JPH0855626A - Nonaqueous solvent battery - Google Patents
Nonaqueous solvent batteryInfo
- Publication number
- JPH0855626A JPH0855626A JP6192374A JP19237494A JPH0855626A JP H0855626 A JPH0855626 A JP H0855626A JP 6192374 A JP6192374 A JP 6192374A JP 19237494 A JP19237494 A JP 19237494A JP H0855626 A JPH0855626 A JP H0855626A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- porous carbon
- carbon
- active material
- 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
Classifications
-
- Y02E60/122—
Landscapes
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、負極活物質にアルカリ
金属、正極活物質にオキシハロゲン化物を用いた非水溶
媒電池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 improvement of a non-aqueous solvent battery using an alkali metal as a negative electrode active material and an oxyhalide as a positive electrode active material.
【０００２】[0002]
【従来の技術】負極活物質として、リチウム、ナトリウ
ム等のアルカリ金属を用い、塩化チオニルや塩化スルフ
リル等のオキシハロゲン化物を電解液の溶媒及び正極活
物質とし、かつそれ自体不活性な多孔質炭素層を主材と
するものを正極として構成されている非水溶媒電池は、
エネルギー密度が大きく、貯蔵特性に優れ、しかも作動
温度範囲が広いという特徴をもち、電卓、時計、メモリ
ーのバックアップ電源として多用されている。このよう
な電池の最大の特徴は、正極活物質として塩化チオニル
などの液状オキシハロゲン化物を用いることにあり、多
孔性の正極表面で液状活物質が電気化学的に還元される
ことにより電池反応が進行する。中でも負極にリチウム
を用い、塩化チオニルを主正極活物質としたいわゆるリ
チウム・塩化チオニル電池は、特にエネルギー密度が大
きいために注目されている。2. Description of the Related Art As an anode active material, an alkali metal such as lithium or sodium is used, and an oxyhalide such as thionyl chloride or sulfuryl chloride is used as a solvent for an electrolytic solution and a cathode active material, and porous carbon which is inactive in itself The non-aqueous solvent battery configured with the layer as the main material as the positive electrode is
It has a large energy density, excellent storage characteristics, and a wide operating temperature range, and is widely used as a backup power source for calculators, clocks, and memories. The greatest feature of such a battery is that a liquid oxyhalide such as thionyl chloride is used as the positive electrode active material, and the battery reaction is electrochemically reduced by the electrochemical reduction of the liquid active material on the porous positive electrode surface. proceed. Above all, a so-called lithium / thionyl chloride battery using lithium as a negative electrode and using thionyl chloride as a main positive electrode active material has attracted attention because of its particularly high energy density.
【０００３】一般に円筒型のリチウム・塩化チオニル系
の非水溶媒電池は、缶体内面にリチウム製の負極を配設
し、この負極内側の缶体内にセパレータを介して金網等
の金属集電体を内存した多孔質炭素体からなる正極を収
納すると共に、該正極に塩化チオニルを主成分とし、正
極活物質を兼ねる電解液を含浸させた構造になってい
る。こうした構造の電池においては、正極の特性により
電池放電特性が大きく影響され、正極活物質の電気化学
的反応に対する触媒的活性度、気孔率、電気的導電性等
が重要な因子となる。Generally, in a cylindrical lithium-thionyl chloride non-aqueous solvent battery, a negative electrode made of lithium is disposed on the inner surface of the can, and a metal current collector such as a wire mesh is disposed inside the negative electrode via a separator. In addition to accommodating a positive electrode composed of a porous carbon body containing therein, the positive electrode is impregnated with an electrolytic solution containing thionyl chloride as a main component and also serving as a positive electrode active material. In a battery having such a structure, the battery discharge characteristics are greatly affected by the characteristics of the positive electrode, and the catalytic activity, porosity, electrical conductivity, etc. of the positive electrode active material for the electrochemical reaction are important factors.
