JPH0654663B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0654663B2 JPH0654663B2 JP60013003A JP1300385A JPH0654663B2 JP H0654663 B2 JPH0654663 B2 JP H0654663B2 JP 60013003 A JP60013003 A JP 60013003A JP 1300385 A JP1300385 A JP 1300385A JP H0654663 B2 JPH0654663 B2 JP H0654663B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- aqueous electrolyte
- active material
- lithium
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 (イ) 産業上の利用分野 本発明は酸化第二銅を正極活物質する非水電解液電池に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a non-aqueous electrolyte battery containing cupric oxide as a positive electrode active material.
(ロ) 従来の技術 酸化第二銅を正極活物質とし、リチウム又はリチウム合
金を負極活物質とする非水電解液電池は例えば特公昭59
-33935号公報で公知であり、その電池電圧は約1.4Ｖ程
度であるので電子機器の電源に汎用されている酸化銀電
池や水銀電池と互換使用し得る利点がある。(B) Conventional technology A non-aqueous electrolyte battery using cupric oxide as a positive electrode active material and lithium or a lithium alloy as a negative electrode active material is disclosed in, for example, Japanese Patent Publication Sho 59.
-33935, the battery voltage is about 1.4 V, so that it has an advantage that it can be used interchangeably with a silver oxide battery or a mercury battery that is widely used as a power source for electronic devices.
ところが、この種電池は保存時、正極活物質としての酸
化第二銅が分解して電解液中に金属銅が溶解し、この金
属銅がリチウム負極表面に析出して内部抵抗が上昇し電
池の放電容量が低下するという問題がある。However, in this type of battery, during storage, cupric oxide as the positive electrode active material is decomposed and metallic copper is dissolved in the electrolytic solution, and the metallic copper is deposited on the surface of the lithium negative electrode to increase the internal resistance of the battery. There is a problem that the discharge capacity decreases.
(ハ) 発明が解決しようとする問題点 本発明は酸化第二銅を正極活物質とし、リチウムまたは
リチウム合金を負極活物質とする非水電解液電池の保存
特性を改善することを目的とするものである。(C) Problems to be Solved by the Invention The present invention aims to improve the storage characteristics of a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material and lithium or a lithium alloy as a negative electrode active material. It is a thing.
(ニ) 問題点を解決するための手段 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、酸化第二銅を活物質とする正極と
を備える非水電解液電池であって、正極に硫化鉄及び硫
化第二銅からなる二成分添加剤を、酸化第二銅に対して
５〜４０重量％添加したことを特徴とするものである。(D) Means for Solving the Problems The present invention provides a non-aqueous electrolytic solution comprising a negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolytic solution, and a positive electrode using cupric oxide as an active material. A battery is characterized in that a two-component additive composed of iron sulfide and cupric sulfide is added to the positive electrode in an amount of 5 to 40% by weight with respect to cupric oxide.
(ホ) 作 用 酸化第二銅を活物質とする正極に硫化鉄及び硫化第二銅
を添加すると、酸化第二銅の分解が抑制されると共に、
硫化鉄、硫化第二銅の一部が溶解して生成される硫黄
が、リチウム負極表面に皮膜として析出し、リチウム負
極表面に金属銅が析出するのを抑制することができる。(E) Working Addition of iron sulfide and cupric sulfide to the positive electrode whose active material is cupric oxide suppresses the decomposition of cupric oxide, and
It is possible to prevent sulfur produced by dissolving part of iron sulfide and cupric sulfide from being deposited as a film on the surface of the lithium negative electrode and depositing metallic copper on the surface of the lithium negative electrode.
(ヘ) 実施例 以下本発明の実施例について詳述する。(F) Examples Hereinafter, examples of the present invention will be described in detail.
市販特級の酸化第二銅に対して硫化鉄15重量％及び硫化
第二銅15重量％を混合した正極合剤85重量％に、導電剤
としてのアセチレンブラック及び黒鉛を10重量％、結着
剤としてのフッ素樹脂粉末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℃の温度で熱処理して正極とする。85% by weight of a positive electrode mixture, which is 15% by weight of iron sulfide and 15% by weight of cupric sulfide mixed with commercial grade cupric oxide, 10% by weight of acetylene black and graphite as a conductive agent, and a binder. After adding 5% by weight of fluororesin powder as a mixture and mixing thoroughly, this mixture is pressure-molded at a pressure of about 2 ton / cm 2 to obtain a molded body having a diameter of 15.0 mm and a thickness of 1.1 mm. 200 ~
Heat treatment is performed at a temperature of 300 ° C to obtain a positive electrode.
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。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モル／溶解させたもので
あり、セパレータに含浸して用い直径20.0mm、厚み2.5m
mの電池(Ａ)を作成した。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. The electrolyte is a mixed solvent of propylene carbonate and 1.2 dimethoxyethane in which 1 mol / mol of lithium perchlorate is dissolved and used by impregnating the separator with a diameter of 20.0 mm and a thickness of 2.5 m.
A battery (A) of m was prepared.
第１図は本発明電池の縦断面図を示し、(１)は酸化第二
銅を活物質とし硫化鉄及び硫化第二銅を添加した正極、
(２)はリチウム負極、(３)は電解液を含浸したセパレー
タである。又(４)は正極リング、(５)は正極集電体、
(６)は負極集電体、(７)(８)は正負極外装缶、(９)は絶
縁パッキングである。FIG. 1 shows a vertical cross-sectional view of a battery of the present invention, (1) is a positive electrode containing cupric oxide as an active material and iron sulfide and cupric sulfide added thereto,
(2) is a lithium negative electrode, and (3) is a separator impregnated with an electrolytic solution. Also, (4) is the positive electrode ring, (5) is the positive electrode current collector,
(6) is a negative electrode current collector, (7) and (8) are positive and negative electrode outer cans, and (9) is an insulating packing.
