアルミニウムをラ
ミネートしたもの、ＤがＳＵＳ３２９Ｊ１のステンレス
鋼単体の電圧／電流特性である。金属の溶解反応は、ア
ノード側であり（セルとしてはカソード側）電圧をスイ
ープさせると、本発明のＡは１．６Ｖ、Ｂは１．７Ｖ、
従来Ｃは＋２．６Ｖ、Ｄは＋１．２Ｖ近辺より、溶解反
応が大きくなる。前述の各々の電圧は、電流密度１μＡ
／ｃｍ2 の時の電圧とした。In FIG. 3, the present invention A is SUS317J4L,
B is SUS329J4L for stainless steel alone, as a comparative example, C is SUS329J1 laminated with aluminum, and D is SUS329J1 stainless steel alone for voltage / current characteristics. The metal dissolution reaction is on the anode side (cathode side as a cell). When the voltage is swept, A of the present invention is 1.6 V, B is 1.7 V,
In the conventional C, the dissolution reaction becomes larger than at +2.6 V and at D around +1.2 V. Each of the aforementioned voltages has a current density of 1 μA
/ Cm 2 .
【００１９】尚、図３はスイープ繰り返し、１２回目の
プロフィールである。セルの最高使用電圧２．８Ｖの場
合、セルのカソード側（図３中ではアノード側）にかか
る最大電圧は＋１．２Ｖを実測としていることから（ち
なみにアトード側は１．６Ｖ）Ａ，Ｂいづれもセルカソ
ード側電圧より大きいので、正極ケース内の溶解反応が
起こらない。また、Ｄは＋１．２Ｖより溶解反応が開始
することから、セルのカソード側にかかる電圧１．２Ｖ
と同じなため、ステンレス鋼単体での使用には問題があ
る。Ｃについては、電圧スイープにより、アルミニウム
表面に酸化膜を形成することから、溶解反応開始電圧が
高くなっている。FIG. 3 shows the profile of the twelfth sweep. In the case where the maximum operating voltage of the cell is 2.8 V, the maximum voltage applied to the cathode side (the anode side in FIG. 3) of the cell is actually measured at +1.2 V (note that 1.6 V is used for the atodo side). Is higher than the cell cathode side voltage, so that no dissolution reaction occurs in the positive electrode case. Further, since the dissolution reaction starts from +1.2 V at D, the voltage applied to the cathode side of the cell is 1.2 V.
Therefore, there is a problem in using stainless steel alone. As for C, since the oxide film is formed on the aluminum surface by the voltage sweep, the dissolution reaction start voltage is high.
【００２０】一般的にステンレス鋼の耐食性は、Ｃｒ，
Ｍｏの量に大きく作用され、他にＮｉ，Ｃｕ，Ｎも耐食
性を上げる成分といわれている。耐食性の指標として、
ピッティングインデックス（ＰＩ）があり、ＰＩ＝Ｃｒ
％＋３×Ｍｏ％＋１６＋Ｎ％で表３に表わされ、高い
程、耐食性に優れている。Generally, the corrosion resistance of stainless steel is Cr,
It is greatly affected by the amount of Mo, and Ni, Cu, and N are also said to be components that increase corrosion resistance. As an index of corrosion resistance,
There is a pitting index (PI), PI = Cr
% + 3 × Mo% + 16 + N% are shown in Table 3. The higher the value, the better the corrosion resistance.
【００２１】[0021]
【表３】 [Table 3]
【００２２】しかし、ＰＩ値４５〜５０以上になると材
料の加工性や機械的特性が悪くなり正極ケースとしての
仕様を十分満足できない。However, when the PI value is 45 to 50 or more, the workability and mechanical properties of the material are deteriorated, and the specifications as the positive electrode case cannot be sufficiently satisfied.
【００２３】また、ＰＩ値と類似した耐食性の評価は、
J.Kolts, J. B. C. Wu. P. E. Manning, and A. I. Asp
hahani, "Highly Alloyed Austenitic Material for Co
rrosion Resistance", Corrosion Reviews, 6(4), P279
〜326(1986).に記載されている。The evaluation of the corrosion resistance similar to the PI value is as follows.
