JPS62229663A - Nonaqueous reserve cell - Google Patents
Nonaqueous reserve cellInfo
- Publication number
- JPS62229663A JPS62229663A JP7175086A JP7175086A JPS62229663A JP S62229663 A JPS62229663 A JP S62229663A JP 7175086 A JP7175086 A JP 7175086A JP 7175086 A JP7175086 A JP 7175086A JP S62229663 A JPS62229663 A JP S62229663A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- chloride
- electrode active
- oxyhaloid
- electrolyte
- 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 20
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
Abstract
Description
【発明の詳細な説明】
発明の利用分野
本発明は、従来の注液式電池より高率放電時の放電電圧
が高く、容量の大きな注液式の非水電池に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Application of the Invention The present invention relates to a nonaqueous injection type battery that has a higher discharge voltage during high rate discharge and a larger capacity than conventional injection type batteries.
従来の技術とその問題点
正極活物質として塩化チオニル、塩化スルフリル等のオ
キシハライドを、負極活物質には活性金属であるリチウ
ム等を用いる非水電池が開発されている。この種電池で
はオキシハライドが正極活物質と電解液を兼ねており、
エネルギー密度が大きく、血路電圧は３．７■を示すな
ど、優れた特性を有するものの、長期保存後の放電では
、放電初期に負極上に生成した保護膜のため、電圧遅延
が生ずるという問題がある。この電圧遅延を解決するた
め、電池極板と電解質等を添加したオキシハライド溶液
を分離しておき、使用時に電池内へ該オキシハライド溶
液を注入し、電池の活性化を計る、いわゆる注液式の電
池とする方法が取られている。注液式とすることで貯蔵
時の自己放電等による劣化も抑制され、電池寿命のきわ
めて長い優れた電池となる。BACKGROUND ART Non-aqueous batteries have been developed that use an oxyhalide such as thionyl chloride or sulfuryl chloride as a positive electrode active material and an active metal such as lithium as a negative electrode active material. In this type of battery, oxyhalide serves as both the positive electrode active material and the electrolyte.
Although it has excellent characteristics such as a high energy density and a blood circuit voltage of 3.7μ, there is a problem that a voltage delay occurs during discharge after long-term storage due to the protective film formed on the negative electrode at the beginning of discharge. be. In order to solve this voltage delay, the battery electrode plate and the oxyhalide solution to which electrolyte etc. are added are separated, and the oxyhalide solution is injected into the battery during use to activate the battery, a so-called injection method. The method of using batteries is being taken. By using a liquid injection type, deterioration due to self-discharge during storage is also suppressed, resulting in an excellent battery with an extremely long battery life.
従来のこの種注液式非水電池では、オキシハライド中に
電解質として塩化アルミニウムあるいは塩化アルミニウ
ムと塩化リチウムを添加して用いていたが、高率放電時
に分極のため電圧が大きく低・下し、放電容量が充分に
取出せないという問題があった。また、この高率放電時
の電圧低下を改良する目的で、オキシハライド中に塩化
ガリウムを電解質として添加する方法もあるが、この場
合、高率放電時の電圧は飛躍的に向上するものの、すチ
ウムと塩化ガリウムとオキシハライド間の１１反応が早
く、特に高温放電時にはこの副反応のため活物質の利用
率の低下、あるいは、ｎ１反応によるオキシハライドの
消耗に伴なう電解液抵抗の増大により、早期に電圧の低
下を招くという欠点があった。Conventional liquid-injected nonaqueous batteries of this type use aluminum chloride or aluminum chloride and lithium chloride added as an electrolyte to oxyhalide, but the voltage drops significantly due to polarization during high-rate discharge. There was a problem that a sufficient discharge capacity could not be obtained. In addition, in order to improve the voltage drop during high rate discharge, there is a method of adding gallium chloride as an electrolyte to the oxyhalide, but in this case, although the voltage during high rate discharge increases dramatically, The 11 reaction between lithium, gallium chloride, and oxyhalide is fast, and especially during high-temperature discharge, this side reaction reduces the utilization rate of the active material, or increases electrolyte resistance due to consumption of oxyhalide due to the n1 reaction. However, this method had the disadvantage of causing an early voltage drop.
問題点を解決するための手段
発明者らは塩化ガリウムを電解質として用いた注液式オ
キシハライド電池の良好な高率放電性能を維持し、且つ
、高温放電時の副反応を抑えるため、各種添加剤の効果
を調べた結果、塩化アルミニウムを電解液中に添加する
ことにより上述の副反応が著しく抑制されると共に、良
好な高率放電性能が得られるのを見出した。Means for Solving the Problems The inventors developed various additives in order to maintain good high-rate discharge performance of the injection type oxyhalide battery using gallium chloride as an electrolyte and to suppress side reactions during high-temperature discharge. As a result of investigating the effect of the agent, it was found that by adding aluminum chloride to the electrolytic solution, the above-mentioned side reactions were significantly suppressed and good high rate discharge performance was obtained.
本発明は、この事実に基ずき、塩化ガリウムと塩化アル
ミニウムを電解質として用いた注液式オキシハライド電
池を提供するものである。Based on this fact, the present invention provides an injection type oxyhalide battery using gallium chloride and aluminum chloride as electrolytes.
実 施 例 以下、本発明の実施例について詳述する。Example Examples of the present invention will be described in detail below.
第１図は本発明になる電池の一実施例を示す断面図であ
り、図において、１は電槽、２は負極、３はセパレータ
、４は１陽集電体、５は注液管である。FIG. 1 is a sectional view showing an embodiment of the battery according to the present invention. In the figure, 1 is a battery case, 2 is a negative electrode, 3 is a separator, 4 is a positive current collector, and 5 is a liquid injection pipe. be.
正極活物質には塩化チオニルを用い、前記塩化チオニル
に塩化ガリウム１．ＯＭ 、塩化アルミニウム１．０Ｍ
を添加して塩化チオニル溶液とし、放電試験時に注液管
５より電槽内部へ注入し、電池の活性化をはかった。尚
、正穫東電体４にはエキスバンド集電網にバインダーと
してテフロンを用いてアセチレンブラックを固着したも
のを使用し、〜
負極２にはニッケル集電網にリチウム薄膜を圧着して用
いた。また、セパレータ３には多孔度９２％のガラスＩ
ＩＩより成る不織布を用いている。電池の構成は中央に
正型集電体４を、その両側にセパレータ３を介してリチ
ウム負極２を配置したパイセル構造とした。Thionyl chloride is used as the positive electrode active material, and 1.0% of gallium chloride is added to the thionyl chloride. OM, aluminum chloride 1.0M
was added to form a thionyl chloride solution, which was injected into the battery via the injection tube 5 during a discharge test to activate the battery. In addition, for the Masaaki Toden body 4, an extended band current collection network with acetylene black fixed to it using Teflon as a binder was used, and for the negative electrode 2, a lithium thin film was crimped onto a nickel current collection network. In addition, the separator 3 is made of glass I with a porosity of 92%.
A nonwoven fabric made of II is used. The battery had a pi-cell structure in which a positive current collector 4 was placed in the center and lithium negative electrodes 2 were placed on both sides of the positive current collector 4 with separators 3 interposed therebetween.
発明の効果
上述の如く構成した本発明電池＜Ａ）の性能を調べるた
め、注液後、直ちに８５ｎ＋Ａ／ａｄの定電流で放電す
る放電試験を行なった。尚、比較のため従来の電池とし
て４．５Ｍの塩化アルミニウムと０．１Ｍの塩化リチウ
ムを溶解した塩化チオニル溶液を用いたもの（Ｂ）と、
２．０Ｍの塩化ガリウムを溶解した塩化チオニル溶液を
用いたもの（Ｃ）についても同時に試験を行なった。そ
の結果を第２図に示す。Effects of the Invention In order to examine the performance of the battery of the present invention <A) constructed as described above, a discharge test was conducted in which the battery was immediately discharged at a constant current of 85 n+A/ad after injection. For comparison, a conventional battery using a thionyl chloride solution containing 4.5M aluminum chloride and 0.1M lithium chloride (B),
A test (C) using a thionyl chloride solution containing 2.0M gallium chloride was also conducted at the same time. The results are shown in FIG.
本発明による電池（Δ）と従来形電池（Ｂ）とを比較す
ると、本発明電池は放電容！（終止電圧２．５Ｖ ’）
が３倍近くも大きくなった上、電圧も約３００１１ＩＶ
ａ％くなった。また、従来形電池（Ｃ）と比較すると、
放電電圧の平坦性が格段に向上し、電圧も約２００ｍＶ
ａｉ＜なり、極めて優れた電池特性を示した。Comparing the battery according to the present invention (Δ) and the conventional battery (B), the battery according to the present invention has a lower discharge capacity! (Final voltage 2.5V')
is nearly three times larger, and the voltage is approximately 30011IV.
It became a%. Also, compared to the conventional battery (C),
The flatness of the discharge voltage has been significantly improved, and the voltage is approximately 200mV.
ai<, indicating extremely excellent battery characteristics.
この様に電解質に塩化ガリウムと塩化アルミニウムの混
合系を用いることにより、塩化ガリウムのリチウム（負
極）への接触機会が抑制される結果、放電以外の副反応
に関与する分が少なくなり、従来の注液式電池では難し
かった高率放電を可能とし、オキシハライド電池の応用
範囲を拡大することができた。By using a mixed system of gallium chloride and aluminum chloride as the electrolyte in this way, the opportunity for gallium chloride to come into contact with lithium (negative electrode) is suppressed, and as a result, the amount of gallium chloride involved in side reactions other than discharge is reduced. This enabled high-rate discharge, which was difficult with injection-type batteries, and expanded the range of applications for oxyhalide batteries.
尚、上記実施例では、オキシハライドとして塩化チオニ
ルを用いたものを示したが、塩化スルフリルを用いる系
でも同様の効果が得られる。In the above example, thionyl chloride was used as the oxyhalide, but similar effects can be obtained with a system using sulfuryl chloride.
以上の説明から明らかな様に、本発明は従来の注液式非
水電池の問題点を解決し、高率放電の要求される分野へ
も適用可能な、極めて優れた特性を有する注液式非水電
池を提供するものである。As is clear from the above description, the present invention solves the problems of conventional liquid injection type non-aqueous batteries, and has extremely excellent characteristics that can be applied to fields requiring high rate discharge. The present invention provides a non-aqueous battery.
第１図は本発明注液式非水電池の一実施例を示す断面図
、第２図は本発明電池および従来形電池のａ５ｍＡ／−
での定電流放電特性図である。
１・・・・・・電槽 ２・・・・・・負荷３・
・・・・・セパレータ ４・・・・・・正極集電体５
・・・・・・注液管Fig. 1 is a sectional view showing an embodiment of the injectable non-aqueous battery of the present invention, and Fig. 2 is a5mA/- of the inventive battery and the conventional battery.
It is a constant current discharge characteristic diagram. 1...Battery container 2...Load 3.
... Separator 4 ... Positive electrode current collector 5
・・・・・・Liquid injection tube
Claims (1)
金属を用いる注液式非水電池において、電解液に塩化ガ
リウムと塩化アルミニウムを溶解したオキシハライドを
用いたことを特徴とする注液式非水電池。An injection type non-aqueous battery using an oxyhalide as a positive electrode active material and an active metal as a negative electrode active material, characterized in that an oxyhalide in which gallium chloride and aluminum chloride are dissolved is used in the electrolyte. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7175086A JPS62229663A (en) | 1986-03-29 | 1986-03-29 | Nonaqueous reserve cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7175086A JPS62229663A (en) | 1986-03-29 | 1986-03-29 | Nonaqueous reserve cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62229663A true JPS62229663A (en) | 1987-10-08 |
Family
ID=13469519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7175086A Pending JPS62229663A (en) | 1986-03-29 | 1986-03-29 | Nonaqueous reserve cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62229663A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005050772A1 (en) * | 2003-11-21 | 2005-06-02 | Lg Chem, Ltd. | Electrochemical cell having an improved safety |
-
1986
- 1986-03-29 JP JP7175086A patent/JPS62229663A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005050772A1 (en) * | 2003-11-21 | 2005-06-02 | Lg Chem, Ltd. | Electrochemical cell having an improved safety |
| US8304105B2 (en) | 2003-11-21 | 2012-11-06 | Lg Chem, Ltd. | Electrochemical cell having an improved safety |
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