【０００４】ところで、上述した円筒型電池の正極の多
孔質炭素体としては、従来よりアセチレンブラック等の
カーボンブラックにポリテトラフルオロエチレンを結着
剤として添加し、混練した後、所定の形状に成形したも
のが使用されている。このような正極の多孔質炭素体
は、微視的に見るとポリテトラフルオロエチレンがくも
の巣状に繊維化された中にカーボンブラック粒子が補促
されており、正極反応に伴なう放電生成物がカーボンブ
ラックの粒子間に析出する時に生じる正極の体積膨張を
円滑かつ均一に吸収する作用をするため、正極の利用率
の向上に寄与する。このようなくもの巣状の繊維化によ
る結合様式は、ポリテトラフルオロエチレン結着剤の最
大の特徴であり、他の結合剤では実現できない。また、
ポリテトラフルオロエチレンは、液状オキシハロゲン化
物に対する耐久性においても極めて優れている。By the way, as a porous carbon body for the positive electrode of the above-mentioned cylindrical battery, polytetrafluoroethylene is conventionally added to carbon black such as acetylene black as a binder, and the mixture is kneaded and then molded into a predetermined shape. What has been used is being used. Microscopically, such a porous carbon body of the positive electrode has polytetrafluoroethylene fiberized in the form of spider webs, with carbon black particles being reinforced, and the discharge generated by the positive electrode reaction is generated. Since it has a function of smoothly and uniformly absorbing the volume expansion of the positive electrode generated when the substance is deposited between the particles of carbon black, it contributes to the improvement of the utilization rate of the positive electrode. The bonding mode by the comb-like fiberization is the greatest feature of the polytetrafluoroethylene binder and cannot be realized by other binders. Also,
Polytetrafluoroethylene is also extremely excellent in durability against liquid oxyhalides.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、ポリテ
トラフルオロエチレンで結着したカーボンブラックは、
強固な固形物とはならず、粘土状の半固形物であり、こ
れをプレス成形等によって所定形状に成形することによ
り得られる多孔質炭素体は極めてくずれ易い。このため
該多孔質炭素体に金属集電体を内在させ、正極として缶
体内に装填する電池の組立てにおいて、該多孔質炭素体
が割れ、欠け等の不良を生じたり、電池組立て後の機械
的衝撃によって金属集電体から分離したり、セパレータ
との密着性が悪化したりする。その結果、かかる正極を
有する電池は、放電電圧が不規則に低下したり、最悪の
場合は内部ショートを起こす恐れがある。本発明は、正
極の多孔質炭素体における機械的強度の脆弱さによって
生じる電池不良を解消し、かつ放電電圧の安定性及び重
負荷特性の優れた非水溶媒電池を提供しようとするもの
である。However, the carbon black bound with polytetrafluoroethylene is
It is not a solid solid but a clay-like semi-solid, and the porous carbon body obtained by molding this into a predetermined shape by press molding or the like is extremely susceptible to collapse. Therefore, in assembling a battery in which a metal current collector is incorporated in the porous carbon body and is loaded into the can body as a positive electrode, the porous carbon body suffers from defects such as cracking and chipping, and mechanical damage after battery assembly. It may be separated from the metal current collector due to the impact, or the adhesion with the separator may be deteriorated. As a result, in a battery having such a positive electrode, the discharge voltage may drop irregularly, or in the worst case, an internal short circuit may occur. The present invention is intended to provide a non-aqueous solvent battery which eliminates a battery failure caused by the weak mechanical strength of the porous carbon body of the positive electrode and has excellent discharge voltage stability and heavy load characteristics. .
【０００６】[0006]
【課題を解決するための手段】本発明は、アルカリ金属
からなる負極活物質と多孔質炭素体を主構成物とする正
極とオキシハロゲン化物を主成分とする正極活物質を兼
ねる電解液、とから構成される非水溶倍電池において、
該正極の多孔質炭素体に黒鉛系の炭素含有率９８％以上
の炭素繊維を添加配合したことを特徴とする非水溶媒電
池である。The present invention provides a negative electrode active material composed of an alkali metal, a positive electrode containing a porous carbon body as a main constituent, and an electrolytic solution also serving as a positive electrode active material containing oxyhalide as a main component. In a non-water-soluble battery composed of
It is a non-aqueous solvent battery characterized in that a graphite-based carbon fiber having a carbon content of 98% or more is added to the porous carbon body of the positive electrode.
【０００７】炭素繊維の配合割合は、多孔質炭素体に対
して５〜２０重量％の範囲にすることが望ましい。この
理由は、その配合割合を５重量％未満にすると、多孔質
炭素体の保形性、強度が不十分となり、２０重量％を越
えると多孔質炭素体の気孔率を低化させて放電性能に悪
影響を及ぼす恐れがある。The carbon fiber content is preferably in the range of 5 to 20% by weight with respect to the porous carbon material. The reason for this is that if the blending ratio is less than 5% by weight, the shape retention and strength of the porous carbon body become insufficient, and if it exceeds 20% by weight, the porosity of the porous carbon body is lowered and the discharge performance is lowered. May be adversely affected.
【０００８】[0008]
【作用】こうした炭素繊維を併用した結着剤で成形され
た多孔質炭素体は、電池組立て後の放電反応において、
多孔質炭素体からなる正極中に中間反応生成物や放電反
応生成物が蓄積され、電気的に絶縁されていくと考えら
れる。この電気的絶縁を炭素繊維により電気的接触を保
ち、電気導電性をもたせ、電池の放電電圧の安定性が良
好になり、重負荷放電時の電圧も向上できる。また、多
孔質炭素体を強固に固形化できるので、正極の製造工程
や電池組立て時の取扱いが容易となる。[Function] A porous carbon body molded with a binder using such a carbon fiber is used in a discharge reaction after battery assembly.
It is considered that the intermediate reaction product and the discharge reaction product are accumulated in the positive electrode made of the porous carbon body and are electrically insulated. This electrical insulation is maintained in electrical contact with carbon fiber and has electrical conductivity, the stability of the discharge voltage of the battery is improved, and the voltage during heavy load discharge can be improved. In addition, since the porous carbon body can be solidified solidly, it is easy to handle during the positive electrode manufacturing process and battery assembly.
【０００９】[0009]
【実施例】以下、本発明をＡＡサイズのリチウム・塩化
チオニル電池に適用した例について図１を参照して説明
する。EXAMPLE An example in which the present invention is applied to an AA size lithium thionyl chloride battery will be described below with reference to FIG.
【００１０】図中の１は、負極端子を兼ねる上面が開口
された例えばステンレス製の有底円筒形の缶体である。
この缶体１内面には金属リチウムからなる筒状の負極２
が圧着されている。この負極２の内側の缶体１内には正
極３が該負極２内面に配置されたガラス繊維不織布から
なるセパレータ４を介して設けられている。なお、正極
３と缶体１底面との間にもセパレータ４と同じガラス繊
維不織布からなる底紙５が介装されている。前記正極３
は筒状の多孔質炭素体６と、この多孔質炭素体６の中空
部内面に配置された筒状の金網からなる金属集電体７と
から構成されている。こうした正極３は、カーボンブラ
ックにポリテトラフルオロエチレン１０重量％加え、こ
の混合物に対し１０重量％に相当する黒鉛系の炭素含有
率９８％以上の炭素繊維を配合し、エチルアルコールを
加えて混練した後、プレス成形により筒状とし、その中
空部にニッケル製網体の筒状金属集電体を挿入圧接し、
更に１５０℃の真空下で乾燥固化させることにより造ら
れたものである。Reference numeral 1 in the figure denotes a bottomed cylindrical can body made of, for example, stainless steel, the top surface of which serves also as a negative electrode terminal is opened.
A cylindrical negative electrode 2 made of metallic lithium is formed on the inner surface of the can body 1.
Is crimped. Inside the can body 1 inside the negative electrode 2, a positive electrode 3 is provided via a separator 4 made of a glass fiber nonwoven fabric arranged on the inner surface of the negative electrode 2. A bottom paper 5 made of the same glass fiber non-woven fabric as the separator 4 is also interposed between the positive electrode 3 and the bottom surface of the can body 1. The positive electrode 3
Is composed of a cylindrical porous carbon body 6 and a metal current collector 7 made of a cylindrical wire mesh and arranged on the inner surface of the hollow portion of the porous carbon body 6. In such a positive electrode 3, 10% by weight of polytetrafluoroethylene was added to carbon black, 10% by weight of this mixture was mixed with graphite-based carbon fibers having a carbon content of 98% or more, and ethyl alcohol was added and kneaded. After that, it is formed into a tubular shape by press molding, and a tubular metal current collector made of a nickel net is inserted into the hollow portion and press-contacted,
Further, it is produced by drying and solidifying under a vacuum of 150 ° C.
【００１１】また、前記正極３の上方の缶体１内には前
記セパレータ４に支持された中央に穴を有する絶縁紙８
が配置されている。前記缶体１の上面開口部にはメタル
トップ９がレーザー溶接等により封冠されている。この
メタルトップ９の中心には穴１０が開口されており、こ
の穴１０には、パイプ状正極端子１１がガラスシール材
１２により該メタルトップ９に対して電気的に絶縁され
た状態で固定されている。この正極端子１１はその下端
に取付けたリード線１３を介して前記正極３の金属集電
体７に接続されている。更に、前記缶体１内には前記パ
イプ状正極端子１１から注入された電解液１４が収容さ
れている。この電解液１４は四塩化アルミニウムリチウ
ム（ＬｉＡｌＣｌ4 ）を例えば１．２モル/l溶解した塩
化チオニル（ＳＯＣｌ2 ）からなる。なお、前記パイプ
状正極端子１１には例えばステンレス製の鍔付きの栓体
１５が挿入され、該端子１１先端と挿入された栓体１５
とをレーザー溶接することにより該正極端子１１の孔が
封口されている。In addition, in the can body 1 above the positive electrode 3, an insulating paper 8 having a central hole supported by the separator 4 is provided.
