JPH07254407A - Unamalgamated zinc alkaline battery - Google Patents

Unamalgamated zinc alkaline battery

Info

Publication number
JPH07254407A
JPH07254407A JP6899194A JP6899194A JPH07254407A JP H07254407 A JPH07254407 A JP H07254407A JP 6899194 A JP6899194 A JP 6899194A JP 6899194 A JP6899194 A JP 6899194A JP H07254407 A JPH07254407 A JP H07254407A
Authority
JP
Japan
Prior art keywords
zinc
negative electrode
battery
added
positive electrode
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.)
Pending
Application number
JP6899194A
Other languages
Japanese (ja)
Inventor
Masatomo Oohashi
真智 大橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FDK Twicell Co Ltd
Original Assignee
Toshiba Battery Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Battery Co Ltd filed Critical Toshiba Battery Co Ltd
Priority to JP6899194A priority Critical patent/JPH07254407A/en
Publication of JPH07254407A publication Critical patent/JPH07254407A/en
Pending legal-status Critical Current

Links

Classifications

    • Y02E60/12—

Abstract

PURPOSE:To restrict deterioration of a zinc utilization factor, and improve discharging characteristics by adding CaO, MgO, AlO in specified quantity to a gel zinc negative electrode comprising negative electrode active material mainly comprizing unamalgamated zinc powder mixed with gelatinizer and alkaline electrolyte. CONSTITUTION:To zinc powder and gelatinizer comprizing polyacrylic acid, CaO, MgO by 10-10000ppm respectively, and Al2O3 by 10-1000ppm to zinc are added and mixed. Electrolyte of alkaline solution comprising potassium hydroxide is added to this mix to be agitated to provide a gel zinc negative electrode 7, and a positive electrode catalyst layer 5 is composed of active coal, graphite, manganese dioxide, etc. In a positive electrode case 1 also acting as a positive electrode terminal and having an air hole 2 at a bottom part, an air diffusion paper 3, a water repellent film 4, a layer 5, a separator 6, and the negative electrode 7 are inserted in order from the bottom part. An aperture part of the case 1 is folded toward a sealing plate 8 also acting as a negative electrode terminal on it through a gasket 9 of nylon to seal a battery. Deterioration of a zinc utilization factor by unamalgamated property can thus be restricted, thereby discharging characteristics can be improved.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、アルカリ電池の無水銀
化に伴う亜鉛利用率低下を抑制し、優れた放電特性を持
つ高性能アルカリ電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-performance alkaline battery which suppresses a decrease in zinc utilization rate due to the use of anhydrous silver in an alkaline battery and has excellent discharge characteristics.

【０００２】[0002]

【従来の技術】従来、亜鉛を負極としたアルカリ電池は
水銀が含まれていた。これは負極活物質である亜鉛が腐
食して水素ガスを発生し、漏液や破裂等の危険性がある
ため、それを防止する目的で水銀を添加していた。ま
た、水銀は水素過電圧を高めるとともに水素ガスを抑制
するだけでなく、亜鉛粉末粒子間に良好な導電性物質と
して存在するので、放電反応においても亜鉛利用率が良
く、電池の放電特性に大きく影響していた。2. Description of the Related Art Conventionally, alkaline batteries using zinc as a negative electrode have contained mercury. This is because the negative electrode active material zinc corrodes to generate hydrogen gas, and there is a risk of liquid leakage or rupture. Therefore, mercury was added for the purpose of preventing it. Further, mercury not only enhances hydrogen overvoltage and suppresses hydrogen gas, but also exists as a good conductive substance between zinc powder particles, so the zinc utilization rate is good even in the discharge reaction, and it greatly affects the discharge characteristics of the battery. Was.

【０００３】近年、低公害化が求められてきたため、水
銀の含有率を低減させた電池の研究、開発がなされるよ
うになった。しかしながら、水銀含有率の低減は、従来
の有水銀に比べて、亜鉛粉末粒子間の接触が悪くなるの
で亜鉛利用率が低下し、十分な放電特性が得ることがで
きない。このため、亜鉛粉末粒子間の接触を良好にする
ため、ゲル化剤を改良して大粒径のゲル化剤（特開平３
−８９４５８号）を用いたものがある。このゲル化剤は
ゲル化剤粒子間に亜鉛粉末粒子を押しやり、亜鉛粉末粒
子の接触を良くして放電特性を向上させているが、接触
箇所が亜鉛粉末粒子間の接触部分だけであるため、亜鉛
利用率という点では、放電反応に寄与しない部分が残る
ことになるため、十分な放電特性を得ていない。また、
少量の汞化亜鉛を使用しているため、社会一般に水銀の
イメージを拭えていないなどの問題があった。In recent years, there has been a demand for low pollution, so that research and development of batteries having a reduced content rate of mercury have been made. However, the reduction of the mercury content makes the contact between zinc powder particles worse as compared with the conventional mercury-containing particles, so that the zinc utilization rate decreases and sufficient discharge characteristics cannot be obtained. Therefore, in order to improve the contact between the zinc powder particles, the gelling agent has been improved to have a large particle size (Japanese Patent Laid-Open No. Hei 3)
-89458). This gelling agent pushes the zinc powder particles between the gelling agent particles to improve the contact between the zinc powder particles and improve the discharge characteristics, but the contact point is only the contact point between the zinc powder particles. In terms of the zinc utilization rate, a portion that does not contribute to the discharge reaction remains, so that sufficient discharge characteristics are not obtained. Also,
Since a small amount of zinc fluoride is used, there is a problem that society is not wiping the image of mercury.

【０００４】[0004]

【発明が解決しようとする課題】さらに近年では、生活
環境への関心の高まりの中で、少量とはいえ有害な水銀
が電池中に含有されていることは問題であり、無水銀化
した電池の開発が望まれていた。しかし、無水銀化した
電池は、亜鉛粉末粒子間の接触が悪く、亜鉛利用率低下
に伴い、放電特性が低下する。また、電池内に多量の未
反応亜鉛を残すためガス発生量を増加させることとな
る。こうして発生したガスは電池の内部圧力を上げ、電
池総高を高くしたり、場合によっては漏液、破裂の危険
性があった。Further, in recent years, with increasing interest in the living environment, it is a problem that a small amount of harmful mercury is contained in the battery. Was desired to be developed. However, in a battery made of anhydrous silver, the contact between zinc powder particles is poor, and the discharge characteristics deteriorate as the zinc utilization rate decreases. Moreover, since a large amount of unreacted zinc remains in the battery, the gas generation amount is increased. The gas thus generated raises the internal pressure of the battery, raises the total height of the battery, and may cause liquid leakage or rupture in some cases.

【０００５】しかしながら、上記のような問題を解決す
るために、ゲル化剤の種類、ゲル亜鉛負極中の亜鉛配合
比、亜鉛粉末などを改良した負極活物質の開発が試みら
れてきたが、亜鉛粉末粒子間の接触、亜鉛利用率の向上
には限界があった。However, in order to solve the above problems, attempts have been made to develop a negative electrode active material in which the type of gelling agent, the zinc compounding ratio in the gel zinc negative electrode, the zinc powder, etc. are improved. There was a limit to contact between powder particles and improvement of zinc utilization.

【０００６】本発明は、無水銀化に伴う亜鉛利用率の低
下を抑制し、優れた放電特性を持つ高性能アルカリ電池
の提供を目的とするものである。It is an object of the present invention to provide a high performance alkaline battery which suppresses a decrease in zinc utilization rate due to the conversion to anhydrous silver and has excellent discharge characteristics.

【０００７】[0007]

【課題を解決するための手段】本発明は、無汞化亜鉛粉
末を主体とする負極活物質に、ゲル化剤とアルカリ電解
液とを混合したゲル状亜鉛負極を有するアルカリ電池に
おいて、該ゲル状亜鉛負極に酸化カルシウム（Ｃａ
Ｏ）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム
（Ａｌ2 Ｏ3 ）のうちいずれか１種類以上を添加するこ
とで、無水銀化に伴う亜鉛利用率の低下を抑制し、優れ
た放電特性を有する高性能なアルカリ電池を提供するも
のである。The present invention provides an alkaline battery having a gelled zinc negative electrode in which a gelling agent and an alkaline electrolyte are mixed in a negative electrode active material mainly composed of unremoved zinc powder. Calcium oxide (Ca
O), magnesium oxide (MgO), and aluminum oxide (Al 2 O 3 ) are added to suppress a decrease in zinc utilization rate due to the formation of anhydrous silver and have excellent discharge characteristics. It provides a high-performance alkaline battery.

【０００８】[0008]

【作用】本発明は、ＣａＯ、ＭｇＯ及びＡｌ2 Ｏ3 のう
ちいずれか１種類以上を添加するが、一般に、金属酸化
物は溶解性が悪いため、電解液と反応しない。そのた
め、ゲル状亜鉛負極に添加した場合、亜鉛粉末粒子表面
付近では、金属酸化物自体が抵抗となり、亜鉛利用率が
低下するため、放電特性が低下する。しかし、上記の添
加物は溶解性が高いため、ＣａＯ、ＭｇＯ及びＡｌ2 Ｏ
3 が電解液と反応してＣａ2+、Ｍｇ2+及びＡｌ3+のイオ
ンになり、これが亜鉛粉末粒子表面全体に導電性の良好
な無機物として拡散して存在する。また、該無機物が、
亜鉛粉末粒子表面に濡れ性を持った状態で存在するた
め、電解液との接触も良好になる。その結果、亜鉛利用
率の低下を抑制し、放電特性を大幅に向上させる作用が
ある。したがって、ゲル状亜鉛負極に溶解度の高い金属
酸化物のＣａＯ、ＭｇＯ及びＡｌ2 Ｏ3 のうちいずれか
１種類以上を添加することにより、優れた放電特性を持
つアルカリ電池を提供することができる。In the present invention, any one or more of CaO, MgO and Al 2 O 3 is added, but in general, metal oxides have poor solubility and therefore do not react with the electrolytic solution. Therefore, when added to the gelled zinc negative electrode, the metal oxide itself becomes a resistance near the surface of the zinc powder particles, and the zinc utilization rate decreases, so that the discharge characteristics deteriorate. However, since the above additives have high solubility, CaO, MgO and Al 2 O
3 reacts with the electrolytic solution to form ions of Ca 2+ , Mg 2+ and Al 3+ , which are diffused and exist on the entire surface of the zinc powder particle as an inorganic material having good conductivity. In addition, the inorganic substance,
Since the zinc powder particles are present on the surface of the zinc powder particles in a wettable state, the contact with the electrolytic solution is also good. As a result, it has an effect of suppressing a decrease in zinc utilization rate and significantly improving discharge characteristics. Therefore, by adding at least one of the highly soluble metal oxides CaO, MgO and Al 2 O 3 to the gelled zinc negative electrode, it is possible to provide an alkaline battery having excellent discharge characteristics.

【０００９】[0009]

【実施例】以下、本発明の実施例を図１を用いて説明す
る。 実施例１〜１６ 本発明の実施例として、Ｒ４４タイプ（直径１１．６ｍ
ｍ、高さ５．４ｍｍ）のボタン型空気電池を用いた。図
中の１は正極端子を兼ねる正極ケースで、底部に空気を
取り入れる空気孔２が設けられている。３はセルロー
ス、ポリプロピレン等からなる空気拡散紙、４はポリテ
トラフルオロエチレンよりなる撥水膜、５は活性炭、黒
鉛、二酸化マンガン及びポリテトラフルオロエチレンか
らなる正極触媒層である。６はセパレータで、耐アルカ
リ性の不織布よりなるバリヤーを用いている。７は亜鉛
粉末及びポリアクリル酸からなるゲル化剤に、上記添加
物を添加して混合した後、水酸化カリウムからなるアル
カリ水溶液の電解液を加え、撹拌して得たゲル状亜鉛負
極、８は負極端子を兼ねる封口板、９はナイロンよりな
るガスケット、１０は未使用時に保存特性を向上させる
ため、水分、炭酸ガス等が電池内に入るのを防止するた
めのシール紙である。また、電池封口については、封口
板８にガスケット１０を介して正極ケース１の開口部を
折曲することで電池を封口した。この構成の電池におけ
るゲル状亜鉛負極にＣａＯ、ＭｇＯ及びＡｌ2 Ｏ3 を表
１に示すような配合でそれぞれ添加し、実施例１〜１６
のボタン型空気電池を作製した。EXAMPLE An example of the present invention will be described below with reference to FIG. Examples 1 to 16 As examples of the present invention, R44 type (diameter 11.6 m
m, height 5.4 mm) button type air battery was used. Reference numeral 1 in the figure denotes a positive electrode case which also serves as a positive electrode terminal, and has an air hole 2 for taking in air at the bottom. 3 is an air diffusion paper made of cellulose, polypropylene or the like, 4 is a water repellent film made of polytetrafluoroethylene, and 5 is a positive electrode catalyst layer made of activated carbon, graphite, manganese dioxide and polytetrafluoroethylene. Reference numeral 6 is a separator, which uses a barrier made of an alkali resistant non-woven fabric. 7 is a gelled zinc negative electrode obtained by adding the above additives to a gelling agent consisting of zinc powder and polyacrylic acid, mixing them, and then adding an electrolytic solution of an alkaline aqueous solution consisting of potassium hydroxide and stirring the mixture. Is a sealing plate that also serves as a negative electrode terminal, 9 is a gasket made of nylon, and 10 is a seal paper for preventing moisture, carbon dioxide gas, etc. from entering the battery in order to improve storage characteristics when not in use. Regarding the battery sealing, the battery was sealed by bending the opening of the positive electrode case 1 through the gasket 10 on the sealing plate 8. Examples 1 to 16 were prepared by adding CaO, MgO and Al 2 O 3 in the composition shown in Table 1 to the gelled zinc negative electrode in the battery of this configuration.
A button-type air battery was manufactured.

【００１０】比較例１ ゲル状亜鉛負極として、上記の添加物を添加しない以外
は実施例と同様のボタン型空気電池を作製した。Comparative Example 1 A button type air battery was prepared as in Example 1 except that the above additives were not added as a gel zinc negative electrode.

【００１１】比較例２ ゲル状亜鉛負極として、水銀を添加した汞化亜鉛を用
い、上記の添加物を添加しない以外は実施例と同様のボ
タン型空気電池を作製した。Comparative Example 2 A button type air battery was manufactured in the same manner as in Example except that mercury-added zinc hydride was used as the gelled zinc negative electrode and the above additives were not added.

【００１２】上記のようにして作製した本発明の実施例
１〜１６及び比較例１，２の電池について、温度２０℃
−湿度６０％のもとで、２５０Ωで連続放電を行い、終
止電圧１．０Ｖまでの放電持続時間を測定した。その放
電持続時間を表１に示す。Regarding the batteries of Examples 1 to 16 of the present invention and Comparative Examples 1 and 2 produced as described above, the temperature was 20 ° C.
-Under a humidity of 60%, continuous discharge was carried out at 250 Ω, and the discharge duration until the final voltage of 1.0 V was measured. The discharge duration is shown in Table 1.

【００１３】[0013]

【表１】 [Table 1]

【００１４】表１の結果により、本発明の実施例１〜１
６のいずれの場合でも、有水銀である比較例２と同等、
もしくはそれ以上の良好な放電特性を示した。さらに、
電池分解を行ったが、未反応亜鉛はほとんどなかった。
また、ＣａＯ及びＭｇＯの添加量を１０〜１００００ｐ
ｐｍとしたが、１０ｐｐｍよりも少なくなると負極内で
の拡散が少ないため、亜鉛利用率の効果が少なく、１０
０００ｐｐｍを超えると負極中の亜鉛配合比が減少する
ため、放電特性が低下した。Ａｌ2 Ｏ3 においても１０
〜１０００ｐｐｍの添加量であるが、１０ｐｐｍよりも
少なくなると負極内での拡散が少ないため、亜鉛利用率
の効果が少なく、１０００ｐｐｍを超えると負極中の亜
鉛配合比が減少するため、放電特性が低下した。これに
対して比較例１では放電特性が良くなかった。また、電
池分解を行ったところ、多量の未反応亜鉛が残ってい
た。From the results of Table 1, Examples 1 to 1 of the present invention
In any case of 6, the same as Comparative Example 2 containing mercury,
Or, it showed more excellent discharge characteristics. further,
The battery was disassembled, but there was almost no unreacted zinc.
Also, the addition amount of CaO and MgO is 10 to 10,000 p
However, if it is less than 10 ppm, the diffusion rate in the negative electrode is small, and the effect of zinc utilization is small.
If it exceeds 000 ppm, the zinc blending ratio in the negative electrode decreases, and the discharge characteristics deteriorate. 10 for Al 2 O 3
Although the amount of addition is up to 1000 ppm, if it is less than 10 ppm, the diffusion rate in the negative electrode is small, and the effect of zinc utilization is small. did. On the other hand, in Comparative Example 1, the discharge characteristics were not good. When the battery was disassembled, a large amount of unreacted zinc remained.

【００１５】上記の結果からも明らかなように、ゲル状
亜鉛負極にＣａＯ、ＭｇＯ及びＡｌ2 Ｏ3 のうちいずれ
か１種類以上を添加することで、亜鉛利用率低下を抑制
し、優れた放電特性を示すことが判る。添加量として
は、ＣａＯ及びＭｇＯでは１０〜１００００ｐｐｍ、Ａ
ｌ2 Ｏ3 では１０〜１０００ｐｐｍとするのが最も好ま
しい。また、２種類以上を添加するとさらに良好な放電
特性が得られることが判る。As is clear from the above results, by adding at least one of CaO, MgO and Al 2 O 3 to the gelled zinc negative electrode, it is possible to suppress a decrease in zinc utilization rate and obtain an excellent discharge. It can be seen that the characteristics are exhibited. The addition amount of CaO and MgO is 10 to 10,000 ppm, A
Most preferably the 10~1000ppm in l 2 O 3. Further, it is understood that even better discharge characteristics can be obtained by adding two or more kinds.

【００１６】なお、実施例において、ボタン型空気電池
について説明したが、他のアルカリマンガン電池、酸化
銀電池等の粒状亜鉛をゲル状亜鉛負極活物質に用いる電
池においても、適宜配合比を変更することで、同様の効
果が得られる。Although the button type air battery has been described in the examples, the compounding ratio is appropriately changed also in other batteries such as alkaline manganese battery and silver oxide battery using granular zinc as the gelled zinc negative electrode active material. Therefore, the same effect can be obtained.

【００１７】[0017]

【発明の効果】以上詳述したように本発明によれば、無
汞化亜鉛粉末を主体とする負極活物質にゲル化剤とアル
カリ電解液とを混合したゲル状亜鉛負極を有する無汞化
亜鉛アルカリ電池において、該ゲル状亜鉛負極にＣａ
Ｏ、ＭｇＯ、Ａｌ2 Ｏ3 のうちいずれか１種類以上を添
加することで、無水銀化に伴う亜鉛利用率低下を抑制
し、優れた放電特性を持つ高性能なアルカリ電池を提供
することができる。As described above in detail, according to the present invention, there is provided a gel-free zinc negative electrode in which a gelling agent and an alkaline electrolyte are mixed with a negative electrode active material mainly composed of zinc-free powder. In a zinc-alkaline battery, the gel zinc negative electrode contains Ca
By adding at least one of O, MgO, and Al 2 O 3 , it is possible to provide a high-performance alkaline battery that suppresses a decrease in zinc utilization rate due to the formation of anhydrous silver and has excellent discharge characteristics. it can.

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

【図１】本発明の本実施例のボタン型空気電池を示す断
面図である。FIG. 1 is a cross-sectional view showing a button type air battery of this embodiment of the present invention.

【符号の説明】[Explanation of symbols]

１ 正極ケース ５ 正極触媒層 ６ セパレータ ７ ゲル状亜鉛負極 ８ 封口板 DESCRIPTION OF SYMBOLS 1 Positive electrode case 5 Positive electrode catalyst layer 6 Separator 7 Gel-like zinc negative electrode 8 Sealing plate

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 無汞化亜鉛粉末を主体とする負極活物質
に、ゲル化剤とアルカリ電解液とを混合したゲル状亜鉛
負極を有する無汞化亜鉛アルカリ電池において、該ゲル
状亜鉛負極に、酸化カルシウム、酸化マグネシウム、酸
化アルミニウムのいずれか１種類以上を添加することを
特徴とする無汞化亜鉛アルカリ電池。1. A gel-free zinc alkaline battery having a gel-like zinc negative electrode in which a gelling agent and an alkaline electrolyte are mixed in a negative electrode active material mainly composed of zinc-free zinc powder. A zinc-free alkaline battery which is characterized by adding at least one of calcium oxide, magnesium oxide, and aluminum oxide. 【請求項２】 該酸化カルシウムを１０〜１００００ｐ
ｐｍ、酸化マグネシウムを１０〜１００００ｐｐｍ、酸
化アルミニウムを１０〜１０００ｐｐｍの範囲で、いず
れか１種類以上を添加することを特徴とする請求項１記
載の無汞化亜鉛アルカリ電池。2. The calcium oxide is added in an amount of 10 to 10000 p.
The unsolicited zinc alkaline battery according to claim 1, wherein any one or more of pm, magnesium oxide of 10 to 10000 ppm and aluminum oxide of 10 to 1000 ppm are added. 【請求項３】 該酸化カルシウム、酸化マグネシウム及
び酸化アルミニウムのうち２種類以上を添加することを
特徴とする請求項１、２記載の無汞化亜鉛アルカリ電
池。3. The unsolicited zinc alkaline battery according to claim 1, wherein two or more kinds of calcium oxide, magnesium oxide and aluminum oxide are added.
JP6899194A 1994-03-15 1994-03-15 Unamalgamated zinc alkaline battery Pending JPH07254407A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6899194A JPH07254407A (en) 1994-03-15 1994-03-15 Unamalgamated zinc alkaline battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6899194A JPH07254407A (en) 1994-03-15 1994-03-15 Unamalgamated zinc alkaline battery

Publications (1)

Publication Number Publication Date
JPH07254407A true JPH07254407A (en) 1995-10-03

Family

ID=13389647

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6899194A Pending JPH07254407A (en) 1994-03-15 1994-03-15 Unamalgamated zinc alkaline battery

Country Status (1)

Country Link
JP (1) JPH07254407A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006004900A (en) * 2004-05-20 2006-01-05 Sony Corp Alkaline dry battery
US8039150B2 (en) * 2005-04-20 2011-10-18 Revoit Technology Ltd. Agglomerated zinc powder anode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006004900A (en) * 2004-05-20 2006-01-05 Sony Corp Alkaline dry battery
US8039150B2 (en) * 2005-04-20 2011-10-18 Revoit Technology Ltd. Agglomerated zinc powder anode

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