J.Kolts, JBC Wu.PE Manning, and AI Asp
hahani, "Highly Alloyed Austenitic Material for Co
rrosion Resistance ", Corrosion Reviews, 6 (4), P279
326 (1986).
【００２４】図４は、この文献から抜粋された図で、Ｆ
ｅ−Ｎｉ−Ｃｒ−Ｍｏ合金の組成とピッティングの臨界
温度の関係を示している。Ｆｅ−Ｎｉ−Ｃｒ−Ｍｏ合金
の腐食は４％ＮａＣｌ＋１％Ｆｅ2 （ＳＯ4 ）3 ＋０．
０１ＭＨＣｌ液中で調べられた。FIG. 4 is a diagram extracted from this document.
The relationship between the composition of the e-Ni-Cr-Mo alloy and the critical temperature of pitting is shown. The corrosion of the Fe—Ni—Cr—Mo alloy is 4% NaCl + 1% Fe 2 (SO 4 ) 3 +0.
Investigated in 01M HCl solution.
【００２５】この図４からＣｒ％＋２．４Ｍｏ％の合計
値が高いほど孔食温度が高くなっている。このグラフか
ら本発明のＳＵＳ３１７Ｊ４ＬとＳＵＳ３２９Ｊ４Ｌの
それぞれのＣｒ％とＭｏ％で Picting Temperatune (孔
食温度) を試算してみると、５５〜７０℃となり、腐食
はかなり高温側にあることが推定される。From FIG. 4, the higher the total value of Cr% + 2.4Mo%, the higher the pitting temperature. From this graph, when Picting Temperatune (pitting temperature) is calculated for Cr% and Mo% of SUS317J4L and SUS329J4L of the present invention, respectively, it is 55 to 70 ° C., and it is presumed that the corrosion is considerably higher. .
【００２６】（実施例３）高Ｎｉオーステナイトステン
レス鋼板（厚さ０．２ｍｍ）のＳＵＳ３１７Ｊ４Ｌおよ
び高耐食オーステナイト・フェライト系二相ステンレス
鋼板（厚さ０．２ｍｍ）のＳＵＳ３２９Ｊ４Ｌを抜き絞
り加工して、正極ケースを作製した。また比較例とし
て、図６に示すように、Ａｌ−ＳＵＳ３２９Ｊ１でアル
ミニウム層４０μｍ、ＳＵＳ３２９Ｊ１層０．１６ｍｍ
及びＳＵＳ３２９Ｊ１ステンレス鋼単体０．２ｍｍの正
極ケースを作製した。上記の正極ケースを用いて図１に
示す電気化学セル（電気二重層キャパシタ）を組立て
た。さらに、詳述すると分極性電極１２、１２’の活性
炭繊維布（比表面積２０００ｍ2 ／ｇ）をディスク状に
打ち抜いておき、次に前述した正極ケース１１と負極ケ
ース１６の各々の内底部に導電ペースト１３、１３’を
塗布した後、前記のディスク状活性炭繊維布を挿入し、
圧着後１００℃で２時間乾燥した。このようにして得た
正極に２００℃で３０分乾燥したガラス繊維口紙からな
るディスク状セパレータ１４を載置し、有機電解液とし
て１モルのテトラエチルリン酸のホウフッ化塩を溶解し
たプロピレンカーボネイトの所定量を注入し、負極ケー
スにはポリピロレン製のガスケット１５を押し込んだ
後、正極ケースと負極ケースを合体させ、セルを組立て
た。(Example 3) SUS317J4L of a high Ni austenitic stainless steel plate (thickness: 0.2 mm) and SUS329J4L of a high corrosion resistant austenitic ferritic duplex stainless steel plate (thickness: 0.2 mm) were drawn and drawn. A case was made. As a comparative example, as shown in FIG. 6, Al-SUS329J1 has an aluminum layer of 40 μm and a SUS329J1 layer of 0.16 mm.
And a positive electrode case of SUS329J1 stainless steel single piece of 0.2 mm. The electrochemical cell (electric double layer capacitor) shown in FIG. 1 was assembled using the above positive electrode case. More specifically, the activated carbon fiber cloth (specific surface area: 2000 m 2 / g) of the polarizable electrodes 12 and 12 ′ is punched in a disk shape. After applying the pastes 13 and 13 ', the disk-shaped activated carbon fiber cloth is inserted,
It dried at 100 degreeC after compression bonding for 2 hours. A disk-shaped separator 14 made of glass fiber paper dried at 200 ° C. for 30 minutes was placed on the positive electrode thus obtained, and propylene carbonate in which 1 mol of borofluoride of tetraethylphosphoric acid was dissolved as an organic electrolyte was prepared. After injecting a predetermined amount, a gasket 15 made of polypyrrolene was pushed into the negative electrode case, and then the positive electrode case and the negative electrode case were combined to assemble the cell.
【００２７】上記のセルについて、７０℃の雰囲気中で
２．８Ｖを印加し、５００時間後の容量減少率と交流内
部抵抗（１ｋＨｚで測定）の上昇率を測定した結果と、
上記セルの正極ケース及び負極ケースを合体させて、正
極ケースを内方にかしめて封口する際に発生する前記ケ
ースの周縁部のステンレス鋼又はアルミニウムのバリ発
生率を次表に示す。ＡがＳＵＳ３１７Ｊ４Ｌ、ＢがＳＵ
Ｓ３２９Ｊ４Ｌ、ＣがＡｌ／ＳＵＳ３２９ＪＩ、ＤがＳ
ＵＳ３２９ＪＩを正極ケースとして使用した電気化学セ
ルを示す。With respect to the above-mentioned cell, 2.8 V was applied in an atmosphere of 70 ° C., and after 500 hours, the capacity reduction rate and the rise rate of the AC internal resistance (measured at 1 kHz) were measured.
The following table shows the rate of occurrence of burrs of stainless steel or aluminum at the peripheral portion of the case, which is generated when the positive electrode case and the negative electrode case of the above cell are combined, and the positive electrode case is caulked inward and sealed. A is SUS317J4L, B is SU
S329J4L, C is Al / SUS329JI, D is S
1 shows an electrochemical cell using US329JI as a positive electrode case.
【００２８】[0028]
【表４】 [Table 4]
【００２９】表４の結果をみると、本発明は正極ケース
にアルミニウム層がなくとも、アルミニウム層があるＣ
と比較すると同等以上の結果が得られている。また従来
のアルミニウム層がない正極ケースでは変化率が顕著と
なり、信頼性に乏しくなる。As can be seen from the results shown in Table 4, the present invention shows that even if the positive electrode case does not have an aluminum layer,
As compared with, the same or better results were obtained. In the case of the conventional positive electrode without an aluminum layer, the rate of change becomes remarkable, and the reliability is poor.
【００３０】また、セル封口時のバリは本発明のＡ，Ｂ
と比較例には無く、Ｃについてはアルミニウム層の剥離
によるアルミニウムのバリ発生率が１０％程度みられ
た。The burrs at the time of closing the cell are the same as those of A and B of the present invention.
And Comparative Example, and about C, about 10% of the burr generation rate of aluminum due to peeling of the aluminum layer was observed.
【００３１】（実施例４）電極として、有機半導体であ
るポリアセンを正極及び負極に用いて実施例３と同様に
してセルを組立てた。また、これ等のセルの実施例３と
同様の特性値を表４に示す。なお、表中Ａ，Ｂ，Ｃ，Ｄ
は各々実施例３と同じ正極ケースを用いている。Example 4 A cell was assembled in the same manner as in Example 3 except that polyacene, which was an organic semiconductor, was used as the positive electrode and the negative electrode as electrodes. Table 4 shows characteristic values of these cells similar to those of Example 3. In the table, A, B, C, D
Use the same positive electrode case as in Example 3.
