JP4374430B2 - Cathode active material for alkaline electrolyte battery and alkaline electrolyte battery using the same - Google Patents
Cathode active material for alkaline electrolyte battery and alkaline electrolyte battery using the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、従来のＡｇ2Ｏより電気抵抗が低く、銀の使用量の少ないアルカリ電解液電池用正極活物質およびそれを用いたアルカリ電解液電池に関するものである。
【０００２】
【従来の技術】
アルカリ電解液電池、例えば酸化銀電池は正極活物質として、従来酸化銀Ａｇ2Ｏを用いていたが、Ａｇ2Ｏは導電性が低く、電池の内部抵抗が高くなり電池の放電容量の低下をもたらすため、Ａｇ2Ｏを部分的に還元して金属銀を析出させ導電性を持たせたり、正極合剤に黒鉛のような導電性の物質を導電補助剤として添加したりして使われていた。
【０００３】
【発明が解決しようとする課題】
しかしながら、析出した金属銀は作用物質ではないため、内部抵抗の問題が解消されても、電池の放電容量の低下をもたらす。また、導電補助剤を添加するとその嵩密度が小さいため正極合剤中でかなりの体積を占めることになる。従ってその内部抵抗の問題が解消されても、正極活物質である酸化銀の占める割合が減少し、電池の放電容量が減少してしまう。
一方、近年電子機器、時計用の電源として小型化、及び長期信頼性のニーズが高まっており今後も酸化銀電池等のアルカリ電解液電池の高性能化の要求に応えていく必要がある。しかし、上記の問題点により放電容量の低下がみられており導電補助剤の必要のない導電性酸化銀等の正極活物質が必要である。
また、近年の技術の進歩にともなって、アルカリ電解液電池、例えば酸化銀電池材料コストの中で、正極活物質である酸化銀の占める割合が年々増加していき、原材料中の銀を少なくさせることが必要になってきた。
したがって本発明の目的は、正極合剤の放電容量あたりの高価な銀の使用量を削減可能であるとともに、正極合剤として黒鉛のような導電補助剤を添加せずに、または少量添加するだけで、放電容量が高容量の電池を得ることの可能な、アルカリ電解液電池用の正極活物質とその製造方法およびそれを用いたアルカリ電解液電池を提供することにある。
【０００４】
【課題を解決するための手段】
そこで本発明者は上述の従来の問題を解決すべく鋭意努力した結果、湿式反応時に銀塩とコバルト塩を所定の量的割合で添加し、その際に酸化剤を作用させることにより銀とコバルトの含む酸化物を調製し正極活物質とすることで、正極合剤の放電容量あたりの高価な銀の使用量を削減可能であるとともに、正極合剤として黒鉛のような導電補助剤を添加せずに、または少量添加するだけで、放電容量が高容量の電池を得ることが可能となり、前記課題が解決できることを見出し本発明に到達した。
すなわち本発明は第１に、Ａｇ：Ｃｏがモル比で０．９：０．１〜０．４：０．６（ただしＡｇとＣｏのモル比の合計を１．０とする）の割合となるように銀塩とコバルト塩とをアルカリ水溶液と混合し、得られる懸濁液に酸化剤を作用させることにより調製することを特徴とするアルカリ電解液電池用正極活物質の製造方法；第２に、前記アルカリ水溶液と混合した銀塩が、前記懸濁液中で、平均価数が＋１．１以上の酸化銀となることを特徴とする第１に記載のアルカリ電解液電池用正極活物質の製造方法；第３に、Ａｇ、Ｃｏを、モル比でＡｇ：Ｃｏ＝０．９：０．１〜０．４：０．６（ただしＡｇとＣｏのモル比の合計を１．０とする）の割合で含む酸化物であることを特徴とするアルカリ電解液電池用正極活物質；第４に、前記第１〜３のいずれかに記載の正極活物質を用いたことを特徴とするアルカリ電解液電池を提供するものである。
【０００５】
【発明の実施の形態】
製法としては、第１段階としてアルカリと酸化剤の共存液中に硝酸銀を添加し、平均価数が＋１よりも大きな酸化銀を得る。より好ましくは平均価数が、＋１．１以上、さらに好ましくは＋１．５以上の酸化銀とする。特に好ましいのは全てが＋２価酸化銀になることが望ましいが、実際には＋２価酸化銀の含有率が高い、＋１価酸化銀と＋２価酸化銀との混合物として析出した懸濁液を得ることが多い。
第２段階としてこの懸濁液中に、硝酸銀に対して硝酸コバルトを所定の割合で、例えば、モル比で、Ａｇ：Ｃｏ＝１：１となるように添加する。ここで主にコバルトオキシ水酸化物が生成する。このときに酸化銀の還元等の変化は生じない。この段階の終了ｐＨは１０以上であることが望ましい。
第３段階としてこのアルカリ溶液中で酸化銀とコバルトオキシ水酸化物とが反応してコバルト酸銀を生成する。反応途中での＋１価酸化銀の明瞭な増加はみられなかった。
第１段階から第３段階までの反応はアルカリと酸化剤の共存下で行われる。この沈殿生成物を十分洗浄し、１００℃以下の温度で乾燥して黒色粉末を得る。
本発明で得られた反応生成物はＸ線回折により銀とコバルトの複合酸化物のＡｇＣｏＯ2であることが確認された。
以下さらに詳細な条件を示す。
第１段階から第３段階までに用いる上記アルカリとしては、通常のアルカリが使用可能であるが、特に苛性アルカリ、例えばＫＯＨ、ＮａＯＨ、ＬｉＯＨ等が好ましい。これは、酸化銀を得るためには強アルカリが好ましいからである。その意味からもｐＨは１０以上が好ましい。
上記第１段階で得られる懸濁液中の酸化銀の平均価数を＋１．１以上、より好ましくは＋１．５以上とすることにより、酸化銀の価数を上げることでコバルトとの反応性を高め、最終的にＡｇＣｏＯ2、あるいはＡｇとＣｏを含む酸化物を、特別な装置による煩雑な操作を必要とせずに、常圧のもとで１００℃以下の温度で得ることが可能となる。
上記酸化剤としては、通常の酸化剤が使用可能であり、例えばＫ2Ｓ2Ｏ８、ＫＭｎＯ４、Ｈ2Ｏ2、オゾン、ＮａＣｌＯ等が使用可能である。
酸化剤の添加は、上記のように第１段階でアルカリと共存させておいてもよいが、酸化銀が析出した後の第２段階で硝酸コバルトを添加する前に酸化剤を添加しても、第３段階で酸化剤を添加しても、いずれでもよい。
上記添加する硝酸銀と添加する硝酸コバルトの割合は、モル比で、Ａｇ：Ｃｏ＝０．９：０．１〜０．４：０．６の範囲であり、より好ましくは、Ａｇ：Ｃｏ＝０．４５：０．５５〜０．５５：０．４５である。Ａｇ：Ｃｏ＝０．９：０．１よりＣｏの含有量が低いと、十分な導電性が得られないため、またＡｇの使用量を充分低減できないため、好ましくない。また、Ａｇ：Ｃｏ＝０．４：０．６よりＣｏの含有量が高いと放電曲線の平坦性が充分得られないため好ましくない。これらの点からも、Ａｇ：Ｃｏ＝０．４５：０．５５〜０．５５：０．４５が特に好ましい。
硝酸銀と添加する硝酸コバルトの割合が、モル比で、Ａｇ：Ｃｏ＝０．５：０．５よりＣｏが多い場合は、Ａｇ：Ｃｏ＝０．５５：０．４５までは、ＡｇＣｏＯ2にＣｏが固溶していると考えられる。Ａｇ：Ｃｏ＝０．９：０．１〜０．５：０．５の範囲では、Ａｇ2Ｏ、ＡｇＣｏＯ2相の混合相、あるいはＡｇとＣｏを含む酸化物となる。
乾燥温度は、ある程度低い方が乾燥中の凝集が少なくなり好ましい。その点からも、また必要な乾燥エネルギーが少量に抑えることができる点からも、１００℃以下の温度か好ましい。凝集を抑える点からは、真空乾燥するのがより好ましい。
最終的得られたＡｇＣｏＯ2、あるいはＡｇとＣｏを含む酸化物は、Ａｇ2Ｏに比べて、導電性の良好なものであった。
このようにして得られたＡｇＣｏＯ2、あるいはＡｇとＣｏを含む酸化物粉末の電池特性を、該粉末を用いて、例えば、図１に示す構造の酸化銀電池を作製し、以下の方法で評価した。
一例として、得られた粉末に炭素を０．５重量％添加して混合し、これを５トン／cm2の圧力で成形し直径１１mmのペレットを作製し、これを正極剤１として正極缶２に入れ、電解液として３５重量％ＫＯＨ水溶液を数滴滴下した。セロハンと綿不織布からなるセパレーター３を正極剤１の上に置く。亜鉛アマルガムと微量のアクリル酸系のゲル化剤とＫＯＨ３５重量％溶液とを混合し負極剤５とした。負極剤５を負極缶６に充填し、正極缶２とはナイロンガスケット４を介してかしめ機によって結合した。正極缶２には内側のステンレスにニッケルメッキしたものを用い、負極缶６には外側がニッケル、内側が銅、中間がステンレスであるような複合材を用いた。電池の大きさは、直径が１１．６ｍｍ、高さが約３mmである。これは公称容量８０ｍＡｈの一酸化銀電池に近似する。容量は１５ｋΩの抵抗を用いて放電させて測定した。終了電圧は１．２Ｖとした。
本発明で得られた複合酸化物を用いるアルカリ電解液電池は、ＡｇＣｏＯ2の重量エネルギー密度は理論密度として２７０ｍＡｈ／ｇ前後と言われているが、理論密度相当に見合うだけのエネルギーが得られた。従来の酸化銀Ａｇ2Ｏと比較しても遜色がなく、さらにＡｇの使用量の少ない電池とすることができる。
【０００６】
【実施例１】
１モルのＫ2Ｓ2Ｏ8を含む１０モル／ＬのＮａＯＨ溶液１．０Ｌに１モル／Ｌの硝酸銀溶液を２００ｃｃ添加し、１０分間撹拌保持した。その後、同様に撹拌しながら１モル／Ｌの硝酸コバルト溶液２００ｃｃを添加した。このときのｐＨは１３〜１４として。この酸化銀とコバルト化合物を含む液を４０℃で１０時間撹拌した後、生成沈殿物を溶液から分離し、十分洗浄して３５℃で風乾した。更に、１００℃で加熱乾燥した後この試料をサンプルミルにて粉砕し黒色粉末を得た。
【０００７】
このようにして得られた粉末の電池特性を、該粉末を用いて図１に示す構造の酸化銀電池を作製し、以下の方法で評価した。
得られた粉末に炭素を０．５重量％添加して混合し、これを５トン／cm2の圧力で成形し直径１１mmのペレットを作製し、これを正極剤１として正極缶２に入れ、電解液として３５％ＫＯＨ水溶液を数滴滴下した。セロハンと綿不織布からなるセパレーター３を正極剤１の上に置く。亜鉛アマルガムと微量のアクリル酸系のゲル化剤とＫＯＨ３５重量％溶液とを混合し負極剤５とした。負極剤５を負極缶６に充填し、正極缶２とはナイロンガスケット４を介してかしめ機によって結合した。正極缶２には内側のステンレスにニッケルメッキしたものを用い、負極缶６には外側がニッケル、内側が銅、中間がステンレスであるような複合材を用いた。電池の大きさは、直径が１１．６ｍｍ、高さが約３mmである。これは公称容量８０ｍＡｈの一酸化銀電池に近似する。容量は１５ｋΩの抵抗を用いて放電させて測定した。終了電圧は１．２Ｖとした。
本発明で得られた複合酸化物は初期電圧が１．６３Ｖの範囲を示した。
【０００８】
【実施例２】
実施例１と同様の条件で得た生成物を風乾した後真空中８０℃で乾燥した。電池特性の評価は実施例１と同様の方法で測定した。
【０００９】
【実施例３】
５モルのＫＭｎＯ4を含む１０モル／ＬのＮａＯＨ溶液１．０Ｌに１モル／Ｌの硝酸銀溶液を２００ｃｃ添加し、１０分間撹拌保持した。その後、同様に撹拌しながら１モル／Ｌの硝酸コバルト溶液２００ｃｃを添加した。この酸化銀とコバルト化合物を含む液を７０℃で１０時間撹拌した後、生成沈殿物を溶液から分離し、十分洗浄して３５℃で風乾した。更に、１００℃で加熱乾燥した後この試料をサンプルミルにて粉砕し黒色粉末を得た。
【００１０】
【実施例４】
１モルのＫ2Ｓ2Ｏ8を含む１０モル／ＬのＮａＯＨ溶液１．０Ｌに１モル／Ｌの硝酸銀溶液を２００ｃｃ添加し、１０分間撹拌保持した。その後、同様に撹拌しながら０．５モル／Ｌの硝酸コバルト溶液２００ｃｃを添加した。以下実施例１と同様の方法で行った。
【００１１】
【実施例５】
１モルのＫ2Ｓ2Ｏ8を含む１０モル／ＬのＮａＯＨ溶液１．０Ｌに０．９モル／Ｌの硝酸銀溶液を２００ｃｃ添加し、１０分間撹拌保持した。その後、同様に撹拌しながら０．１モル／Ｌの硝酸コバルト溶液２００ｃｃを添加した。以下実施例１同様の方法で行った。
【００１２】
【実施例６】
実施例１と同様の方法で作製した粉末を５トン／cm2の圧力で成形し直径１１mm、厚み０．７mmのペレットを作製した。以下実施例１と同様の方法で電池特性を測定した。
【００１３】
【実施例７】
実施例４と同様の方法で作製した粉末を５トン／cm2の圧力で成形し直径１１mm、厚み０．７mmのペレットを作製した。以下実施例１と同様の方法で電池特性を測定した。
実施例２〜７においても実施例１と同様に理論エネルギー密度に見合うだけのエネルギーが得られた。
【００１４】
【比較例】
酸化銀Ａｇ2Ｏを用いて実施例１と同様の方法で電池を作製し、その電池特性をみた。
銀の使用量はＡｇＣｏＯ2に比較して重量で約４０％多い。
初期電圧は１．５４Ｖ、電池容量は８０ｍＡｈであった。
【００１５】
【発明の効果】
本発明の複合酸化物粉末は正極活物質として使用することにより、従来の酸化銀電池Ａｇ2Ｏより銀の使用量を少なくすることができ、かつ高い電池容量を安定して発現できるアルカリ電解液電池を提供する事ができた。
【図面の簡単な説明】
【図１】本発明の導電性複合酸化物を正極活物質として用いた酸化銀電池の電池特性の評価を行うために作製した電池の構造を示す断面図である。
【符号の説明】
１ 正極剤
２ 正極缶
３ セパレーター
４ ガスケット
５ 負極剤
６ 負極缶[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive electrode active material for an alkaline electrolyte battery that has a lower electrical resistance than conventional Ag 2 O and uses less silver, and an alkaline electrolyte battery using the same.
[0002]
[Prior art]
Alkaline electrolyte batteries, such as silver oxide batteries, conventionally used silver oxide Ag 2 O as the positive electrode active material. However, Ag 2 O has low conductivity, increases the internal resistance of the battery, and decreases the discharge capacity of the battery. Therefore, Ag 2 O is partially reduced to deposit metal silver to give conductivity, or a conductive material such as graphite is added to the positive electrode mixture as a conductive auxiliary agent. It was.
[0003]
[Problems to be solved by the invention]
However, since the deposited silver metal is not an active substance, the discharge capacity of the battery is reduced even if the problem of internal resistance is solved. Further, when a conductive auxiliary agent is added, its bulk density is small, so that a considerable volume is occupied in the positive electrode mixture. Therefore, even if the problem of the internal resistance is solved, the proportion of silver oxide, which is the positive electrode active material, decreases, and the discharge capacity of the battery decreases.
On the other hand, in recent years, there has been a growing need for downsizing and long-term reliability as a power source for electronic devices and watches, and it will be necessary to meet the demand for higher performance of alkaline electrolyte batteries such as silver oxide batteries. However, the discharge capacity is reduced due to the above problems, and a positive electrode active material such as conductive silver oxide which does not require a conductive auxiliary agent is required.
In addition, with the advancement of technology in recent years, the proportion of silver oxide, which is a positive electrode active material, increases year by year in the alkaline electrolyte battery, for example, silver oxide battery material cost, and the silver in the raw material is reduced It has become necessary.
Therefore, the object of the present invention is to reduce the amount of expensive silver used per discharge capacity of the positive electrode mixture and to add a small amount without adding a conductive auxiliary agent such as graphite as the positive electrode mixture. Then, it is providing the positive electrode active material for alkaline electrolyte batteries which can obtain a battery with a high discharge capacity, its manufacturing method, and an alkaline electrolyte battery using the same.
[0004]
[Means for Solving the Problems]
Accordingly, as a result of diligent efforts to solve the above-mentioned conventional problems, the present inventors added silver salt and cobalt salt in a predetermined quantitative ratio during wet reaction, and at that time, an oxidant was allowed to act on the silver and cobalt. As a positive electrode active material, the amount of expensive silver used per discharge capacity of the positive electrode mixture can be reduced and a conductive additive such as graphite can be added as a positive electrode mixture. The inventors have found that a battery having a high discharge capacity can be obtained by adding a small amount without adding a small amount, and the present invention has been found to solve the above problems.
That is, according to the present invention, first, the ratio of Ag: Co in a molar ratio of 0.9: 0.1 to 0.4: 0.6 (provided that the total molar ratio of Ag and Co is 1.0) A method for producing a positive electrode active material for an alkaline electrolyte battery, comprising: mixing a silver salt and a cobalt salt with an alkaline aqueous solution and allowing an oxidant to act on the resulting suspension; 2. The positive electrode active material for an alkaline electrolyte battery according to claim 1, wherein the silver salt mixed with the alkaline aqueous solution becomes silver oxide having an average valence of +1.1 or more in the suspension. Third, Ag and Co are mixed at a molar ratio of Ag: Co = 0.9: 0.1 to 0.4: 0.6 (provided that the total molar ratio of Ag and Co is 1.0). A positive electrode active material for an alkaline electrolyte battery, characterized by comprising: There is provided an alkaline electrolyte battery characterized by using the positive electrode active material according to any one to three of the.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
As a manufacturing method, silver nitrate is added to the coexisting liquid of an alkali and an oxidizing agent as a first step to obtain silver oxide having an average valence larger than +1. More preferably, the silver oxide has an average valence of +1.1 or more, more preferably +1.5 or more. Particularly preferred is that all become +2 silver oxide, but in practice, a suspension containing a high content of +2 silver oxide and precipitated as a mixture of +1 silver oxide and +2 silver oxide is obtained. There are many cases.
As a second step, cobalt nitrate is added to this suspension at a predetermined ratio, for example, molar ratio, Ag: Co = 1: 1 with respect to silver nitrate. Here, cobalt oxyhydroxide is mainly produced. At this time, no change such as reduction of silver oxide occurs. The final pH at this stage is preferably 10 or more.
As a third step, silver oxide and cobalt oxyhydroxide react in this alkaline solution to produce silver cobaltate. There was no clear increase in + 1valent silver oxide during the reaction.
The reaction from the first stage to the third stage is performed in the presence of an alkali and an oxidizing agent. This precipitated product is sufficiently washed and dried at a temperature of 100 ° C. or lower to obtain a black powder.
The reaction product obtained in the present invention was confirmed to be AgCoO 2 which is a composite oxide of silver and cobalt by X-ray diffraction.
More detailed conditions are shown below.
As the alkali used in the first stage to the third stage, a normal alkali can be used, but caustic alkali such as KOH, NaOH, LiOH and the like are particularly preferable. This is because strong alkali is preferable to obtain silver oxide. In that sense, the pH is preferably 10 or more.
Reactivity with cobalt by increasing the valence of silver oxide by setting the average valence of silver oxide in the suspension obtained in the first step to +1.1 or more, more preferably +1.5 or more. Finally, it is possible to obtain AgCoO 2 or an oxide containing Ag and Co at a temperature of 100 ° C. or lower under normal pressure without requiring a complicated operation with a special apparatus. .
As the oxidizing agent, a conventional oxidizing agent can be used, for example, K 2 S 2 O 8, KMnO 4, H 2 O 2, ozone, NaClO and the like can be used.
The oxidant may be added together with the alkali in the first stage as described above, but the oxidant may be added before the cobalt nitrate is added in the second stage after the silver oxide is deposited. The oxidizing agent may be added in the third stage, either of which may be used.
The ratio of the silver nitrate to be added to the cobalt nitrate to be added is in the range of Ag: Co = 0.9: 0.1 to 0.4: 0.6, more preferably Ag: Co = 0. .45: 0.55-0.55: 0.45. If the content of Co is lower than Ag: Co = 0.9: 0.1, sufficient conductivity cannot be obtained, and the amount of Ag used cannot be sufficiently reduced, which is not preferable. Further, if the content of Co is higher than Ag: Co = 0.4: 0.6, the flatness of the discharge curve cannot be obtained sufficiently, which is not preferable. Also from these points, Ag: Co = 0.45: 0.55-0.55: 0.45 is particularly preferable.
When the ratio of silver nitrate and cobalt nitrate to be added is more than Ag: Co = 0.5: 0.5 in terms of molar ratio, AgCoCo is mixed with AgCoO 2 until Ag: Co = 0.55: 0.45. Is considered to be a solid solution. In the range of Ag: Co = 0.9: 0.1 to 0.5: 0.5, a mixed phase of Ag 2 O, AgCoO 2 phase, or an oxide containing Ag and Co is obtained.
The drying temperature is preferably lower to some extent because aggregation during drying is reduced. In view of this point and the point that the necessary drying energy can be suppressed to a small amount, a temperature of 100 ° C. or lower is preferable. From the viewpoint of suppressing aggregation, vacuum drying is more preferable.
The finally obtained AgCoO 2 or an oxide containing Ag and Co had better conductivity than Ag 2 O.
The battery characteristics of the thus obtained AgCoO 2 or oxide powder containing Ag and Co are used to produce, for example, a silver oxide battery having the structure shown in FIG. 1 and evaluated by the following method. did.
As an example, 0.5% by weight of carbon is added to the obtained powder and mixed, and this is molded at a pressure of 5 ton / cm 2 to produce a pellet having a diameter of 11 mm. Then, several drops of 35 wt% KOH aqueous solution were dropped as an electrolytic solution. A
In the alkaline electrolyte battery using the composite oxide obtained in the present invention, the weight energy density of AgCoO 2 is said to be around 270 mAh / g as the theoretical density, but energy sufficient for the theoretical density was obtained. . Compared with conventional silver oxide Ag 2 O, the battery is not inferior, and a battery with a small amount of Ag can be obtained.
[0006]
[Example 1]
200 cc of a 1 mol / L silver nitrate solution was added to 1.0 L of a 10 mol / L NaOH solution containing 1 mol of K 2 S 2 O 8, and the mixture was stirred for 10 minutes. Thereafter, 200 cc of a 1 mol / L cobalt nitrate solution was added while stirring in the same manner. The pH at this time is 13-14. After the liquid containing silver oxide and the cobalt compound was stirred at 40 ° C. for 10 hours, the produced precipitate was separated from the solution, washed sufficiently, and air-dried at 35 ° C. Further, after heat drying at 100 ° C., this sample was pulverized by a sample mill to obtain a black powder.
[0007]
The battery characteristics of the powder thus obtained were evaluated by the following method, using the powder to produce a silver oxide battery having the structure shown in FIG.
Carbon was added to the obtained powder in an amount of 0.5% by weight, and this was molded at a pressure of 5 ton / cm 2 to produce a pellet with a diameter of 11 mm. Several drops of 35% KOH aqueous solution were dropped as an electrolytic solution. A
The composite oxide obtained by the present invention showed an initial voltage in the range of 1.63V.
[0008]
[Example 2]
The product obtained under the same conditions as in Example 1 was air dried and then dried at 80 ° C. in vacuum. The battery characteristics were evaluated by the same method as in Example 1.
[0009]
[Example 3]
200 cc of a 1 mol / L silver nitrate solution was added to 1.0 L of a 10 mol / L NaOH solution containing 5 mol of KMnO 4, and the mixture was held for 10 minutes with stirring. Thereafter, 200 cc of a 1 mol / L cobalt nitrate solution was added while stirring in the same manner. After the liquid containing silver oxide and cobalt compound was stirred at 70 ° C. for 10 hours, the produced precipitate was separated from the solution, washed sufficiently, and air-dried at 35 ° C. Further, after heat drying at 100 ° C., this sample was pulverized by a sample mill to obtain a black powder.
[0010]
[Example 4]
200 cc of a 1 mol / L silver nitrate solution was added to 1.0 L of a 10 mol / L NaOH solution containing 1 mol of K 2 S 2 O 8, and the mixture was stirred for 10 minutes. Thereafter, 200 cc of a 0.5 mol / L cobalt nitrate solution was added with stirring in the same manner. Thereafter, the same method as in Example 1 was performed.
[0011]
[Example 5]
200 cc of a 0.9 mol / L silver nitrate solution was added to 1.0 L of a 10 mol / L NaOH solution containing 1 mol of K 2 S 2 O 8, and the mixture was stirred for 10 minutes. Thereafter, 200 cc of a 0.1 mol / L cobalt nitrate solution was added while stirring in the same manner. Thereafter, the same method as in Example 1 was performed.
[0012]
[Example 6]
A powder produced by the same method as in Example 1 was molded at a pressure of 5 ton / cm 2 to produce a pellet having a diameter of 11 mm and a thickness of 0.7 mm. The battery characteristics were then measured in the same manner as in Example 1.
[0013]
[Example 7]
The powder produced by the same method as in Example 4 was molded at a pressure of 5 ton / cm 2 to produce a pellet having a diameter of 11 mm and a thickness of 0.7 mm. The battery characteristics were then measured in the same manner as in Example 1.
In Examples 2 to 7, as in Example 1, energy sufficient for the theoretical energy density was obtained.
[0014]
[Comparative example]
A battery was produced in the same manner as in Example 1 using silver oxide Ag 2 O, and the battery characteristics were examined.
The amount of silver used is about 40% higher by weight than AgCoO 2 .
The initial voltage was 1.54 V and the battery capacity was 80 mAh.
[0015]
【The invention's effect】
By using the composite oxide powder of the present invention as a positive electrode active material, the amount of silver used can be reduced as compared with the conventional silver oxide battery Ag 2 O, and an alkaline electrolyte capable of stably expressing a high battery capacity. I was able to provide batteries.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a cross-sectional view showing the structure of a battery prepared for evaluating battery characteristics of a silver oxide battery using the conductive composite oxide of the present invention as a positive electrode active material.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Positive electrode agent 2 Positive electrode can 3 Separator 4
Claims (5)
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| JP10856399A JP4374430B2 (en) | 1999-04-15 | 1999-04-15 | Cathode active material for alkaline electrolyte battery and alkaline electrolyte battery using the same |
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| JP10856399A JP4374430B2 (en) | 1999-04-15 | 1999-04-15 | Cathode active material for alkaline electrolyte battery and alkaline electrolyte battery using the same |
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| JP4374430B2 true JP4374430B2 (en) | 2009-12-02 |
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