JPS59146155A - Production method of nonaqueous electrolyte cell - Google Patents

Abstract

PURPOSE:To produce nonaqueous electrolyte cell reliably excellent in discharge performance by using a light metal for a negative electrode and using a mixture mold of CuO and a conductive material or a conductive material and a binding agent heat-treated at a relatively low temperature for a positive electrode. CONSTITUTION:In a nonaqueous electrolyte cell using Li, K, Na, Ca, Mg, Al for a negative electrode and CuO for a positive electrode respectively, the positive electrode is produced as follows. That is, CuO molded with a conductive material alone or a mixture of a conductive material and a binding agent is heat- treated within a temperature range of 50-250 deg.C to form the positive electrode. Accordingly, only by simply changing process operations, the reduction of the effective active material quantity of the positive electrode can be prevented and the discharge capacity of the nonaqueous electrolyte cell can be improved reliably and largely.

Description

【発明の詳細な説明】 この発明は非水電解液電池の製造方法の特に正極活物質
として酸化第二銅を用いる非水電解液電池の製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a non-aqueous electrolyte battery, particularly to a method for manufacturing a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material.

周知のごとく、酸化第二銅を正極活物質として用いる非
水電解液電池における有効な活物質は、一般にＣｕＯで
現わされる酸化第二銅である。この酸化第二銅ＣｕＯは
導電材申独かまたは導Ｎ月と結着剤の両者と混合されて
所定の合剤形状に成形されたのち、脱水と焼結の為に高
温度で熱処理される。この場合、非水電解液電池は一般
に結合水も含めて水分を極度に嫌うため、従来に於いて
は充分に高い潤度具体的には３００’Ｃ以上の温度をか
けて熱処理を行なっていた。しかしながらこの様な高温
度で熱処理を行なう結果、その酸化第二銅ＣｕＯの一部
が還元されてＣ１１２０あるいはＣ０になり、これによ
り有効活物質量が減少して放電容量の低下をきたしてい
た。これを防ぐ為に従来においては、熱処理雰囲気とし
て還元雰囲気を用いない方法９例えば真空中で熱処理を
づ゛ることなどが考えられていた。しかし、本発明者ら
が知得したところによると、たとえ還元雰囲気中でなく
とも熱処理を行なうことによりかなりの量の酸化第二銅
ＣｕＯがＣｕｚＯあるいはＣＩに還元され、これが放電
容量の低下の大きな原因とな−）でいることが判明した
。As is well known, an effective active material in a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material is cupric oxide, generally represented by CuO. This cupric oxide CuO is mixed with a conductive material or both a conductive material and a binder, formed into a predetermined mixture shape, and then heat treated at high temperatures for dehydration and sintering. . In this case, since non-aqueous electrolyte batteries are generally extremely averse to moisture, including bound water, conventionally heat treatment was carried out at sufficiently high moisture levels, specifically at temperatures of 300'C or higher. . However, as a result of heat treatment at such a high temperature, a portion of the cupric oxide CuO is reduced to C1120 or C0, thereby reducing the amount of effective active material and lowering the discharge capacity. In order to prevent this, conventional methods have been considered that do not use a reducing atmosphere as the heat treatment atmosphere, for example, carrying out the heat treatment in a vacuum. However, the present inventors have learned that even if heat treatment is not performed in a reducing atmosphere, a considerable amount of cupric oxide CuO is reduced to CuzO or CI, which causes a large decrease in discharge capacity. It turned out that the cause was -).

一＝般に酸化銅を強熱した場合は、酸化銅そのものが強
力な酸化剤としで働くことは良く知られている。真空中
でも、３５０℃近辺においてはすでに分解は起こってい
ると考えられるのである。雰囲気ガスが水素あるいは一
酸化炭素のような場合には２５０℃１メ下でも容易に酸
化銅は分解されるとされている。It is well known that when copper oxide is ignited, the copper oxide itself acts as a strong oxidizing agent. It is thought that decomposition has already occurred at around 350°C even in a vacuum. It is said that when the atmospheric gas is hydrogen or carbon monoxide, copper oxide is easily decomposed even at 1 meter below 250°C.

この発明は以上のような従来の問題を鑑みて成されたも
ので、その目的とするところは、正極に酸化第二銅を用
いた非水電解液電池の放電性能を、その製造工程の極め
て簡単な変更だけでもって確実に向トさせられるように
した非水電解液電池の製造方法を提供することにある。This invention was made in view of the above-mentioned conventional problems, and its purpose is to improve the discharge performance of non-aqueous electrolyte batteries using cupric oxide as the positive electrode by improving the manufacturing process. It is an object of the present invention to provide a method for manufacturing a non-aqueous electrolyte battery that can be reliably adapted to the current situation with only simple changes.

上記目的を達成するためにこの発明は、負極に１ｉ、に
、Ｎａ、Ｃａ、ＡＩ、ＭＯ等の軽金属、正極に酸化第二
銅をそれぞれ用いる非水電解液電池に於いて、上記正極
は、酸化第二銅に導電材単独または、導電材と結着剤を
混合して成形したものを５０℃〜２５０℃の温度範囲ぐ
熱処理して１ｎられることを特徴どする。In order to achieve the above object, the present invention provides a non-aqueous electrolyte battery in which the negative electrode uses a light metal such as 1, Na, Ca, AI, or MO, and the positive electrode uses cupric oxide. It is characterized by being formed by molding cupric oxide with a conductive material alone or a mixture of a conductive material and a binder and heat-treating it at a temperature range of 50°C to 250°C.

以上のように、この発明にＪ、る製造り法では、２Ｆ記
熱処理温度の範囲を５０℃−２５０℃に設定するという
極めて血中な工程操作であるが、これにより正極活物質
中の酸化第二銅Ｃ１−１０ｈ＜Ｃｕ　？０あるいはＣＬ
Ｉに還元されてその有効活物質量が減ｊ０することを確
実に防止することができ、そしてこの結果以下に示すよ
うに放電性能、特に放電容量の大幅な向−１−を１ｑる
ことが出来たのである。As mentioned above, in the manufacturing method according to this invention, the 2F heat treatment temperature range is set at 50°C to 250°C, which is a very complicated process operation, but this process reduces the oxidation in the positive electrode active material. Cupric C1-10h<Cu? 0 or CL
It is possible to reliably prevent the amount of effective active material from being reduced to I, and as a result, as shown below, it is possible to significantly improve the discharge performance, especially the discharge capacity. It was possible.

また、」−記の温度範囲による脱水処理を行なっても、
最終的に製造された製品の中から残留水分による不良品
が出ることはなかった。つまり、上記温度範囲でも実際
には充分な脱水処理が行なわれることを確認することが
出来た。また、酸化第ニー銅Ｃｕ○とともに使用される
上記導電材どしてカーボンを用いる場合、このカーボン
が上記熱処理時の熱によって酸化第二銅Ｃｔ＋Ｏ中の酸
素と反応するのを防止するために、上記温度範囲は８０
℃〜１５０℃程度の範囲内に設定Ｊることが望ま（）い
。In addition, even if dehydration treatment is performed in the temperature range indicated in "-",
There were no defective products due to residual moisture among the final manufactured products. In other words, it was confirmed that sufficient dehydration treatment was actually performed even in the above temperature range. Furthermore, when carbon is used as the conductive material used together with cupric oxide Cu○, in order to prevent this carbon from reacting with the oxygen in cupric oxide Ct+O due to the heat during the heat treatment, The above temperature range is 80
It is desirable to set the temperature within a range of approximately 150°C to 150°C.

実施例 酸化第二銅ＣｕＯと導電材（グラファイト）が９０：１
０で混合して成形されたものを、減圧下１２０℃で６時
間熱処理して正極成形合剤を得た。Example Cupric oxide CuO and conductive material (graphite) are 90:1
The mixed and molded mixture was heat-treated at 120° C. for 6 hours under reduced pressure to obtain a positive electrode molding mixture.

この合剤と、プロピレンカーボネイトとジメトキシエタ
ンの１＝１の混合溶媒に塩素酸リチウムを１モル濃度溶
解してなる電解液と、ポリプロピレン不織布よりなるセ
パレータとを用いてＡＡサイズの非水電解液電池を組み
立てた。またこれと比較するために、上記熱処理を減圧
下３５０℃の温度で６時間行なってなる正極成形合剤を
用いた同型の電池を組み立てた。そして、前者の電池Ａ
および後者の電池Ｂをそれぞれ４０Ωの定抵抗放電条件
でもってその放電持続時間および端子電圧を連続して測
定してみたところ、それぞれ図に示すような放電特性面
１！Ａ、Ｂを得た。各曲線Ａ、Ｂはそれぞれ１００個ず
つのサンプルについて測定を行ない、その平均的な特性
を示したものである。Using this mixture, an electrolytic solution prepared by dissolving lithium chlorate at a 1 molar concentration in a 1=1 mixed solvent of propylene carbonate and dimethoxyethane, and a separator made of polypropylene nonwoven fabric, an AA-sized non-aqueous electrolyte battery is produced. assembled. For comparison, a battery of the same type was assembled using a positive electrode molding mixture that had been subjected to the heat treatment described above at a temperature of 350° C. for 6 hours under reduced pressure. And the former battery A
When we continuously measured the discharge duration and terminal voltage of the latter battery B under a constant resistance discharge condition of 40Ω, we found that the discharge characteristics of each battery are 1! as shown in the figure. I got A and B. Each of the curves A and B shows the average characteristics obtained by measuring 100 samples each.

同図にて明らかなように、この発明により製造された電
池Ａの放電特性は、特に放電容量は、明らかに従来の電
池Ｂのそれよりも大幅に向上している。As is clear from the figure, the discharge characteristics of the battery A manufactured according to the present invention, particularly the discharge capacity, are clearly significantly improved over those of the conventional battery B.

以−Ｖのようにこの発明による製造方法にＪ：れば、極
めて簡単な工程操作の変更だｉ′ｊでもって正極の有効
活物質量の減損を防止して放電容量を確実。By using the manufacturing method according to the present invention as shown in FIG. 5, the discharge capacity can be ensured by preventing loss of the effective active material amount of the positive electrode through extremely simple changes in process operations.

かつ大幅に向上させることができる。and can be significantly improved.

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

図はこの発明により製造される電池Ａと従来の方法によ
り製造される電池Ｂの放電特性を比較して示す図である
。The figure is a diagram showing a comparison of the discharge characteristics of a battery A manufactured by the present invention and a battery B manufactured by a conventional method.

Claims (1)

【特許請求の範囲】[Claims] （１）負極にリチウム、カリウム　、ナトリウム　。 力Ｊレシウム、アルミニウム、マグネシウムなどの軒金
属、正極に酸化第二銅をそれぞれ用いる非水電解液電池
において、上記正極は、酸化第二銅にｓＮ材単独または
導電材と結着剤を混合して成形したものを５０℃〜２５
０℃の温度範囲で熱処理して得られることを特徴とする
非水電解液電池の製造方法。 （２、特許請求の範囲（１）の方法に於いて、上記導電
材としてカーボンを用いるとともに、上記温度範囲を８
０℃〜１５０℃とすることを特徴とする非水電解液電池
の製造方法。(1) Lithium, potassium, and sodium for the negative electrode. In nonaqueous electrolyte batteries that use eaves metals such as lesium, aluminum, and magnesium, and cupric oxide for the positive electrode, the positive electrode is made of cupric oxide mixed with an SN material or a conductive material and a binder. The molded product is heated to 50°C to 25°C.
A method for producing a non-aqueous electrolyte battery, characterized in that it is obtained by heat treatment in a temperature range of 0°C. (2. In the method of claim (1), carbon is used as the conductive material, and the temperature range is
A method for manufacturing a non-aqueous electrolyte battery, characterized in that the temperature is 0°C to 150°C.