【００３２】[0032]
【表５】 [Table 5]
【００３３】（実施例５）電極として、正極にポリアセ
ン、負極にリチウムイオンをドーピングしたポリアセン
と有機電解液として０．５モルの過塩酸リチウムを溶解
したプロピレンカーボネイトを用いて実施例３と同様に
してセルを組立てた。また、これ等のセルについて、６
０℃の雰囲気中で３．３Ｖを印加し、５００時間後の容
量減少率交流内部抵抗（１ｋＨｚで測定）の上昇率及び
バリ発生率について表６に示す。なお、表中のＡ，Ｂ，
Ｃ，Ｄは各々実施例３と同じ正極ケースを用いている。Example 5 The same procedure as in Example 3 was carried out except that polyacene was used for the positive electrode, polyacene doped with lithium ions for the negative electrode, and propylene carbonate in which 0.5 mol of lithium perhydrochloride was dissolved as the organic electrolyte. The cell was assembled. Also, for these cells, 6
3.3 V is applied in an atmosphere of 0 ° C., and the capacity reduction rate after 500 hours. The rise rate of AC internal resistance (measured at 1 kHz) and the burr generation rate are shown in Table 6. In the table, A, B,
C and D each use the same positive electrode case as in the third embodiment.
【００３４】[0034]
【表６】 [Table 6]
【００３５】（実施例６）電極として、正極に二酸化マ
ンガン、負極にリチウム金属と有機電解液として、１モ
ルの過塩素酸リチウムを溶解したプロピレンカーボネイ
トとＤＭＥの混合溶液を用いて実施例３と同様にしてセ
ルを組立てた。また、これ等のセルについて、６０℃雰
囲気中で５００時間保存後の特性値について、表７に示
す。なお、表中のＡ，Ｂ，Ｃ，Ｄは各々実施例３と同じ
正極ケースを用いている。Example 6 A mixture of propylene carbonate and DME in which 1 mol of lithium perchlorate was dissolved as manganese dioxide for the positive electrode, lithium metal for the negative electrode and an organic electrolytic solution for the negative electrode was used. A cell was assembled in the same manner. Table 7 shows the characteristic values of these cells after storage in a 60 ° C. atmosphere for 500 hours. A, B, C, and D in the table each use the same positive electrode case as in the third embodiment.
【００３６】[0036]
【表７】 [Table 7]
【００３７】[0037]
【発明の効果】本発明により、低コストの高耐食性の材
料でかつセルの生産性を高め、しかも高耐圧性の電気化
学セルを得ることができる。According to the present invention, it is possible to obtain an electrochemical cell which is made of a low-cost, high-corrosion-resistant material, has high cell productivity, and has a high pressure resistance.
【図１】本発明の電気化学セルを示す半縦断面図であ
る。FIG. 1 is a semi-longitudinal sectional view showing an electrochemical cell of the present invention.
【図２】各種ステンレス鋼の孔食電位の温度依存性であ
る。FIG. 2 shows the temperature dependence of the pitting potential of various stainless steels.
【図３】各種金属の電圧?電流曲線を示す図である。FIG. 3 is a diagram showing voltage-current curves of various metals.
【図４】文献より引用されたＣｒ及びＭｏ含有率と孔食
温度との関係を示す図である。FIG. 4 is a diagram showing the relationship between the Cr and Mo contents quoted from the literature and the pitting temperature.
【図５】従来の電気化学セルの一例の電気二重層キャパ
シタの半縦断面図である。FIG. 5 is a half longitudinal sectional view of an electric double layer capacitor as an example of a conventional electrochemical cell.
【図６】従来の正極ケースの縦断面図と一部拡大図であ
る。FIG. 6 is a longitudinal sectional view and a partially enlarged view of a conventional positive electrode case.
１ 正極ケース ２、２’電極 ３、３’集電体 ５ ガスケット ６ 負極ケース ７ セパレータ １１ 正極ケース １２、１２’電極 １３、１３’導電性ペースト １４ セパレータ １５ ガスケット １６ 負極ケース REFERENCE SIGNS LIST 1 positive electrode case 2, 2 ′ electrode 3, 3 ′ current collector 5 gasket 6 negative electrode case 7 separator 11 positive electrode case 12, 12 ′ electrode 13, 13 ′ conductive paste 14 separator 15 gasket 16 negative electrode case
Claims (2)
極ケースとセパレータと非水電解液とから構成された電
気化学セルにおいて、前記正極ケースがＮｉ２４．００
〜２６．００％、Ｃｒ２２．００〜２４．００％、Ｍｏ
５．００〜６．００％、Ｎ０．１７０〜０．２２０％、
Ｍｎ≦１．００％、Ｓｉ≦１．００％、Ｃ≦０．０３０
％である高Ｎｉオーステナイトステンレス鋼であること
を特徴とする電気化学セル。1. An electrochemical cell comprising a negative electrode case and a positive electrode case in which electrodes are incorporated, a separator and a non-aqueous electrolyte, wherein the positive electrode case is Ni24.00.
~ 26.00%, Cr22.00 ~ 24.00%, Mo
5.00 to 6.00%, N 0.170 to 0.220%,
Mn ≦ 1.00%, Si ≦ 1.00%, C ≦ 0.030
% Of high Ni austenitic stainless steel.
極ケースとセパレータと非水電解液とから構成された電
気化学セルにおいて、前記正極ケースがＮｉ５．５０〜
７．５０％、Ｃｒ２４．００〜２６．００％、Ｍｏ２．
５０〜３．５０％、Ｎ０．０８〜０．２０％、Ｍｎ≦
１．５０％、Ｓｉ≦１．００％、Ｃ≦０．０３０％であ
るオーステナイト・フェライトの二相ステンレス鋼であ
ることを特徴とする電気化学セル。2. An electrochemical cell comprising a negative electrode case and a positive electrode case in which electrodes are incorporated, a separator, and a non-aqueous electrolyte, wherein the positive electrode case has Ni of 5.50 or more.
7.50%, Cr 24.0 to 26.00%, Mo2.
50 to 3.50%, N 0.08 to 0.20%, Mn ≦
An electrochemical cell comprising an austenitic ferrite duplex stainless steel having 1.50%, Si ≦ 1.00%, and C ≦ 0.030%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000291062A JP3576948B2 (en) | 1992-11-26 | 2000-09-25 | Electrochemical cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31729692 | 1992-11-26 | ||
| JP4-317296 | 1992-11-26 | ||
| JP2000291062A JP3576948B2 (en) | 1992-11-26 | 2000-09-25 | Electrochemical cell |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24159393A Division JP3195475B2 (en) | 1992-11-26 | 1993-09-28 | Electrochemical cell |
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| Publication Number | Publication Date |
|---|---|
| JP2001118546A true JP2001118546A (en) | 2001-04-27 |
| JP3576948B2 JP3576948B2 (en) | 2004-10-13 |
Family
ID=26568981
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000291062A Expired - Lifetime JP3576948B2 (en) | 1992-11-26 | 2000-09-25 | Electrochemical cell |
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| Country | Link |
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| JP (1) | JP3576948B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005064028A1 (en) * | 2003-12-26 | 2005-07-14 | Matsushita Electric Industrial Co., Ltd. | Material of case for storage cell |
| JP2006179840A (en) * | 2004-11-25 | 2006-07-06 | Matsushita Electric Ind Co Ltd | Coin-shaped electrochemical element and its manufacturing method |
| EP1986255A3 (en) * | 2007-04-20 | 2010-04-28 | Nissan Motor Co., Ltd. | Secondary battery with non-aqueous electrolyte and corrosion-resistant collector |
-
2000
- 2000-09-25 JP JP2000291062A patent/JP3576948B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005064028A1 (en) * | 2003-12-26 | 2005-07-14 | Matsushita Electric Industrial Co., Ltd. | Material of case for storage cell |
| CN100449025C (en) * | 2003-12-26 | 2009-01-07 | 松下电器产业株式会社 | Material of case for storage cell |
| US7515395B2 (en) | 2003-12-26 | 2009-04-07 | Panasonic Corporation | Material of case for storage cell |
| JP2006179840A (en) * | 2004-11-25 | 2006-07-06 | Matsushita Electric Ind Co Ltd | Coin-shaped electrochemical element and its manufacturing method |
| JP4665513B2 (en) * | 2004-11-25 | 2011-04-06 | パナソニック株式会社 | Method for producing coin-type electrochemical device |
| EP1986255A3 (en) * | 2007-04-20 | 2010-04-28 | Nissan Motor Co., Ltd. | Secondary battery with non-aqueous electrolyte and corrosion-resistant collector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3576948B2 (en) | 2004-10-13 |
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