Is arranged. A metal top 9 is capped at the upper opening of the can body 1 by laser welding or the like. A hole 10 is opened at the center of the metal top 9, and a pipe-shaped positive electrode terminal 11 is fixed to the hole 10 by a glass sealing material 12 in a state electrically insulated from the metal top 9. ing. The positive electrode terminal 11 is connected to the metal current collector 7 of the positive electrode 3 via a lead wire 13 attached to the lower end thereof. Further, the electrolytic solution 14 injected from the pipe-shaped positive electrode terminal 11 is accommodated in the can body 1. The electrolytic solution 14 is made of thionyl chloride (SOCl 2 ) in which lithium aluminum tetrachloride (LiAlCl 4 ) is dissolved, for example, 1.2 mol / l. A plug body 15 made of, for example, stainless steel with a collar is inserted into the pipe-shaped positive electrode terminal 11, and the plug body 15 is inserted into the tip of the terminal 11.
The hole of the positive electrode terminal 11 is sealed by laser welding of and.
【００１２】比較例１ カーボンブラックにポリテトラフルオロエチレンを１０
重量％加え、この混合物にエチルアルコールを加え混練
する。なお、この混合物には炭素繊維を配合しない。こ
の後、実施例と同様に筒状に成形し、この成形体の中空
部に筒状金属集電体を挿入圧接し、更に１５０℃の真空
下で乾燥固化させて正極を作製した。こうした正極を用
いた以外、実施例と同構造の電池を組立てた。Comparative Example 1 Carbon black containing 10 parts of polytetrafluoroethylene
% By weight, and ethyl alcohol is added to this mixture and kneaded. No carbon fiber was added to this mixture. After that, it was formed into a tubular shape in the same manner as in Example, a tubular metal current collector was inserted into the hollow portion of the formed body under pressure contact, and further dried and solidified under vacuum at 150 ° C. to produce a positive electrode. A battery having the same structure as that of the example was assembled except that such a positive electrode was used.
【００１３】比較例２ カーボンブラックにポリテトラフルオロエチレンを１０
重量％加え、この混合物に炭素含有率９５％の炭素繊維
を配合し、エチルアルコールを加え混練する。この後、
実施例と同様に筒状に成形し、この成形体の中空部に筒
状金属集電体を挿入圧接し、更に１５０℃の真空下で乾
燥固化させて正極を作製した。こうした正極を用いた以
外、実施例と同構造の電池を組立てた。ここで、本実施
例及び比較例１、比較例２について、正極を缶体内に装
填する等の組立て工程での正極（多孔質炭素体）の割
れ、欠け等の不良発生個数、並びに図２の３００Ω負荷
での放電曲線に示すように、良品（Ａ）のように放電終
止まで平担な電圧を維持しない不良品（Ｂ）の電池の数
を調べた。その結果を下記表１に示した。Comparative Example 2 Polytetrafluoroethylene 10 was added to carbon black.
% By weight, carbon fibers having a carbon content of 95% are mixed with this mixture, and ethyl alcohol is added and kneaded. After this,
A positive electrode was manufactured by forming a cylindrical shape in the same manner as in the example, inserting and pressing a cylindrical metal current collector into the hollow portion of the formed body, and further drying and solidifying under vacuum at 150 ° C. A battery having the same structure as that of the example was assembled except that such a positive electrode was used. Here, regarding the present Example and Comparative Examples 1 and 2, the number of defective occurrences such as cracking and chipping of the positive electrode (porous carbon body) in the assembling process such as loading the positive electrode into the can body, and FIG. As shown in the discharge curve at a load of 300Ω, the number of defective (B) batteries, which did not maintain a flat voltage until the end of discharge, like the good product (A), was examined. The results are shown in Table 1 below.
【００１４】[0014]
【表１】 [Table 1]
【００１５】また、本実施例及び比較例１、比較例２の
電池について、重負荷放電特性を調べた。これらの結果
を図３に示す。なお図中のＡは本実施例の電池の特性
線、Ｂは比較例１の電池の特性線、Ｃは比較例２の電池
の特性線を夫々示す。上記表１及び図３から明らかなよ
うに、本発明の電池は従来の電池に比べて正極の多孔質
炭素体の割れ、欠けが極めて少なく、放電電圧の安定
性、重負荷特性の点でも優れていることがわかる。The heavy load discharge characteristics of the batteries of this example and Comparative Examples 1 and 2 were examined. The results are shown in FIG. In the figure, A is the characteristic line of the battery of this example, B is the characteristic line of the battery of Comparative Example 1, and C is the characteristic line of the battery of Comparative Example 2. As is clear from Table 1 and FIG. 3, the battery of the present invention has significantly less cracks and cracks in the porous carbon body of the positive electrode than the conventional battery, and is excellent in terms of discharge voltage stability and heavy load characteristics. You can see that
【００１６】[0016]
【発明の効果】以上詳述したように、本発明によれば正
極の多孔質炭素体の機械的強度を改善して該炭素体の脆
弱さによる電池不良を解消でき、更に放電電圧の安定性
及び重負荷放電特性の優れた非水溶媒電池である。As described in detail above, according to the present invention, the mechanical strength of the porous carbon body of the positive electrode can be improved to eliminate the battery failure due to the brittleness of the carbon body, and the stability of the discharge voltage can be improved. And a non-aqueous solvent battery excellent in heavy load discharge characteristics.
【図１】本発明の一実施例を示すリチウム・塩化チオニ
ル電池の断面図である。FIG. 1 is a cross-sectional view of a lithium thionyl chloride battery showing an embodiment of the present invention.
【図２】リチウム・塩化チオニル電池における、時間経
過に伴なう放電電圧の変化を示す線図である。FIG. 2 is a diagram showing a change in discharge voltage over time in a lithium thionyl chloride battery.
【図３】重負荷放電特性を示す線図である。FIG. 3 is a diagram showing a heavy load discharge characteristic.
１…缶体 ２…負極 ３…正極 ６…多孔質炭素体 ７…金属集電体 ９…メタルトップ 11…パイプ状正極端子 14…電解液 DESCRIPTION OF SYMBOLS 1 ... Can body 2 ... Negative electrode 3 ... Positive electrode 6 ... Porous carbon body 7 ... Metal current collector 9 ... Metal top 11 ... Pipe-shaped positive electrode terminal 14 ... Electrolyte
Claims (1)
孔質炭素体を主構成物とする正極と、オキシハロゲン化
物を主成分とする正極活物質を兼ねる電解液、とから構
成される非水溶媒電池において、 該正極の多孔質炭素体に黒鉛系の炭素含有率が９８％以
上の炭素繊維を添加配合したことを特徴とする非水溶媒
電池。1. A non-aqueous composition comprising a negative electrode active material composed of an alkali metal, a positive electrode containing a porous carbon body as a main constituent, and an electrolytic solution containing oxyhalide as a main component and also serving as a positive electrode active material. In a solvent battery, a non-aqueous solvent battery characterized in that a graphite-based carbon fiber having a carbon content of 98% or more is added to the porous carbon body of the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6192374A JPH0855626A (en) | 1994-08-16 | 1994-08-16 | Nonaqueous solvent battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6192374A JPH0855626A (en) | 1994-08-16 | 1994-08-16 | Nonaqueous solvent battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0855626A true JPH0855626A (en) | 1996-02-27 |
Family
ID=16290233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6192374A Pending JPH0855626A (en) | 1994-08-16 | 1994-08-16 | Nonaqueous solvent battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0855626A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178270A (en) * | 2013-03-26 | 2013-06-26 | 武汉中原长江科技发展有限公司 | Anode of high-energy lithium/thionyl chloride battery and preparation method of anode |
| CN115548246A (en) * | 2022-08-30 | 2022-12-30 | 哈尔滨工程大学 | Preparation method of lithium thionyl chloride battery positive electrode reaction carrier material |
-
1994
- 1994-08-16 JP JP6192374A patent/JPH0855626A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178270A (en) * | 2013-03-26 | 2013-06-26 | 武汉中原长江科技发展有限公司 | Anode of high-energy lithium/thionyl chloride battery and preparation method of anode |
| CN115548246A (en) * | 2022-08-30 | 2022-12-30 | 哈尔滨工程大学 | Preparation method of lithium thionyl chloride battery positive electrode reaction carrier material |
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