ついで本発明電池の優位性を調べるために、酸化第二銅
正極に硫化鉄及び硫化第二銅を添加しないことを除いて
他は本発明電池と同様の比較電池(Ｂ)を作成した。Then, in order to examine the superiority of the battery of the present invention, a comparative battery (B) similar to the battery of the present invention was prepared except that iron sulfide and cupric sulfide were not added to the cupric oxide positive electrode.
第２図はこれらの電池を温度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 at a temperature of 60 ° C. and a humidity of 90%.
又、第３図はこれら電池の20℃、5.6kl定負荷放電時の
放電特性を示し、実線は初期特性、破線は電池組立後、
温度60℃、湿度90％の条件下で20日間保存した後の放電
特性を示す。In addition, Fig. 3 shows the discharge characteristics of these batteries when discharged at a constant load of 5.6 kl at 20 ° C. The solid line shows the initial characteristics, and the broken line shows the battery after assembly.
The discharge characteristics after storage for 20 days at a temperature of 60 ° C and a humidity of 90% are shown.
第２図及び第３図より本発明電池(Ａ)は比較電池(Ｂ)に
比して特に高温、高湿下における保存特性が改善されて
いるのがわかる。It can be seen from FIGS. 2 and 3 that the battery (A) of the present invention has improved storage characteristics especially under high temperature and high humidity as compared with the comparative battery (B).
この理由を考察するに、本発明電池において酸化第二銅
を活物質とする正極に硫化鉄及び硫化第二銅を添加する
と、酸化第二銅の分解が抑制されると共に硫化鉄、硫化
第二銅の一部が溶解して生成される硫黄がリチウム負極
表面に皮膜として析出するため、たとえ酸化第二銅が分
解して電解液中に金属銅が溶解してもリチウム負極表面
に金属銅が析出するのを抑制しうるので内部抵抗の上昇
が抑えられ保存特性が改善されると考えられる。尚、硫
黄の皮膜は放電によって容易に破壊されるため放電特性
に悪影響を与えることはない。Considering this reason, when iron sulfide and cupric sulfide are added to the positive electrode having cupric oxide as an active material in the battery of the present invention, decomposition of cupric oxide is suppressed and iron sulfide and cupric sulfide are suppressed. Since sulfur produced by dissolving a part of copper is deposited as a film on the surface of the lithium negative electrode, even if cupric oxide is decomposed and metallic copper is dissolved in the electrolytic solution, metallic copper remains on the surface of the lithium negative electrode. It is considered that since the precipitation can be suppressed, the increase in internal resistance is suppressed and the storage characteristics are improved. Since the sulfur film is easily destroyed by discharge, it does not adversely affect the discharge characteristics.
(ト) 発明の効果 上述した如く、酸化第二銅を活物質とする正極を備えた
非水電解液電池において、正極に硫化鉄及び硫化第二銅
からなる二成分添加剤を、酸化第二銅に対して５〜４０
重量％添加することにより、保存特性に優れた非水電解
液電池を得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) Effects of the Invention As described above, in a non-aqueous electrolyte battery including a positive electrode using cupric oxide as an active material, a two-component additive composed of iron sulfide and cupric sulfide is added to the positive 5-40 for copper
A non-aqueous electrolyte battery having excellent storage characteristics can be obtained by adding it in a weight percentage, and its industrial value is extremely large.
第１図は本発明電池の縦断面図、第２図は内部抵抗と保
存期間との関係を示す図、第３図は電池の放電特性を示
す。 (１)……正極、(２)……負極、(３)……セパレータ、
(４)……正極リング、(５)……正極集電体、(６)……負
極集電体、(７)(８)……正負極外装缶、(９)……絶縁パ
ッキング、(Ａ)……本発明電池、(Ｂ)……比較電池。FIG. 1 is a vertical cross-sectional view of the battery of the present invention, FIG. 2 is a diagram showing the relationship between internal resistance and storage period, and FIG. 3 is a discharge characteristic of the battery. (1) …… Positive electrode, (2) …… Negative electrode, (3) …… Separator,
(4) …… Positive electrode ring, (5) …… Positive electrode current collector, (6) …… Negative electrode current collector, (7) (8) …… Positive and negative electrode outer can, (9) …… Insulating packing, ( A) ... Invention battery, (B) ... Comparison battery.
Claims (1)
負極と、非水電解液と、酸化第二銅を活物質とする正極
とを備えるものであって、前記正極に硫化鉄及び硫化第
二銅からなる二成分添加剤を前記酸化第二銅に対して５
〜４０重量％添加したことを特徴とする非水電解液電
池。1. A negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolyte, and a positive electrode using cupric oxide as an active material, wherein the positive electrode is iron sulfide or second sulfide. A two-component additive made of copper was added to the cupric oxide in an amount of 5
A non-aqueous electrolyte battery characterized by being added in an amount of -40% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60013003A JPH0654663B2 (en) | 1985-01-25 | 1985-01-25 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60013003A JPH0654663B2 (en) | 1985-01-25 | 1985-01-25 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61173455A JPS61173455A (en) | 1986-08-05 |
| JPH0654663B2 true JPH0654663B2 (en) | 1994-07-20 |
Family
ID=11821000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60013003A Expired - Lifetime JPH0654663B2 (en) | 1985-01-25 | 1985-01-25 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0654663B2 (en) |
-
1985
- 1985-01-25 JP JP60013003A patent/JPH0654663B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61173455A (en) | 1986-08-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |