JP2765906B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2765906B2 JP2765906B2 JP1008366A JP836689A JP2765906B2 JP 2765906 B2 JP2765906 B2 JP 2765906B2 JP 1008366 A JP1008366 A JP 1008366A JP 836689 A JP836689 A JP 836689A JP 2765906 B2 JP2765906 B2 JP 2765906B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- metal
- electrolytic solution
- current collector
- dioxolane
- 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
-
- 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
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 イ．産業上の利用分野 本発明は非水電解液電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous electrolyte battery.
ロ．従来の技術 二酸化マンガン、フッ化炭素などを活物質とする正極
と、リチウム、ナトリウムなどの軽金属よりなる負極
と、非水電解液とを具備した電池は高エネルギー密度を
有し且つ自己放電が少ないという利点を有するため注目
されており、電卓、腕時計、メモリーバックアップ或い
はカメラ用駆動電源として用いられている。B. 2. Description of the Related Art A battery including a positive electrode using manganese dioxide, fluorocarbon, or the like as an active material, a negative electrode formed of a light metal such as lithium or sodium, and a nonaqueous electrolyte has a high energy density and low self-discharge. It has attracted attention because it has the advantage of being used as a calculator, a wristwatch, a memory backup, or a driving power supply for a camera.
ハ．発明が解決しようとする課題 ところで、この種電池の負極集電用金属としては耐食
性などの見地からニッケルが用いられているが、電池が
異常使用され過放電を受けて転極放電状態になっても、
ニッケルは電気化学的に安定であり、転極放電状態が持
続するため電解液の分解が起こりガス発生が生じ安定性
の面で問題があった。C. Problems to be Solved by the Invention By the way, nickel is used as the negative electrode current collector metal of this type of battery from the viewpoint of corrosion resistance and the like. Also,
Nickel is electrochemically stable, and since the reversal discharge state is maintained, decomposition of the electrolytic solution occurs, generating gas and causing a problem in stability.
ニ．課題を解決するための手段 本発明の要旨とするところは、 正極と、リチウム、ナトリウムなどの軽金属よりなる
負極と、ニッケル金属からなる負極集電体と、少なくと
もジオキソラン系の溶媒を含む電解液と、溶解電位が前
記負極構成軽金属より高く且つ前記負極集電体であるニ
ッケル金属より低い重金属とを具備し、 前記重金属が前記負極と電気的に接続され且つ電解液
と接触していることを特徴とする非水電解液電池 にある。D. Means for Solving the Problems The gist of the present invention is to provide a positive electrode, a negative electrode made of a light metal such as lithium and sodium, a negative electrode current collector made of a nickel metal, and an electrolytic solution containing at least a dioxolane-based solvent. A heavy metal having a dissolution potential higher than the light metal constituting the negative electrode and lower than nickel metal serving as the negative electrode current collector, wherein the heavy metal is electrically connected to the negative electrode and is in contact with the electrolytic solution. Non-aqueous electrolyte battery.
ホ．作用 溶解電位が負極構成軽金属より高く且つ負極集電体よ
り低い重金属、例えば鉄、亜鉛、マンガン等を負極と電
気的に接続すると共に、電解液に接触させておくと、電
池の通常反応時には上記重金属は負極金属によりアノー
ド、防食されることになり安定に金属の状態が存在して
いるが、転極放電状態時には負極の電位が本来の電位よ
り貴な方向にシフトし、重金属が電解液中に溶出する。E. Action When the dissolution potential is higher than the negative electrode constituting light metal and lower than the negative electrode current collector, and a heavy metal such as iron, zinc, manganese, etc. is electrically connected to the negative electrode, and is kept in contact with the electrolyte, the above-mentioned during normal reaction of the battery The heavy metal is anodic protected by the negative electrode metal, so that the state of the metal exists stably.However, during the reversal discharge state, the potential of the negative electrode shifts to a more noble direction than the original potential, and the heavy metal becomes in the electrolyte. To elute.
一方、1,3ジオキソラン、４メチルジオキソラン、1,2
ジオキソラン、２メトキシジオキソラン等のジオキソラ
ン系の溶媒は他の溶媒に比して重合し易い性質のもので
あり、通常は重合禁止剤を添加して実用に供している。On the other hand, 1,3 dioxolan, 4-methyldioxolan, 1,2
Dioxolane-based solvents such as dioxolane and 2-methoxydioxolane have a property of being easily polymerized as compared with other solvents, and are usually put to practical use with a polymerization inhibitor added thereto.
しかしながら、水分界面活性剤、重金属イオン等の存
在によってジオキソラン系の溶媒は重合が促進され容易
にゲル化する。However, the dioxolane-based solvent is easily gelled by the promotion of the polymerization due to the presence of the water surfactant, heavy metal ions and the like.
それ故、前記重金属とジオキソラン系の溶媒とを組合
わせることにより、通常反応時に支障をきたすことな
く、転極放電時のみ重金属の溶出に伴う電解液のゲル化
により電解液の電導度が著しく低下し、転極放電々流を
抑えることが可能となり、電解液の分解を抑制すること
ができる。Therefore, by combining the heavy metal and a dioxolane-based solvent, the conductivity of the electrolyte is significantly reduced due to gelation of the electrolyte accompanying elution of the heavy metal only at the time of reversal discharge, without causing any trouble during the normal reaction. However, it is possible to suppress the inversion of the reversal discharge, and it is possible to suppress the decomposition of the electrolytic solution.
尚、水分、界面活性剤もジオキソラン系の溶媒を重合
させるものであるが、これらを用いると通常放電反応に
支障をきたすため好ましくない。In addition, water and a surfactant also polymerize a dioxolane-based solvent. However, if these are used, they usually hinder the discharge reaction, which is not preferable.
本発明の要点はジオキソラン系の溶媒が重合し易いと
いう性質を巧みに利用するものであり、しかも通常の反
応時には何ら弊害を与えないものである。The gist of the present invention is to skillfully utilize the property that a dioxolane-based solvent is easily polymerized, and does not cause any harm at the time of a normal reaction.
ヘ．実 施 例 負極活性物としてリチウム金属、対極に白金板、参照
板にリチウム金属、電解液として1,3ジオキソラン溶媒
に１モル/lLiClO4を溶解したものを用いてテストセルを
作成し実験を行った。作用極であるリチウムの集電体と
してNi板を用い、且つこのNi板の重金属としてFe、Zn及
びMnを夫々電気的に接続すると共にこれら重金属が電解
液に浸るように組立て、定電位電解を行った。F. Example A test cell was prepared using lithium metal as the negative electrode active material, platinum plate as the counter electrode, lithium metal as the reference plate, and 1 mol / l LiClO 4 dissolved in 1,3 dioxolane solvent as the electrolyte, and an experiment was conducted. Was. A Ni plate was used as a current collector of lithium serving as a working electrode, and Fe, Zn, and Mn were electrically connected as heavy metals of the Ni plate, and the heavy metals were assembled so that they were immersed in an electrolytic solution. went.
そして転極放電状態をシュミレートするため、リチウ
ム極側をプラス（アノード）として、対極の白金板との
間に3Vの電圧を印加した。Then, in order to simulate the reversal discharge state, a voltage of 3 V was applied between the lithium electrode side plus (anode) and the platinum plate of the counter electrode.
図はこれらのテストセルにおける電流値の経時変化を
示し、図よりFe、Zn及びMnを接続したものはNiを接続し
たものに比して、早朝に電流が低下し、転極放電時にお
ける安全性に優れることがわかる。The figure shows the change over time in the current values of these test cells.The figure shows that the connection of Fe, Zn, and Mn resulted in a decrease in the current in the early morning compared to the connection of Ni, and the safety at the time of reversal discharge. It turns out that it is excellent.
この理由は、溶出した重金属イオンにより電解液が重
合したことによるものであり、テスト後の電解液は全て
重合していた。又、3Vを印加した際のリチウム作用極の
電位はリチウム参照極に対し、＋1.0〜1.5V程度の値を
示しており、本来のリチウムの電位よりも貴であったこ
とも確認された。The reason for this is that the electrolytic solution was polymerized by the eluted heavy metal ions, and the electrolytic solution after the test was all polymerized. In addition, the potential of the lithium working electrode when 3 V was applied showed a value of about +1.0 to 1.5 V with respect to the lithium reference electrode, and it was also confirmed that the potential was higher than the original lithium potential. .
尚、重金属の用い方としては実施例で示したように、
負極集電体としてのNi板に重金属を接続する方法以外
に、負極集電体をこれらの重金属で構成するか、又は負
極缶をこれら重金属で構成しても同様の効果が得られ
る。In addition, as shown in the examples, the use of heavy metals is as follows.
In addition to the method of connecting a heavy metal to a Ni plate as a negative electrode current collector, a similar effect can be obtained by forming the negative electrode current collector with these heavy metals or forming the negative electrode can with these heavy metals.
ト．発明の効果 上述した如く、非水電解液電池において、電解液を構
成する溶媒としてジオキソラン系の溶媒を用いると共
に、溶解電位が負極構成金属より高く且つ負極集電体よ
り低い重金属を負極と電気的に接続すると共に電解液と
接触させることにより、通常反応時は正常に反応が進行
し、転極放電のように負極が貴な電位にシフトする異常
の場合には、重金属が電解液中にイオンとして溶出して
電解後の重合を促進し、転極電々流を抑制して安全性を
高めることができるものであり、その工業的価値は極め
て大である。G. Effect of the Invention As described above, in a nonaqueous electrolyte battery, a dioxolane-based solvent is used as a solvent constituting an electrolytic solution, and a heavy metal having a dissolution potential higher than a negative electrode constituent metal and lower than a negative electrode current collector is electrically connected to the negative electrode. By contacting with the electrolyte and contacting it with the electrolyte, the reaction proceeds normally during the normal reaction, and in the case of abnormalities where the negative electrode shifts to a noble potential such as inversion discharge, heavy metals are contained in the electrolyte. And promotes polymerization after electrolysis, and suppresses reversal current to enhance safety, and its industrial value is extremely large.
尚、前述したような転極放電が生じる可能性は商用電
源との組合せによるメモリーバックアップ用電池として
用い、保護素子が故障した場合、或いは２ヶ以上直列に
用いる組電池を電源として用い１ヶの電池が何らかの原
因で他の電池より極端に性能が劣化し、且つ機器側の回
路に異常があり電流が流れ続けた場合等である。In addition, the possibility of the above-mentioned reversal of discharge occurs when used as a memory backup battery in combination with a commercial power supply, when the protection element is broken down, or when one or more assembled batteries used in series are used as the power supply. This is the case where the performance of the battery is extremely deteriorated as compared with other batteries for some reason, and there is an abnormality in the circuit on the device side, and the current continues to flow.
図面は各種重金属を負極に電気接続し、定電位電解を行
った際の経時変化を示すものであり、横軸は時間、縦軸
は電流（初期電流を100とした任意単位a.μ，）を示
す。The drawing shows the change over time when various heavy metals are electrically connected to the negative electrode and constant potential electrolysis is performed. The horizontal axis is time, and the vertical axis is current (arbitrary unit a.μ, where the initial current is 100). Is shown.
Claims (1)
属よりなる負極と、ニッケル金属からなる負極集電体
と、少なくともジオキソラン系の溶媒を含む電解液と、
溶解電位が前記負極構成軽金属より高く且つ前記負極集
電体であるニッケル金属より低い重金属とを具備し、 前記重金属が前記負極と電気的に接続され且つ電解液と
接触していることを特徴とする非水電解液電池。1. A positive electrode, a negative electrode made of a light metal such as lithium or sodium, a negative electrode current collector made of nickel metal, and an electrolytic solution containing at least a dioxolane-based solvent.
And a heavy metal having a dissolution potential higher than the light metal constituting the negative electrode and lower than the nickel metal serving as the negative electrode current collector, wherein the heavy metal is electrically connected to the negative electrode and is in contact with the electrolytic solution. Non-aqueous electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008366A JP2765906B2 (en) | 1989-01-17 | 1989-01-17 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008366A JP2765906B2 (en) | 1989-01-17 | 1989-01-17 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02189866A JPH02189866A (en) | 1990-07-25 |
| JP2765906B2 true JP2765906B2 (en) | 1998-06-18 |
Family
ID=11691240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1008366A Expired - Fee Related JP2765906B2 (en) | 1989-01-17 | 1989-01-17 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2765906B2 (en) |
-
1989
- 1989-01-17 JP JP1008366A patent/JP2765906B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02189866A (en) | 1990-07-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |