JPS62123659A - Organic electrolyte battery - Google Patents

Abstract

PURPOSE:To eliminate a falling phenomenon in initial voltage that was a defect of an oxidized copper-lithium battery as well as to set working voltage also to somewhere around 1.5V, by using a positive electrode active material mixing a lower oxide of manganese in oxidized copper. CONSTITUTION:This battery is made up of a positive electrode consisting of a mixture of oxidized copper and a lower oxide of manganese, a negative electrode consisting of alkali metal and an organic electrolyte. Voltage in the discharge initial stage is the higher the larger in a mixed quantity of manganese sesquioxide in design, so that a falling phenomenon at the discharge initial stage is relieved. And, when the mixed quantity of the manganese sesquioxide becomes increased, discharge capacity becomes lessened. From the voltage falling phenomenon and the discharge capacity aforesaid, a proper mixing ratio between the oxidized copper and the lower oxide of manganese is in a range of 90/10-50/50.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は有機電解質電池、特に正極に酸化銅、負極にリ
チウムを用いる１、５ｖ系の有機電解質電池の改良に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improvement in an organic electrolyte battery, particularly a 1.5V type organic electrolyte battery using copper oxide for the positive electrode and lithium for the negative electrode.

従来の技術 この種の有機電解質リチウム電池は大別に３ｖ系と１．
６ｖ系の２つの系統がある。１．５ＶＩＪチウム電池は
、従来からある水溶液系電解を用いたアルカリ電池等と
電圧のｌｆ換性があり、かつ有機電解質電池としての特
長である耐漏液性、長期保存性と有しており、これ−ま
で金属の酸化物、硫化物、４〆ｔ ハロゲン化物等の種々の正極活読物質が検討さねシ１で
きだ。なかでも酸化銅を正極活物質に用いたりチウム電
池はその代表的々ものとして既に実用化されている。BACKGROUND OF THE INVENTION This type of organic electrolyte lithium battery is roughly divided into 3V type and 1.
There are two 6v systems. The 1.5VIJ lithium battery has voltage lf interchangeability with conventional alkaline batteries using aqueous electrolysis, and also has the characteristics of an organic electrolyte battery, such as leak resistance and long-term storage. Until now, various positive electrode active materials such as metal oxides, sulfides, and halides have not been studied. Among these, lithium batteries that use copper oxide as a positive electrode active material are already in practical use as representative examples.

発明が解決しようとする問題点 しかし、この種の電池は、その放電特性、特に放電初期
における電圧特性に問題がある。すなわち、第２図に示
すように、放電を開始してから電３　′・−・ 圧が安定する捷でに電圧の落ち込み現象がみられる。従
って電池の電圧が重要視される電子ウォッチ等の電源と
しては、精度などに悪影響を及ぼすおそれがある。Problems to be Solved by the Invention However, this type of battery has problems with its discharge characteristics, particularly its voltage characteristics at the initial stage of discharge. That is, as shown in FIG. 2, a voltage drop phenomenon is observed at the point where the voltage becomes stable after the start of discharge. Therefore, as a power source for electronic watches, etc., where battery voltage is important, there is a risk that the accuracy etc. will be adversely affected.

寸だ放電電圧も約１．３〜１．４ｖと水溶液系電池であ
る酸化銀電池の約１．５５Ｖに比較してやや低く、完全
に互換性があると言いきれなかった。The discharge voltage was also approximately 1.3 to 1.4V, which was slightly lower than the approximately 1.55V of a silver oxide battery, which is an aqueous solution battery, so it could not be said that they were completely compatible.

本発明はこのような酸化銅リチウム電池の放電初期の電
圧落ち込み現象を抑制するとともに、作動電圧を１．６
ｖ伺近甘で」−げ、従来の１．５ｖ系電池との互換性を
よりもたせることを目的としたものである。The present invention suppresses such a voltage drop phenomenon in the early stage of discharge of a copper oxide lithium battery, and also reduces the operating voltage to 1.6.
This is intended to improve compatibility with conventional 1.5V batteries.

問題点を解決するだめの手段 この問題点を解決するために本発明は正極活物質として
、酸化銅にマンガンの低級酸化物を混合したものを用い
たものである。Alternative Means to Solve the Problem In order to solve this problem, the present invention uses a mixture of copper oxide and a lower oxide of manganese as the positive electrode active material.

作用 このような構成によれば、マンガンの低級酸化物の放電
電圧は初期段階で酸化銅のそれより高い。Effect: According to such a configuration, the discharge voltage of the lower manganese oxide is higher than that of the copper oxide in the initial stage.

こねは酸化銅にマンガンの低級酸化物を混合したことに
エリ、放電初期から／ｌ＋−成電極と１〜て効率よく反
応し、電圧の落ち込みが抑制されるとともに作動電圧も
酸化銅単独の場合の１．３〜１．４ｖから１．５付近に
上がるからである。The reason for this is that copper oxide is mixed with a lower manganese oxide, which reacts efficiently with the /l + - forming electrode from the early stage of discharge, suppressing the drop in voltage and lowering the operating voltage compared to copper oxide alone. This is because the voltage rises from 1.3 to 1.4V to around 1.5V.

実施例 以下、本発明の実施例を第１図を用いて説明する。Example Embodiments of the present invention will be described below with reference to FIG.

第１図は本発明の１．５ｖ系扁乎形有機電解質電池を示
す。　図において （１）ハステンレス鋼製の１１−極ケ・−スであり、内
部に正極合剤？）が充填されている。３はセパレータ、
（４）はステンレス鋼製の負極封目板であり、内面に負
極リチウム←）が圧着されている。正極合剤２と負極リ
チウム５とはポリプロピレンからなるセパレータ（３）
を介して対向し、プロピレンカーボネイト、１，２ジメ
トキシエタン、過塩素酸リチウムからなる電解液を注入
した後、絶縁パツキン（６）を介して封口され、直径９
．５１＃Ｊ厚さ２．７酎の電池が構成される。FIG. 1 shows a 1.5V flat type organic electrolyte battery of the present invention. In the figure, (1) is an 11-electrode case made of stainless steel, with a positive electrode mixture inside. ) is filled. 3 is a separator,
(4) is a negative electrode sealing plate made of stainless steel, and negative electrode lithium ←) is crimped onto the inner surface. The positive electrode mixture 2 and the negative electrode lithium 5 are separators (3) made of polypropylene.
After injecting an electrolytic solution consisting of propylene carbonate, 1,2 dimethoxyethane, and lithium perchlorate, the tubes were sealed via an insulating packing (6), and a diameter of 9.
．． A 51#J battery with a thickness of 2.7 mm is constructed.

ここで正極合剤（２）は、正極活物質として、酸化６“
−パ 銅ど三二酸化マンガンとの混合物を用い、その配合比を
重量比で１ｏｏ１０　、９０／１０　、７０／３０　、
　ｅｓｏ１５ｏ　。Here, the positive electrode mixture (2) is an oxidized 6"
- Using a mixture of copper and manganese sesquioxide, the weight ratio of the mixture is 1oo10, 90/10, 70/30,
eso15o.

３０／７０　、　Ｏ／１００とし、これら１００重量部
に導電材のアセチレンブラックを５重量部、結着剤のポ
リ４フツ化エチレンを６重量部の割合で混合した後、一
定重量を計量し、加圧成型して正極合剤とｌ〜だ。それ
ぞれの正極合剤を用い前述したように電池を構成した。30/70, O/100, and 100 parts by weight were mixed with 5 parts by weight of acetylene black as a conductive material and 6 parts by weight of polytetrafluoroethylene as a binder, and then weighed to a certain weight. It is pressure molded and made into a positive electrode mixture. Batteries were constructed using each of the positive electrode mixtures as described above.

ここで電池ムは酸化銅と三二酸化マンガンの比率が１０
０１０のもの、Ｂは９０／１０Ｃは７０／３０．Ｄば６
　ｏ１５０　、　Ｅは３０／７０．Ｆは０／１００のも
のである。Here, the ratio of copper oxide and manganese sesquioxide in the battery is 10.
010, B is 90/10C is 70/30. Dba6
o150, E is 30/70. F is 0/100.

第３図に示すように、放電初期の電圧は三二酸化マンガ
ンの混合量が多い程高くなっており、放電初期の電圧落
ち込み現象が軽減されている。As shown in FIG. 3, the voltage at the beginning of discharge becomes higher as the amount of manganese sesquioxide mixed increases, and the voltage drop phenomenon at the beginning of discharge is reduced.

第４図はり）〜促）の電池放電容量を示したものであり
三二酸化マンガンの混合量が多くなると放電容量が小さ
くなっている。第６図には電池（Ａ）　＃　（ｃ）　ｒ
便）の３０にΩの負荷でのそれぞれの放電カーブを示す
。図からあきらかなように本発明の電池（Ｃ）は初期電
圧２作動電圧とも従来品（Ａ）に比較し？、ｐ（，６ベ
ー７ 三二酸化マンガン単独の電池促）より放電容量は大きく
なっている。Figure 4 shows the battery discharge capacity of the batteries 1) to 3), and as the amount of manganese sesquioxide mixed increases, the discharge capacity decreases. Figure 6 shows the battery (A) # (c) r
Figure 30 shows the respective discharge curves under a load of Ω. As is clear from the figure, the battery of the present invention (C) has both initial voltage and operating voltage compared to the conventional product (A). The discharge capacity is larger than that of the battery containing manganese sesquioxide alone.

これら電圧の低下現象と放電容量から酸化銅とマンガン
の低級酸化物との混合化は９０／１０〜６０／６０が適
切である。In view of these voltage drop phenomena and discharge capacity, it is appropriate to mix copper oxide and lower manganese oxide in a ratio of 90/10 to 60/60.

また実施例ではマンガンの低級酸化物として三二酸化マ
ンガンを月ｊい／こがＮ７ご酸化マンガンヲ耳［いても
同様の効果が１！１ら１１だ。捷だ純粋な三二酸化マン
ガン、四三酸化マンガン以外に二酸化マンガンを６００
〜９００’（Ｊ、の温度で加熱処理して得られるマンガ
ンの低級酸化物を混合することによっても同様の効果が
得られた。In addition, in the example, the same effect was obtained even if manganese sesquioxide was used as a lower oxide of manganese. 600% manganese dioxide in addition to pure manganese sesquioxide and trimanganese tetraoxide
A similar effect was obtained by mixing a lower oxide of manganese obtained by heat treatment at a temperature of ~900' (J).

発明の効果 初期電圧の落ち込み現象を解消するとともに作動電圧も
１．５ｖ付近になり、１．６ｖ系電池として既存のアル
カリ水溶液系電池の放電特性により近似した特性になる
という効果が？Ｉられる。Effects of the invention In addition to eliminating the initial voltage drop phenomenon, the operating voltage is also reduced to around 1.5V, and as a 1.6V battery, the discharge characteristics are more similar to those of existing alkaline aqueous batteries. I get caught.

７　ペー。7 p.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明の一実施例による有機電解質電池の断面
図、第２図は従来の電池の放電初期の電圧立下りを示Ｉ
７た図、第３図は酸化銅と三二酸化マンガンとの混合比
と、放電初期における最低電圧との関係を示した図、第
４図は酸化銅と三二酸化マンガンとの混合比と、放電容
量との関係を示した図、第６図は従来品、及び本発明の
電池の放電特性図である。 １は正極ケース、２は正極合剤、３はセパレータ、４け
負極封口板、６は負極リチラム、６は絶縁パツキン。 代理人の氏名　午理士　中　尾　敏　男　ほか１名１−
一正、ネジデー又 勇　１　図　　　　　　　　　２−　　・・１１３−ｍ
−ヒバーし−グ ＋−−−１−極材で隈 ５−−−リワづ＝−シフ４ Ｇ−−一輯釆裂ハーノキシ 第　２　図 故１ｔ−詩面Ｃｈｒ）−FIG. 1 is a cross-sectional view of an organic electrolyte battery according to an embodiment of the present invention, and FIG. 2 shows the voltage fall of a conventional battery at the initial stage of discharge.
Figure 7 shows the relationship between the mixing ratio of copper oxide and manganese sesquioxide and the lowest voltage at the initial stage of discharge, and Figure 4 shows the relationship between the mixing ratio of copper oxide and manganese sesquioxide and the discharge voltage. FIG. 6, which shows the relationship with capacity, is a discharge characteristic diagram of the conventional battery and the battery of the present invention. 1 is a positive electrode case, 2 is a positive electrode mixture, 3 is a separator, 4-digit negative electrode sealing plate, 6 is a negative electrode lithium, and 6 is an insulating packing. Name of agent: Attorney Toshio Nakao and 1 other person 1-
Kazumasa, Nejiday Matayu 1 Figure 2-...113-m
- Hibarshi - Gu + - - 1 - Goku material de kuma 5 - Riwazu = - Schiff 4 G - - Part 1 of the 3rd edition of Harnoxi No. 2 Figure 1t - Poetry Chr) -

Claims (4)

【特許請求の範囲】[Claims] （１）酸化銅とマンガン低級酸化物との混合物からなる
正極と、アルカリ金属からなる負極と、有機電解液とか
ら構成したことを特徴とする有機電解質電池。(1) An organic electrolyte battery comprising a positive electrode made of a mixture of copper oxide and a lower manganese oxide, a negative electrode made of an alkali metal, and an organic electrolyte. （２）酸化銅とマンガンの低級酸化物との混合化が、重
量比で９０：１０〜５０：５０である特許請求の範囲第
１項の有機電解質電池。(2) The organic electrolyte battery according to claim 1, wherein the copper oxide and the lower manganese oxide are mixed in a weight ratio of 90:10 to 50:50. （３）マンガンの低級酸化物が三二酸化マンガン（Ｍｎ
＿２Ｏ＿３）または四三酸化マンガン（Ｍｎ＿３Ｏ＿４
）である特許請求の範囲第１項または第２項記載の有機
電解質電池。(3) The lower oxide of manganese is manganese sesquioxide (Mn
_2O_3) or trimanganese tetroxide (Mn_3O_4
) The organic electrolyte battery according to claim 1 or 2. （４）マンガンの低級酸化物が、二酸化マンガンを６０
０〜９００℃で加熱処理したものである特許請求の範囲
第１項から第３項のいずれかに記載の有機電解質電池。(4) Lower oxides of manganese reduce manganese dioxide by 60
The organic electrolyte battery according to any one of claims 1 to 3, which is heat-treated at 0 to 900°C.