JPH0746603B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0746603B2 JPH0746603B2 JP62006535A JP653587A JPH0746603B2 JP H0746603 B2 JPH0746603 B2 JP H0746603B2 JP 62006535 A JP62006535 A JP 62006535A JP 653587 A JP653587 A JP 653587A JP H0746603 B2 JPH0746603 B2 JP H0746603B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- aqueous electrolyte
- open circuit
- circuit voltage
- fexs
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
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負極活物質とし、
酸化第二銅を正極活物質と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 uses lithium or a lithium alloy as a negative electrode active material,
The present invention relates to a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material.
（ロ）従来の技術 この種電池は例えば特公昭59-33935号公報に開示されて
おり、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アルカリ乾電池、水銀電池或いは
銀電池等と互換使用しうる利点がある。(B) Conventional technology This type of battery is disclosed in, for example, Japanese Patent Publication No. 59-33935, and since the battery voltage is about 1.4 V, it is an alkaline dry battery, a mercury battery or It has the advantage that it can be used interchangeably with silver batteries.
（ハ）発明が解決しようとする問題点 ところが、この電池は電池組立後の開回路電圧が約3V程
度と高く、そのため予備放電して開回路電圧を下げるよ
うに対処しているが、保存時にまた開回路電圧が上昇し
使用電子機器に悪影響を与えるという問題がある。(C) Problems to be solved by the invention However, this battery has a high open circuit voltage of about 3 V after the battery is assembled, and therefore, we have taken measures to reduce the open circuit voltage by pre-discharging, but during storage Further, there is a problem that the open circuit voltage rises and adversely affects the electronic equipment used.
本発明は斯る問題点に鑑みなされたものであり、保存時
における開回路電圧の上昇を抑制することを目的とする
ものである。The present invention has been made in view of such problems, and an object thereof is to suppress an increase in open circuit voltage during storage.
（ニ）問題点を解決するための手段 本発明は酸化第二銅を活物質とする正極にFexS（但し0.
55≦ｘ≦0.65）を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 positive electrode using cupric oxide as an active material with FexS (however, 0.
55 ≦ x ≦ 0.65) is added.
（ホ）作用 酸化第二銅に、ｘ値が0.55以上であるFexSを添加すると
FexSの電位が約1.7V程度と低いため、酸化第二銅単独の
場合に比して低い混成電圧が得られることになり開回路
電圧の上昇を抑制しうると共にｘ値が0.65以下であるFe
xSを添加すると放電容量の劣化を抑制することができ
る。それ故、ｘ値が0.55以上で0.65以下であるFexSを添
加すれば保存時の開回路電圧の上昇が抑制でき且放電容
量の劣化の小さい電池を得ることができる。(E) Action When FexS with an x value of 0.55 or more is added to cupric oxide,
Since the FexS potential is as low as about 1.7 V, a lower hybrid voltage can be obtained compared to the case of using cupric oxide alone, which can suppress the increase in open circuit voltage and the x value is 0.65 or less.
Addition of xS can suppress deterioration of discharge capacity. Therefore, by adding FexS having an x value of 0.55 or more and 0.65 or less, it is possible to obtain a battery in which the increase in open circuit voltage during storage can be suppressed and the discharge capacity is less deteriorated.
（ヘ）実施例 市販特級の酸化第二銅75重量％にFe0.6Sを10重量％、導
電剤としての黒鉛10重量％及び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、約２トン／cm
2の圧力で加圧成型して径10.0mm、厚み0.6mm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。(F) Example: Fe0.6S (10% by weight), graphite (10% by weight) as a conductive agent, and fluororesin powder (5% by weight) as a binder were added to 75% by weight of cupric oxide (commercial grade) and mixed well. Later, about 2 tons / cm
A molded body having a diameter of 10.0 mm and a thickness of 0.6 mm is obtained by pressure molding at a pressure of 2 , and the molded body is heat-treated at a temperature of 200 to 300 ° C. to obtain a positive electrode.
負極はリチウム板を約0.4mmの厚みに圧延しこのリチウ
ム圧延板を径10.0mmに打抜いたものを用い、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LiClO4を１モル/l溶解したものを用い、又セパレ
ータとしてポリプロピレン不織布を用いて径20.0mm、厚
み2.5mmの本発明電池（Ａ）を作成した。The negative electrode was prepared by rolling a lithium plate to a thickness of about 0.4 mm and punching out this rolled lithium plate to a diameter of 10.0 mm. The electrolyte was 1 mol / l of LiClO 4 in a mixed solvent of propylene carbonate and 1.2 dimethoxyethane. A battery (A) of the present invention having a diameter of 20.0 mm and a thickness of 2.5 mm was prepared by using the melted material and polypropylene nonwoven fabric as a separator.
尚、本発明電池の優位性を調べるために正極にFe0.6Sを
添加しないことを除いて他は実施例と同様の比較電池
（Ｂ）を作成した。In order to investigate the superiority of the battery of the present invention, a comparative battery (B) similar to that of the example except that Fe0.6S was not added to the positive electrode was prepared.
第１図はこれらの電池を温度60℃、湿度90％の条件下で
保存した時の開回路電圧の経時変化を示す。尚、これら
の電池は電池組立後に理論容量の５％を予備放電して完
成電池としたものである。第１図より本発明電池（Ａ）
は保存時における開回路電圧の上昇が抑制されているの
がわかる。FIG. 1 shows changes with time in open circuit voltage when these batteries were stored under the conditions of temperature of 60 ° C. and humidity of 90%. Incidentally, these batteries were completed batteries by pre-discharging 5% of the theoretical capacity after battery assembly. From FIG. 1, the battery of the present invention (A)
It can be seen that the increase in open circuit voltage during storage is suppressed.
第２図は温度60℃、湿度90％の条件下で30日保存した
後、温度25℃、負荷10kΩで放電した時のFe0.6Sの添加
量に対する開回路電圧及び利用率（実質容量／理論容量
×100）の関係を示す図である。第２図よりFe0.6Sの添
加量としては正極に対して５〜30重量％の範囲が好まし
いことがわかる。Figure 2 shows the open circuit voltage and utilization factor (real capacity / theoretical ratio) with respect to the amount of Fe0.6S added when discharged at a temperature of 25 ° C and a load of 10 kΩ after storage for 30 days at a temperature of 60 ° C and a humidity of 90%. It is a figure which shows the relationship of capacity * 100). It can be seen from FIG. 2 that the addition amount of Fe0.6S is preferably in the range of 5 to 30% by weight with respect to the positive electrode.
第３図は温度60℃、湿度90％の条件下で30日保存した
後、温度25℃、負荷10kΩで放電した時のFexSのｘ値に
対する開回路電圧及び放電容量の関係を示す図である。
第３図より放電容量についてはFexSのｘの値が0.65より
大きくなると低下することがわかる。これはリチウムと
の反応による理論エネルギーがFe0.5S（FeS2）で724Ah/
kg、Fe0.6Sで675Ah/kg、FeSで525Ah/kgのようにｘの値
が大きくなると減少するものであり、ｘの値が0.65より
大きくなるとその減少度合がより顕著になるためである
と考えられる。又、開回路電圧についてはFe0.5S（Fe
S2）単独では約1.9Vと高いのに対しｘの値が0.55以上に
なると約1.7V程度と低くなって酸化第二銅との混成電圧
を低下させる効果がより顕著となることがわかる。FIG. 3 is a diagram showing the relationship between the open circuit voltage and the discharge capacity with respect to the x value of FexS when stored at a temperature of 60 ° C. and a humidity of 90% for 30 days and then discharged at a temperature of 25 ° C. and a load of 10 kΩ. .
