JPH0673302B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0673302B2 JPH0673302B2 JP60057101A JP5710185A JPH0673302B2 JP H0673302 B2 JPH0673302 B2 JP H0673302B2 JP 60057101 A JP60057101 A JP 60057101A JP 5710185 A JP5710185 A JP 5710185A JP H0673302 B2 JPH0673302 B2 JP H0673302B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- aqueous electrolyte
- positive electrode
- aluminum chloride
- 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 - Lifetime
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
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明はリチウム又はリチウム合金を活物質とする負極
と、非水電解液と、正極とを備える非水電解液電池に関
するものである。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte battery including a negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolyte, and a positive electrode.
（ロ）従来の技術 非水電解液電池としては、二酸化マンガンやフッ化炭素
などを正極活物質とする3V系が既に実用化されており、
また例えば特開昭55-137669号公報に開示されているよ
うに酸化第二銅、二硫化鉄、三酸化ビスマスなどを正極
活物質とする1.5V系も提案されている。(B) Conventional technology As a non-aqueous electrolyte battery, a 3V system using manganese dioxide, fluorocarbon, etc. as a positive electrode active material has already been put into practical use.
Also, for example, as disclosed in Japanese Patent Laid-Open No. 55-137669, a 1.5V system using cupric oxide, iron disulfide, bismuth trioxide, etc. as a positive electrode active material has been proposed.
ところでこの種電池は負極活物質として水分との反応性
に富むリチウムを用いるため電池組立に際しては水分の
混入を阻止するように工夫されている。しかしながら、
電池保存中に外部から水分が侵入し、その水分とリチウ
ムとが反応してリチウム極表面に水酸化リチウムよりな
る絶縁被膜が生成して内部抵抗が上昇し、放電容量が低
下するという問題があった。By the way, since this type of battery uses lithium, which is highly reactive with water, as a negative electrode active material, it is devised to prevent the mixing of water during battery assembly. However,
There is a problem that moisture enters from the outside during storage of the battery and the moisture reacts with lithium to form an insulating coating made of lithium hydroxide on the lithium electrode surface, increasing the internal resistance and reducing the discharge capacity. It was
（ハ）発明が解決しようとする問題点 本発明は非水電解液電池の保存特性を改善することを主
たる目的とする。(C) Problems to be Solved by the Invention The main object of the present invention is to improve the storage characteristics of a non-aqueous electrolyte battery.
更に、本発明は特に酸化第二銅、二硫化鉄、三酸化ビス
マスなどを正極活物質とする1.5V系電池の保存後の開回
路電圧の上昇を抑制することを目的とする。1.5V系電池
を組立てた場合、正極中の不純物または活性な部分の影
響で初期の開回路電圧は約3.0Vを示し、1.5V用の回路を
組込んだ機器を損傷する懸念がある。A further object of the present invention is to suppress an increase in open circuit voltage after storage of a 1.5 V system battery that uses cupric oxide, iron disulfide, bismuth trioxide or the like as a positive electrode active material. When a 1.5V battery is assembled, the initial open circuit voltage is about 3.0V due to the influence of impurities or active parts in the positive electrode, and there is a concern that the device incorporating the 1.5V circuit may be damaged.
そこで、従来では電池組立後、前処理放電を行なうこと
によって初期の開回路電圧の上昇部分をカットすること
が一般に行なわれている。しかしながら、この電池を保
存していると、また開回路電圧が上昇するという問題が
あった。Therefore, conventionally, after the battery is assembled, pretreatment discharge is generally performed to cut off the initial rising portion of the open circuit voltage. However, there is a problem that the open circuit voltage rises again when the battery is stored.
（ニ）問題点を解決するための手段 特許請求の範囲第項記載の発明に係る非水電解液電池
は、金属リチウムからなる負極と、溶媒及び溶質からな
る非水電解液と、正極とを備えるものであって、前記非
水電解液に塩化アルミニウムリチウムを0.0001〜0.001
モル/l添加したことを特徴とするものである。(D) Means for Solving the Problems A non-aqueous electrolyte battery according to the invention of claim 1 comprises a negative electrode made of metallic lithium, a non-aqueous electrolyte made of a solvent and a solute, and a positive electrode. It is provided with 0.0001 to 0.001 lithium aluminum chloride in the non-aqueous electrolyte.
It is characterized by the addition of mol / l.
また、特許請求の範囲第項記載の発明に係る非水電解
液電池は、金属リチウムからなる負極と、溶媒及び溶質
からなる非水電解液と、正極とを備えるものであって、
前記非水電解液に塩化アルミニウムを0.001〜0.1モル/l
添加したことを特徴とするものである。Further, the non-aqueous electrolyte battery according to the invention of claims, comprising a negative electrode composed of metallic lithium, a non-aqueous electrolyte solution composed of a solvent and a solute, and a positive electrode,
Aluminum chloride 0.001 ~ 0.1 mol / l in the non-aqueous electrolyte
It is characterized by being added.
（ホ）作用 塩化アルミニウム或いは塩化アルミニウムリチウムを電
解液中に添加すると、アルミニウムイオンがリチウム金
属と置換しリチウム負極表面にリチウム−アルミニウム
被膜が形成されることになる、その結果、例え外部から
水分が侵入してもリチウム−アルミニウム被膜によって
水酸化リチウム絶縁被膜の生成が抑制される。(E) Action When aluminum chloride or lithium aluminum chloride is added to the electrolytic solution, aluminum ions replace lithium metal to form a lithium-aluminum coating on the surface of the lithium negative electrode. As a result, moisture from the outside is removed. Even if it penetrates, the lithium-aluminum coating suppresses the formation of the lithium hydroxide insulating coating.
但し、塩化アルミニウムの添加量が0.0001モル/l未満で
ある場合、又は、塩化アルミニウムリチウムの添加量が
0.001モル/l未満である場合には、充分な厚さのリチウ
ム−アルミニウム被膜がリチウム負極表面に形成されな
いために、外部から水が侵入するとリチウム負極表面に
水酸化リチウム絶縁被膜が形成され、保存特性を充分に
改善することができない。一方、塩化アルミニウムの添
加量が0.001モル/lを超える場合には非水電解液に塩化
アルミニウムが溶解せず塩化アルミニウムが析出し、ま
た塩化アルミニウムリチウムの添加量が0.1モル/lを超
える場合には、保存後の電池の内部抵抗が上昇する。However, when the addition amount of aluminum chloride is less than 0.0001 mol / l, or when the addition amount of lithium aluminum chloride is
If the amount is less than 0.001 mol / l, a lithium-aluminum coating of sufficient thickness cannot be formed on the surface of the lithium negative electrode. The characteristics cannot be improved sufficiently. On the other hand, when the addition amount of aluminum chloride exceeds 0.001 mol / l, aluminum chloride does not dissolve in the non-aqueous electrolyte and aluminum chloride is deposited, and when the addition amount of lithium aluminum chloride exceeds 0.1 mol / l. Causes the internal resistance of the battery to increase after storage.
更に、またアルミニウムイオンが正極中の不純物や活性
な部分と反応して、これらの存在に起因する保存後の開
回路電圧の上昇を抑制することができ、特に1.5V系電池
において有益である。Furthermore, aluminum ions can also react with impurities and active parts in the positive electrode to suppress the rise in open circuit voltage after storage due to their presence, which is particularly useful in 1.5V batteries.
（ヘ）実施例 実施例1. 正極は、市販特級の酸化第二銅85重量％に導電剤として
の黒鉛を10重量％、結着剤としてのフッ素樹脂粉末を５
重量％を加えて充分混合した後、この混合物を約２トン
／cm2の圧力で加圧成型して径15.0mm、厚み1.1mmの成型
体を得、この成型体を200〜300℃の温度で熱処理したる
ものである。(F) Examples Example 1. The positive electrode was composed of 85% by weight of commercially available special grade cupric oxide, 10% by weight of graphite as a conductive agent, and 5% of fluororesin powder as a binder.
After adding wt% and mixing well, this mixture is pressure-molded at a pressure of about 2 tons / cm 2 to obtain a molded body having a diameter of 15.0 mm and a thickness of 1.1 mm. The molded body is heated at a temperature of 200 to 300 ° C. It is heat treated in.
負極はリチウム板を約0.6mmの厚みに圧延し、このリチ
ウム圧延板を径15.0mmに打抜いたものである。The negative electrode is obtained by rolling a lithium plate to a thickness of about 0.6 mm and punching this rolled lithium plate to a diameter of 15.0 mm.
而して電解液はプロピレンカーボネートと1.2ジメトキ
シエタンとの混合溶媒に過塩素酸リチウムを1.0モル/l
溶解させ、さらに塩化アルミニウムを0.001モル/l添加
したものを用い、またセパレータはポリプロピレン不織
布を用いて直径20.0mm、厚み2.5mmの本発明電池(A1)を
作成した。Thus, the electrolyte is 1.0 mol / l lithium perchlorate in a mixed solvent of propylene carbonate and 1.2 dimethoxyethane.
A battery (A 1 ) of the present invention having a diameter of 20.0 mm and a thickness of 2.5 mm was prepared by using a material obtained by dissolving and further adding 0.001 mol / l of aluminum chloride, and using a polypropylene nonwoven fabric as a separator.
実施例2. 実施例１における電解液において、添加剤としての塩化
アルミニウムに代えて塩化アルミニウムリチウムを0.01
モル/l添加することを除いて他は実施例１と同様の本発
明電池(A2)を作成した。第１図は本発明電池の縦断面図
を示し、（１）は酸化第二銅正極であって、正極集電体
（２）を介して正極缶（３）の内底面に圧接されてい
る。（４）はリチウム負極であって負極集電体（５）を
介して負極缶（６）の内底面に圧着されている。（７）
はセパレータ、（８）は絶縁パッキング、（９）は正極
内缶である。Example 2. In the electrolytic solution of Example 1, 0.01% lithium aluminum chloride was used instead of aluminum chloride as an additive.
A battery of the present invention (A 2 ) was prepared in the same manner as in Example 1 except that mol / l was added. FIG. 1 shows a vertical cross-sectional view of the battery of the present invention, in which (1) is a cupric oxide positive electrode, which is pressed against the inner bottom surface of the positive electrode can (3) through the positive electrode current collector (2). . (4) is a lithium negative electrode, which is pressure-bonded to the inner bottom surface of the negative electrode can (6) through the negative electrode current collector (5). (7)
Is a separator, (8) is an insulating packing, and (9) is a positive electrode inner can.
比較例 電解液としてプロピレンカーボネートと1.2ジメトキシ
エタンとの混合溶媒に過塩素酸リチウムを１モル/l溶解
したのみで添加剤を加えないものを用い、他は実施例１
と同様の比較電池（Ｂ）を作成した。Comparative Example As an electrolytic solution, a solution obtained by dissolving 1 mol / l of lithium perchlorate in a mixed solvent of propylene carbonate and 1.2 dimethoxyethane and adding no additive was used.
A comparative battery (B) similar to the above was prepared.
第２図はこれら電池を温度60℃、湿度90％の条件下で保
存した時の内部抵抗の経時変化を示す。FIG. 2 shows changes with time in internal resistance when these batteries were stored under the conditions of a temperature of 60 ° C. and a humidity of 90%.
また、第３図はこれら電池を組立後、理論容量の５％を
前処理放電したのちの開回路電圧の経時変化を示す。Further, FIG. 3 shows a change with time of the open circuit voltage after pre-discharge of 5% of the theoretical capacity after assembling these batteries.
更に、第４図及び第５図は塩化アルミニウム及び塩化ア
ルミニウムリチウムの添加量を夫々種々変化させ、温度
60℃、湿度90％の条件下で１ケ月保存した後の内部抵抗
を比較したものである。Further, in FIGS. 4 and 5, the amounts of aluminum chloride and lithium aluminum chloride added were changed variously, and
This is a comparison of the internal resistance after storage for 1 month at 60 ° C and 90% humidity.
第２図より本発明電池(A1)(A2)は比較電池（Ｂ）に比し
て保存後の内部抵抗の上昇が抑制されているのがわか
る。この理由は本発明電池の場合、電解液に添加した塩
化アルミニウム或いは塩化アルミニウムリチウムのアル
ミニウムイオンがリチウム金属と置換しリチウム負極表
面にリチウム−アルミニウム被膜が形成されることにな
り、その結果、例えば保存時に外部から水分が侵入して
もリチウム−アルミニウム被膜によって水酸化リチウム
絶縁被膜の生成が抑制されるためであると考えられる。It can be seen from FIG. 2 that the batteries (A 1 ) and (A 2 ) of the present invention have suppressed increase in internal resistance after storage as compared with the comparative battery (B). The reason for this is that in the case of the battery of the present invention, aluminum ions of aluminum chloride or lithium aluminum chloride added to the electrolytic solution are replaced with lithium metal to form a lithium-aluminum coating film on the surface of the lithium negative electrode. It is considered that the lithium-aluminum film suppresses the formation of the lithium hydroxide insulating film even when water enters from the outside.
また、第３図より保存後の開回路電圧の上昇が抑制され
ているのがわかる。この理由は塩化アルミニウム或いは
塩化アルミニウムリチウムのアルミニウムイオンが正極
中の不純物や活性な部分と反応することによるものと考
えられる。即ちリチウムは金属の中で最も卑な電位を有
するものであり、正極中の不純物や活性な部分と局部電
池を形成すると第３図の比較電池（Ｂ）のように高い開
回路電圧を示すが、本発明電池の場合、リチウムより優
先してアルミニウムが反応に関与するため開回路電圧の
上昇を抑制することができるのである。尚、比較電池
（Ｂ）の場合においてさえ、開回路電圧は約3.0V程度で
あるため、3.0V系の非水電解液電池においては特に支障
はないが、1.5V系電池においては極めて有害であるた
め、特に1.5V系電池において本発明は有益なるものであ
る。Further, it can be seen from FIG. 3 that the increase in open circuit voltage after storage is suppressed. It is considered that this is because aluminum ions of aluminum chloride or lithium aluminum chloride react with impurities and active portions in the positive electrode. That is, lithium has the lowest base potential among metals, and when a local battery is formed with impurities or an active part in the positive electrode, it exhibits a high open circuit voltage like the comparative battery (B) in FIG. In the case of the battery of the present invention, since aluminum participates in the reaction in preference to lithium, an increase in open circuit voltage can be suppressed. Even in the case of the comparative battery (B), since the open circuit voltage is about 3.0V, there is no problem in the 3.0V non-aqueous electrolyte battery, but it is extremely harmful in the 1.5V battery. Therefore, the present invention is particularly useful in a 1.5V battery.
更に、第４図より塩化アルミニウムの添加量を0.0001〜
0.001モル/lに、また第５図より塩化アルミニウムリチ
ウムの添加量を0.001〜0.1モル/lに、それぞれ規制する
ことにより保存後の内部抵抗の上昇の少ない非水電解液
電池が得られることが分かる。Further, from FIG. 4, the addition amount of aluminum chloride is 0.0001-
By controlling the amount of lithium aluminum chloride added to 0.001 mol / l and 0.001 to 0.1 mol / l from Fig. 5, respectively, it is possible to obtain a non-aqueous electrolyte battery with little increase in internal resistance after storage. I understand.
（ト）発明の効果 上述した如く、金属リチウムからなる負極を備えた非水
電解液電池において、非水電解液に塩化アルミニウム或
いは塩化アルミニウムリチウムを所定量添加することに
より保存後の内部抵抗の上昇を抑制することができ保存
特性を改善しうるものであり、その工業的価値は極めて
大なるものである。(G) Effect of the Invention As described above, in a non-aqueous electrolyte battery provided with a negative electrode made of metallic lithium, the internal resistance after storage is increased by adding a predetermined amount of aluminum chloride or lithium aluminum chloride to the non-aqueous electrolyte. Can be suppressed and the storage characteristics can be improved, and its industrial value is extremely great.
また、特に本発明は正極活物質として酸化第二銅、二硫
化鉄、三酸化ビスマスなどのように負極のリチウムと組
合せて電池電圧が約1.5Vを示す金属化合物を用いた電池
に適用すれば、保存後の開回路電圧を因とする不都合を
抑制しうるという付加的な効果も奏するものである。Further, in particular, the present invention can be applied to a battery using a metal compound having a battery voltage of about 1.5 V in combination with lithium of the negative electrode such as cupric oxide, iron disulfide, and bismuth trioxide as the positive electrode active material. Also, it has an additional effect that it is possible to suppress the inconvenience caused by the open circuit voltage after storage.
第１図は本発明電池の縦断面図、第２図乃至第３図は本
発明電池と比較電池との電池特性比較図であって、第２
図は内部抵抗と保存期間との関係を示す図、第３図は開
回路電圧の経時変化を示す図、また第４図は塩化アルミ
ニウムの添加量と内部抵抗との関係を示す図、第５図は
塩化アルミニウムリチウムの添加量と内部抵抗との関係
を示す図である。 （１）……正極、（２）……正極集電体、（３）……正
極缶、（４）……リチウム負極、（５）……負極集電
体、（６）……負極缶、（７）……セパレータ、（８）
……絶縁パッキング、(A1)(A2)……本発明電池、（Ｂ）
……比較電池。FIG. 1 is a longitudinal sectional view of the battery of the present invention, and FIGS. 2 to 3 are battery characteristic comparison diagrams of the battery of the present invention and a comparative battery.
The figure shows the relationship between the internal resistance and the storage period, FIG. 3 shows the change over time of the open circuit voltage, and FIG. 4 shows the relationship between the added amount of aluminum chloride and the internal resistance. The figure shows the relationship between the amount of lithium aluminum chloride added and the internal resistance. (1) ... Positive electrode, (2) ... Positive electrode collector, (3) ... Positive electrode can, (4) ... Lithium negative electrode, (5) ... Negative electrode collector, (6) ... Negative electrode can , (7) …… Separator, (8)
...... Insulation packing, (A 1 ) (A 2 ) …… Battery of the present invention, (B)
…… Comparison battery.
Claims (4)
質からなる非水電解液と、正極とを備えるものであっ
て、前記非水電解液に塩化アルミニウムを0.0001〜0.00
1モル/l添加したことを特徴とする非水電解液電池。1. A negative electrode comprising metallic lithium, a non-aqueous electrolytic solution comprising a solvent and a solute, and a positive electrode, wherein 0.0001 to 0.00 of aluminum chloride is added to the non-aqueous electrolytic solution.
A non-aqueous electrolyte battery containing 1 mol / l.
鉄、三酸化ビスマスなどのように負極の金属リチウムと
組合せて電池電圧が約1.5Vを示す金属化合物よりなる特
許請求の範囲第項記載の非水電解液電池。2. The positive electrode active material comprises a metal compound such as cupric oxide, iron disulfide, bismuth trioxide, etc., which exhibits a battery voltage of about 1.5 V in combination with metallic lithium of the negative electrode. The non-aqueous electrolyte battery according to the above item.
質からなる非水電解液と、正極とを備えるものであっ
て、前記非水電解液に塩化アルミニウムリチウムを0.00
1〜0.1モル/l添加したことを特徴とする非水電解液電
池。3. A negative electrode comprising metallic lithium, a non-aqueous electrolytic solution comprising a solvent and a solute, and a positive electrode, wherein the non-aqueous electrolytic solution contains lithium aluminum chloride in an amount of 0.00
A non-aqueous electrolyte battery containing 1 to 0.1 mol / l.
鉄、三酸化ビスマスなどのように負極の金属リチウムと
組合せて電池電圧が約1.5Vを示す金属化合物よりなる特
許請求の範囲第項記載の非水電解液電池。4. The positive electrode active material comprises a metal compound such as cupric oxide, iron disulfide, bismuth trioxide, etc., which exhibits a battery voltage of about 1.5 V in combination with metallic lithium of the negative electrode. The non-aqueous electrolyte battery according to the above item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60057101A JPH0673302B2 (en) | 1985-03-20 | 1985-03-20 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60057101A JPH0673302B2 (en) | 1985-03-20 | 1985-03-20 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61216247A JPS61216247A (en) | 1986-09-25 |
| JPH0673302B2 true JPH0673302B2 (en) | 1994-09-14 |
Family
ID=13046112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60057101A Expired - Lifetime JPH0673302B2 (en) | 1985-03-20 | 1985-03-20 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0673302B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL63120A (en) * | 1981-06-18 | 1985-01-31 | Tadiran Israel Elect Ind Ltd | Safety device for electrochemical cells |
| JPS5987774A (en) * | 1982-11-10 | 1984-05-21 | Hitachi Maxell Ltd | Manufacture of solute for nonaqueous electrolyte |
| US4517736A (en) * | 1984-03-21 | 1985-05-21 | Gte Communications Products Corp. | Method of fabrication of an electrochemical cell |
-
1985
- 1985-03-20 JP JP60057101A patent/JPH0673302B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPS61216247A (en) | 1986-09-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |