JPS6041760A - Mercury battery - Google Patents

Abstract

PURPOSE:To provide a mercury battery having steady static performance and discharge capacity by adding a specivied amount of cadmium oxide to a positive mix containing mercuric oxide as main positive active material. CONSTITUTION:1-8pts.wt. cadmium oxide is added to 100pts.wt. mercuric oxide in a positive mix using mercuric oxide as main positive active material. For example, a positive mix 2 is formed in such a manner that 5pts.wt. graphite or acetylene black and 1-5pts.wt. cadmium oxide are mixed to 100pts.wt. mercuric oxide, and the mixture is formed in a form of pellet, then the pellet is pressed in a positive case with a positive ring 3. Since the positive mix containing cadmium oxide is easy to form a pellet, the pellet has uniform density and steady electrolyte absorption amount, and electrolyte penetrates uniformly into the pellet. Since cadmium oxide is converted to cadmium hydroxide by electrolyte, electrolyte penetrates to fine pores of the mix. Therefore, discharge capacity and static performance of a battery are stabilized.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、水銀電池の正極の改良に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to improvements in positive electrodes for mercury batteries.

従来の構成とその問題点 水銀電池は、放電中の電圧変化が少なく、保存性能が優
れており、小形で容積２重は当たりの電気容量が大きい
。また、開路電圧も長期にわたって安定していることか
ら、小形電子機器の電源として、補聴器、カメラの露出
部、開側２に、腕時計。Conventional configuration and its problems Mercury batteries have little voltage change during discharge, excellent storage performance, are small, and have a large electric capacity per double volume. In addition, since the open circuit voltage is stable over a long period of time, it can be used as a power source for small electronic devices such as hearing aids, exposed parts of cameras, open side 2, and wristwatches.

トランシーバ−、ポケットベル等に１史用されている。It has been used for a long time in transceivers, pagers, etc.

近年、機器の小形化に伴い電池の小形化が要求されてい
る。その結果、電池の放電容量、静特性の安定化が問題
となってきている。In recent years, as devices have become smaller, there has been a demand for smaller batteries. As a result, stabilization of the discharge capacity and static characteristics of batteries has become a problem.

従来の水銀電池の正極′ｆ：第１図に示す。図中１は正
極端子を兼ねた金属ケース、２はｉＥ極活物質である酸
化水銀、二酸化マンガンと、導電剤である黒鉛又はアセ
チレンブラック、及び焼成マンガンからなる正極合剤を
粗成形した後、正極リング３とともにケースに加圧成形
し、たものである。A positive electrode 'f of a conventional mercury battery is shown in FIG. In the figure, 1 is a metal case that also serves as a positive electrode terminal, and 2 is a positive electrode mixture consisting of iE electrode active materials mercury oxide and manganese dioxide, conductive agents graphite or acetylene black, and calcined manganese. It is press-molded into a case together with the positive electrode ring 3.

上記の構成では、正極リング下部２ａの合剤密度が高く
なり、電解液の浸透が悪くなる不都合がある。丑だ−Ｊ
二＋４（２合剤組成では、合剤の成形性が小安定で、合
剤重度が不均一となるため、電解液の浸透速度が遅く、
吸液量が安定していない。その結果、電池の放電容量、
静特性が不安定になる。In the above configuration, there is a disadvantage that the mixture density in the lower part 2a of the positive electrode ring becomes high, and penetration of the electrolyte becomes poor. It's ox-J
2+4 (With the 2 mixture composition, the moldability of the mixture is slightly stable and the mixture density is uneven, so the permeation rate of the electrolyte is slow,
The amount of liquid absorbed is not stable. As a result, the discharge capacity of the battery,
Static characteristics become unstable.

発明の目的 本発明は、上記のような欠点を屓消し、ｉ′ｒｆＩ特Ｉ
Ｉ４：、　。OBJECTS OF THE INVENTION The present invention eliminates the above-mentioned drawbacks and
I4:, .

放電容量の安定した水銀電池を提供することをｌ」的と
する。Our objective is to provide a mercury battery with stable discharge capacity.

発明の構成 本発明は、酸化水銀を主なる正極活物質とする正極合剤
中に酸化水銀１００重破部に７・Ｊシて１〜８重濱部の
酸化カドミウムを含治させるものである。Structure of the Invention The present invention is a positive electrode mixture containing mercury oxide as the main positive electrode active material, in which 1 to 8 layers of cadmium oxide is impregnated by 7 J to 100 layers of mercury oxide. .

この構成によれば、合剤の成形ｒ］−７がよく、成形さ
れた合剤の密度が均一になる。傷に１に極すングＦ台（
（２ａの合剤密度が電解液を吸液し２ないほど高くなら
ないため、正極合剤中へ迅速にかつ均−Ｖこ吸液され、
吸液量も安定する。また、ＩＥ正極合剤中ことによって
、さらに電ｌＩＪイ液が雅１１１３＼侵透していく効果
がある。その結果、放′１１容吊、静特性が安定する。According to this configuration, the molding of the mixture r]-7 is good and the density of the molded mixture becomes uniform. It is extremely effective against scratches.
(Since the density of the mixture 2a does not become so high that it absorbs the electrolyte, it is quickly and evenly absorbed into the positive electrode mixture,
The amount of liquid absorbed is also stable. Moreover, depending on the IE positive electrode mixture, there is an effect that the electrolyte liquid further penetrates into the IE cathode mixture. As a result, the suspension and static characteristics become stable.

また、酸化カドミウムは、負極側から発生する水素ガス
を除去するため、′電池の膨張寸／こけ破裂による機器
の破損を防１」−するという利点もある。Furthermore, since cadmium oxide removes hydrogen gas generated from the negative electrode side, it also has the advantage of preventing equipment damage due to battery expansion/molten rupture.

実施例の説明 第２図は本発明の実施例による水銀電池ＭＲ９を示す。Description of examples FIG. 2 shows a mercury cell MR9 according to an embodiment of the invention.

図において、１は厚さ０．３０団の鋼板を段付部下部外
径１３．１　ｍｒｎ　、段付部下ｇＢ　２．６０　ｍｍ
　ｒ段付部下部外径１５．６　ｍｍ　、高さ６．８０　
ｍｍに１Ｊち抜き加工し、二ノク−ルメノキをｈ布し７
たｊ、Ｆ　４會ケースである。２け正極合剤で、活物質
である酸化水銀１００重は部に導電性吻ｔ４である黒鉛
ま／こはアセチレンプラック５ノロ計部、酸化カドミウ
ムを１〜５重量部を混合し、ペレット状に成形した後、
正極リング３とともにＩＥ極ケースに加圧成形したもの
である。４１ｊ上ポリエチレン、ポリプロピレンなどよ
りなるセパレータ、５ｄアルカリ′ｆｉ　＋性液を含ん
だセロース系の含液拐である。６幻−負極合剤で、汞化
率５〜１５係の水化亜鉛粉末と電Ｍ’（液の水酸化カリ
ウム水溶液ど増粘剤のポリアクリル酸ソーダやカルボギ
ンメチルセルロース等との混練物よりなる。７は］１ノ
、さ０．４０　＋ｒｔｙｎのニッケルーステンレス鋼−
鋼の三層クラッド祠を外径１３．８０　ｍｍ　、高さ２
．６０ｍｍに加工し７た封口板、８Ｃポリアミド樹脂、
ポリエチＩ／ノ樹脂、ボリグロピレン４ｆｇ　Ｉｌｅ　
等Ｊ：りなる絶縁ガスヶ、）・であり、このガスケツ）
・８を装着した組立封１」板７内に前記の負極が充填σ
れる。In the figure, 1 is a steel plate with a thickness of 0.30 mm, the outer diameter of the lower part of the stepped part is 13.1 mrn, and the lower part of the stepped part gB is 2.60 mm.
r Stepped part lower part outer diameter 15.6 mm, height 6.80
Punch out 1J to mm, and cloth 7
This is the F4 case. In a 2-piece positive electrode mixture, 100 parts by weight of mercury oxide as an active material, 5 parts by weight of graphite or acetylene plaque as a conductive material, and 1 to 5 parts by weight of cadmium oxide were mixed, and the mixture was made into pellets. After forming into
It is press-molded into the IE electrode case together with the positive electrode ring 3. 41j is a separator made of polyethylene, polypropylene, etc.; 6 Phantom-negative electrode mixture, from a kneading product of zinc hydrate powder with a concentration of 5 to 15 and electrolytic M' (liquid potassium hydroxide aqueous solution, thickeners such as sodium polyacrylate and carbogine methylcellulose). 7 is] 1 no, 0.40 +rtyn nickel-stainless steel-
A three-layer steel clad shrine with an outer diameter of 13.80 mm and a height of 2
．． Sealing plate processed to 60mm, 8C polyamide resin,
Polyethylene I/resin, polyglopylene 4fg Ile
Etc. J: Rinaru insulating gas gasket, ), and this gasket)
・The above-mentioned negative electrode is filled in the assembly seal 1'' plate 7 with 8 attached.
It will be done.

酸化カドミウムを含有した正極合剤は、成形性か摩れて
いるため、加圧成形される際に合剤密度か均一になり、
電解液の吸液量が安定し、さらに合剤へ均一に電解液が
浸透する。また、酸化カドミウムは、電解液中で水酸化
カドミウムに変化することによ−）で、きらに合剤＋１
ｉ１１１部へ電Ｊｑｑ液が浸透していく。その結果、電
池の放電容量と静特性が安定する。Since the positive electrode mixture containing cadmium oxide has poor moldability, the density of the mixture becomes uniform when it is pressure-molded.
The amount of electrolyte absorbed is stabilized, and the electrolyte permeates uniformly into the mixture. In addition, cadmium oxide changes to cadmium hydroxide in the electrolyte solution, resulting in a mixture of +1
The electric Jqq liquid penetrates into the i111 part. As a result, the discharge capacity and static characteristics of the battery are stabilized.

第３図は正極合剤の酸化カドミウムの含有割合を変えた
電池についての電池内部抵抗のバラツキと平均値の関係
を示している。なお、試料数は各々２０個である。酸化
カドミウムの含有、１１１１合を酸化水銀１００重量部
に対して１〜８重石部にした際に内部抵抗が安定し、バ
ラツキが小さくな−）ている。FIG. 3 shows the relationship between the variation in battery internal resistance and the average value for batteries in which the content of cadmium oxide in the positive electrode mixture was changed. Note that the number of samples was 20 for each. When the content of cadmium oxide is 1 to 8 parts by weight per 100 parts by weight of mercury oxide, the internal resistance becomes stable and the variation becomes small.

ま／ζ、第４図は酸化カドミウムの介イ〕−９Ｕ合と放
電ｇ解のバラツキと平均値の関係を示している。Fig. 4 shows the relationship between the dispersion of the discharge g-solution and the average value for the cadmium oxide intercalation [-9U].

この図より、明らかに酸化水銀１００徂搦一部に対して
酸化カドミウムを１〜８重量部含有する際に放電容量が
安定し、バラツギが小さくなっている。From this figure, it is clear that when 1 to 8 parts by weight of cadmium oxide is contained per 100 parts of mercury oxide, the discharge capacity becomes stable and the variation becomes small.

次に酸化水銀１００車量部に対して酸化カドミウム３型
取部を含有する正極合剤を用いた′ε池をＡ１酸化カド
ミウムを含まない正極合剤を用いた電池をＢとして、内
部抵抗、放電容量の標準偏差を比較してみると、次表の
とおりである。なお、試料数に各２０１１６１　テある
。Next, a battery using a positive electrode mixture containing 3 molded portions of cadmium oxide with respect to 100 parts by weight of mercury oxide is designated A1, a battery using a positive electrode mixture containing no cadmium oxide is designated B, and the internal resistance, A comparison of the standard deviations of discharge capacity is shown in the following table. There are 201,161 samples each.

発明の効果 以上の実施＋７１Ｊからも明ら刀・の」、うに、本発明
によれば、容昂、静肪性か安定した水銀電池が得しれる
。It is clear from the implementation of the invention that exceeds the effects of the invention.According to the present invention, a mercury battery that is both accommodating and statically stable can be obtained.

４、図面の簡ｔ１ｊな＋ｉｆｅ　ＩＪ 第１図は従来構成による正極ケースに正極合剤を充填し
た状態を示す縦断１８」図、第２図−木兄１，１ｌ−１
の実施例（ｆこおける′電池の一部を断面Ｖこした側面
図、第３図は合剤の酸化カドミウムの含有Ａ１１合を変
１）；させた際の内部抵抗の推移を示す図、均′５４図
を」、酸化カドミウムの含有割合を変化させた際の放電
容量の推移を示す図である。4. Simplification of the drawings Figure 1 is a vertical cross-section 18'' showing the state in which the positive electrode case is filled with the positive electrode mixture according to the conventional configuration, Figure 2 - Kinoi 1, 1l-1
Example (a side view of a part of the battery in section V, with the cross section V cut out; Figure 3 shows the change in internal resistance when the content of cadmium oxide in the mixture is changed to 1); 54 is a diagram showing the transition of discharge capacity when the content ratio of cadmium oxide is changed.

１・・・正イ愼ケース、２　・　正極合剤、４　セパレ
ータ、５　・・・含液材、６・・　・負極、７−　封１
」板、８・・・・・絶縁力スケット。1...Positive case, 2-Positive electrode mixture, 4 Separator, 5...Liquid-containing material, 6...-Negative electrode, 7- Seal 1
” Board, 8... Insulation power socket.

代理人の氏名　弁μ］！士　中　尾　敏　男　ほか１名
車　１　１］ 第２図 第３図 部 抵 抗ｌＯ ：■Agent's name Benmu]! Toshio Nakao and 1 other car 1 1] Figure 2 Figure 3 Part Resistance lO: ■

Claims (1)

【特許請求の範囲】[Claims] 主なる正極活物質として酸化水銀を１史用する正極合剤
中に酸化水銀１００重量部に灯して１〜８重量部の酸化
カドミウムを含有させたことを特徴とする水銀電池。A mercury battery characterized in that a positive electrode mixture containing mercury oxide as a main positive electrode active material contains 1 to 8 parts by weight of cadmium oxide in addition to 100 parts by weight of mercury oxide.