It can be seen from FIG. 3 that the discharge capacity decreases when the value of x in FexS exceeds 0.65. This is because the theoretical energy due to the reaction with lithium is Fe0.5S (FeS 2 ) and is 724 Ah /
kg, Fe0.6S is 675Ah / kg, FeS is 525Ah / kg, and the value of x decreases as the value of x increases. If the value of x is larger than 0.65, the degree of decrease becomes more remarkable. Conceivable. For open circuit voltage, use Fe0.5S (Fe
It can be seen that S 2 ) alone has a high value of about 1.9 V, whereas when the value of x is 0.55 or more, it decreases to about 1.7 V and the effect of lowering the hybrid voltage with cupric oxide becomes more remarkable.
この理由によりFexSのｘ値は0.55≦ｘ≦0.65の範囲が特
に好ましいことが理解される。For this reason, it is understood that the FexS x value is particularly preferably in the range of 0.55 ≦ x ≦ 0.65.
（ト）発明の効果 上述した如く、酸化第二銅を正極活物質とする非水電解
液電池において、正極にFexS（但し0.55≦ｘ≦0.65）を
添加することにより、保存時の開回路電圧の上昇を抑え
且放電容量の低下を抑制す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 non-aqueous electrolyte battery using cupric oxide as a positive electrode active material, by adding FexS (where 0.55 ≤ x ≤ 0.65) to the positive electrode, the open circuit voltage during storage can be increased. It is possible to suppress an increase in the discharge capacity and a decrease in the discharge capacity.
Its industrial value is extremely large.
第１図は電池の保存時における開回路電圧の経時変化を
示す図、第２図はFe0.6Sの添加量に対する開回路電圧及
び利用率の関係を示す図、第３図はFexSのｘの値に対す
る開回路電圧及び利用率の関係を示す図である。FIG. 1 is a diagram showing a change with time of the open circuit voltage during storage of the battery, FIG. 2 is a diagram showing a relationship between the open circuit voltage and the utilization rate with respect to the added amount of Fe0.6S, and FIG. 3 is a graph of FexS x. It is a figure which shows the relationship of an open circuit voltage and utilization with respect to a value.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−174863（ＪＰ，Ａ) 特開 昭56−84881（ＪＰ，Ａ) 特開 昭55−154072（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-174863 (JP, A) JP-A-56-84881 (JP, A) JP-A-55-154072 (JP, A)
Claims (2)
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、前記正極にFexS（但し0.55≦ｘ≦0.65）を添
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 FexS (where 0.55 ≦ x ≦ 0.65) is applied to the positive electrode. A non-aqueous electrolyte battery characterized by being added.
量％であることを特徴とする特許請求の範囲第項記載
の非水電解液電池。2. The non-aqueous electrolyte battery according to claim 1, wherein the amount of FexS added is 5 to 30% by weight with respect to the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62006535A JPH0746603B2 (en) | 1987-01-14 | 1987-01-14 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62006535A JPH0746603B2 (en) | 1987-01-14 | 1987-01-14 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63175337A JPS63175337A (en) | 1988-07-19 |
| JPH0746603B2 true JPH0746603B2 (en) | 1995-05-17 |
Family
ID=11641045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62006535A Expired - Fee Related JPH0746603B2 (en) | 1987-01-14 | 1987-01-14 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0746603B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5155689A (en) * | 1991-01-17 | 1992-10-13 | By-Word Technologies, Inc. | Vehicle locating and communicating method and apparatus |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55154072A (en) * | 1979-05-17 | 1980-12-01 | Hitachi Maxell Ltd | Non-aqueous electrolyte cell |
| JPS5684881A (en) * | 1979-12-11 | 1981-07-10 | Hitachi Maxell Ltd | Battery with nonaqueous electrolyte |
| JPS57174863A (en) * | 1981-04-20 | 1982-10-27 | Hitachi Maxell Ltd | Organic electrolyte cell |
-
1987
- 1987-01-14 JP JP62006535A patent/JPH0746603B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63175337A (en) | 1988-07-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |