JPS62123658A - Zinc-alkaline battery - Google Patents
Zinc-alkaline batteryInfo
- Publication number
- JPS62123658A JPS62123658A JP60262495A JP26249585A JPS62123658A JP S62123658 A JPS62123658 A JP S62123658A JP 60262495 A JP60262495 A JP 60262495A JP 26249585 A JP26249585 A JP 26249585A JP S62123658 A JPS62123658 A JP S62123658A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- aluminum
- zinc
- negative electrode
- copper
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の分野］
本発明は亜鉛アルカリ電池に関し、詳１ノくけ鉛、イン
ジウム、タリウム、カドミウム、スズ、ビスマス、ガリ
ウム、銀より選ばれる１種以上とアルミニウムおよび銅
を特定の範囲で含有した亜鉛合金を汞化もしくは汞化す
ることなく負極活物質として用いた亜鉛アルカリ電池に
関する。[Detailed Description of the Invention] [Field of the Invention] The present invention relates to a zinc-alkaline battery, in particular one or more selected from lead, indium, thallium, cadmium, tin, bismuth, gallium, and silver, and aluminum and copper. The present invention relates to a zinc-alkaline battery using a zinc alloy containing a specific range as a negative electrode active material without being converted into a liquid or without forming into a liquid.
［発明の背景］
亜鉛を負極活物質として用いたアルカリ電池においては
、水酸化カリウム水溶液等の強アルカリ性電解液を用い
るため、電池を密閉しなければならない。この電池の密
閉は電池の小型化を図る際には特に重要であるが、同時
に電池保存中の亜鉛の腐食により発生する水素ガスを閉
じ込めることになる。従って長期保存中に電池内部のガ
ス圧が高まり、密閉が完全なほど爆発等の危険が伴なう
。[Background of the Invention] In an alkaline battery using zinc as a negative electrode active material, a strong alkaline electrolyte such as an aqueous potassium hydroxide solution is used, so the battery must be sealed. This sealing of the battery is particularly important when attempting to miniaturize the battery, but it also traps hydrogen gas generated due to corrosion of zinc during battery storage. Therefore, during long-term storage, the gas pressure inside the battery increases, and the more completely the battery is sealed, the greater the risk of explosion.
その対策として、負極活物質である亜鉛の腐食を防止し
て、電池内部の水素ガス発生を少なくすることが研究さ
れ、水銀添加による亜鉛の水素過電圧を高めた汞化亜鉛
粉末を負極活物質として用いることが専ら行なわれてい
る。このため、市販されているアルカリ電池の負極活物
質は３．０〜１０重量％重量％水銀が含まれているため
、打金的ニーズとして、より低水銀のもの、あるいは無
水銀の電池の開発が強く要望されるようになり、種々の
研究がなされている。例えば亜鉛中に鉛、ガリウム、イ
ンジウムなどを添加した合金粉末を用いて耐食性を向上
させ、かつ合金粉末の表向平滑化作用による耐食Ｈの一
段の１１１と汞化率を低減化することによる放電性能の
劣化を防止づ−るために、亜鉛より卑な金属であるアル
ミニウム等を添加づることが提案されている。As a countermeasure, research has been conducted to prevent the corrosion of zinc, which is an active material for the negative electrode, and to reduce the generation of hydrogen gas inside the battery. It is used exclusively. For this reason, since the negative electrode active materials of commercially available alkaline batteries contain 3.0 to 10% by weight of mercury, there is a need for the development of lower mercury or mercury-free batteries. There has been a strong demand for this, and various studies have been conducted. For example, the corrosion resistance is improved by using an alloy powder in which lead, gallium, indium, etc. are added to zinc, and the surface smoothing effect of the alloy powder increases the corrosion resistance to 111 and reduces the corrosion rate. In order to prevent performance deterioration, it has been proposed to add aluminum, which is a metal less noble than zinc.
しかしながら、畦鉛にアルミニウムを添加した場合には
、低汞化率にお（Ｊるｈり市竹能並びに耐食性においで
ある稈亀有効であるが、電池の６０℃、３〜４ケ月程度
の長期高調保存において、電池内の水素ガス発生が急激
に増加りる欠点を有し−でいる。これは亜鉛にアルミニ
ウムを添加した場合一般に発生する粒間腐食現象に起因
すると考えられる。このようにアルミニウムを添加した
場合の上記欠点を克服した低水化率亜鉛合金を負極活物
質として用いた電池の確立が今後の重要な課題とされて
いる。However, when aluminum is added to the ridge lead, it is effective in reducing the rate of deterioration (in terms of corrosion resistance and corrosion resistance). During long-term high-temperature storage, hydrogen gas generation within the battery rapidly increases.This is thought to be due to the intergranular corrosion phenomenon that generally occurs when aluminum is added to zinc. An important future challenge is to establish a battery using a low hydration rate zinc alloy as a negative electrode active material, which overcomes the above-mentioned drawbacks when aluminum is added.
［発明の目的］
本発明はかかる現状に鑑み、耐食性、放電性能を劣化さ
せることなく、汞化率を低減化させた負極活物質を用い
た亜鉛アルカリ電池を提供することを目的とする。[Object of the Invention] In view of the current situation, an object of the present invention is to provide a zinc-alkaline battery using a negative electrode active material that has a reduced rate of corrosion without deteriorating corrosion resistance or discharge performance.
［発明の経緯１
本発明者らは、この目的に沿って鋭意研究の結果、１ｌ
ｌｊ鉛を主成分とする負極活物質において、鉛、インジ
ウム、タリウム、カドミウム、スス゛、ビスマス、カリ
ウム、銀より選ばれる１種以上とアルミニウムと銅を特
定量添加すれば、長期高調保存における水素ガス発生量
の急激な増加を防止できると共に、アルミニウムの／ｉ
＆電性能の向上効果も陪害されないことを見出し、本発
明を完成した。[Background of the invention 1 As a result of intensive research in line with this purpose, the inventors have discovered
If one or more selected from lead, indium, thallium, cadmium, soot, bismuth, potassium, and silver, as well as specific amounts of aluminum and copper are added to a negative electrode active material whose main component is lead, hydrogen gas can be maintained during long-term high-temperature storage. In addition to preventing a sudden increase in the amount generated,
& The present invention was completed by discovering that the effect of improving electrical performance was not adversely affected.
［発明の構成］
１なわら本発明は、鉛、インジウム、タリウム、カドミ
ウム、スズ、ビスマス、ガリウム、銀より選ばれる１種
以上を０．００５〜０．５重量％、アルミニウムを０．
００５〜０．５重量％、銅を０．００１〜０．３重量％
含有する亜鉛合金を負極活物質として用いたことを特徴
とする亜鉛アルカリ電池にある。[Structure of the Invention] 1. The present invention includes 0.005 to 0.5% by weight of one or more selected from lead, indium, thallium, cadmium, tin, bismuth, gallium, and silver, and 0.00% by weight of aluminum.
005-0.5% by weight, copper 0.001-0.3% by weight
There is provided a zinc-alkaline battery characterized in that the zinc alloy containing the present invention is used as a negative electrode active material.
本発明において、鉛、インジウム、タリウム、カドミウ
ム、スズ、ヒ゛スマス、ガリウム、銀より選ばれる１種
以上とアルミニウムと銅を特定量感加した亜鉛合金は、
そのまま負極活物質どして用いるか、亜鉛合金を汞化し
た後に負極活物質として用いる。汞化する場合の水銀含
有率は、従来の負極活物質の水銀含有率よりも少ない量
、すなわち３．０重量％未満であるが、より汞化率を低
くし、低公害性を考慮するど１．；）Φ品％以下である
。Ｊ、た、１．０重量％前後またはそれ以下の少量であ
ってもガス発生を抑制することが可能である。特に、排
気機構を備えた空気電池や水素吸収機構を備えた亜鉛ア
ルカリ電池等においては、水素ガスの発生許容量は比較
的大きいので、このような電池に本発明を適用する場合
は、１．０重量％以下の低汞化率または無汞化の亜鉛合
金を負極活物質どして使用することが可能である。In the present invention, the zinc alloy sensitized with one or more selected from lead, indium, thallium, cadmium, tin, ausmuth, gallium, and silver and specific amounts of aluminum and copper is
It can be used as a negative electrode active material as it is, or it can be used as a negative electrode active material after a zinc alloy is made into a starch. The mercury content when it is converted into water is lower than the mercury content of conventional negative electrode active materials, that is, less than 3.0% by weight. 1. ;) Φ product% or less. It is possible to suppress gas generation even with a small amount of about 1.0% by weight or less. In particular, in air batteries equipped with an exhaust mechanism, zinc-alkaline batteries equipped with a hydrogen absorption mechanism, etc., the permissible amount of hydrogen gas generated is relatively large, so when applying the present invention to such batteries, 1. It is possible to use a zinc alloy with a low or non-grading rate of 0% by weight or less as the negative electrode active material.
この負極活物質に用いられる亜鉛合金の鉛、インジウム
、タリウム、カドミウム、スズ、ビスマス、ガリウム、
銀にり選ばれる１種以上の合ｈ１量の含有率は０．００
５〜０．５重量％、アルミニウムの含有率は０．００５
〜０．５重量％、銅の含有率はｏ、ｏｏｉ〜０．３重量
％ど少量で添加効果が発揮される。酊）、インジウム、
タリウム、カドミウム、スズ、ビスマス、ガリウム、銀
より選ばれる１種以上の合泪吊の含有率が０．００５重
量％未満では耐食性向上に効果がなく、０．５重量％を
越えると放電性能が低下する。また、アルミニウムの含
有率が０．００５重量％未満では放電性能の向上効果が
少なく、０．５重量％を越えると水素ガス発生量が大き
くなり好ましくない。銅の含有率が０．００１重量％未
満では粒間腐食の防止効果が少なく、０．３重量％を越
えると放電性能に悪影響を及ぼす。The zinc alloys used in this negative electrode active material include lead, indium, thallium, cadmium, tin, bismuth, gallium,
The content of one or more selected silver pastes is 0.00
5-0.5% by weight, aluminum content is 0.005
The effect of addition is exhibited in small amounts such as ~0.5% by weight and copper content of ~0.3% by weight. intoxication), indium,
If the content of one or more types of thallium selected from thallium, cadmium, tin, bismuth, gallium, and silver is less than 0.005% by weight, it will not be effective in improving corrosion resistance, and if it exceeds 0.5% by weight, the discharge performance will deteriorate. descend. Furthermore, if the aluminum content is less than 0.005% by weight, the effect of improving discharge performance will be small, and if it exceeds 0.5% by weight, the amount of hydrogen gas generated will increase, which is not preferable. If the copper content is less than 0.001% by weight, the effect of preventing intergranular corrosion will be small, and if it exceeds 0.3% by weight, it will adversely affect the discharge performance.
なお、アルミニウムの含有率はｏ、 ｏｏｓ〜０．２重
量％の範囲が特に好ましく、０．２重量％を越えた場合
にはそれほどの含有効果は見られない。Note that the content of aluminum is particularly preferably in the range of o, oos to 0.2% by weight, and if it exceeds 0.2% by weight, no significant effect of the inclusion will be seen.
これら各添加元素の作用効果は充分に解明されていない
が、推定するに亜鉛合金中に含まれている鉛、インジウ
ム、タリウム、カドミウム、スズ、ビスマス、ガリウム
、銀は水素過電圧を高める作用あるいはアルカリ電解液
中で水銀との相乗効果により亜鉛の腐食を抑制する作用
を有すると考えられる。一方、アルミニウムには低汞化
においても放電性能を劣化させない作用を有し、銅はア
ルミニウムの存在下で粒間腐食を防止する作用を有する
。Although the effects of each of these additive elements have not been fully elucidated, it is presumed that the lead, indium, thallium, cadmium, tin, bismuth, gallium, and silver contained in zinc alloys have the effect of increasing the hydrogen overvoltage or the alkali It is thought that it has the effect of inhibiting zinc corrosion due to a synergistic effect with mercury in the electrolyte. On the other hand, aluminum has the effect of not deteriorating the discharge performance even at low temperatures, and copper has the effect of preventing intergranular corrosion in the presence of aluminum.
なお、亜鉛にアルミニウムが存在Ｊる場合の＾渇長期保
存下にお（）る水＊万ス発牛組の急ｉ１な増加の原因に
ついて本発明者は粒間腐食によるものと推定しているが
、そのアルミニウムにＪ、る粒間腐食問題は金属合金分
野では周知のことである。In addition, the inventor presumes that the cause of the sudden increase in the amount of water produced during long-term storage when aluminum is present in zinc is due to intergranular corrosion. However, the problem of intergranular corrosion in aluminum is well known in the metal alloy field.
また、粒間腐食の防止に対して銅が添加効果を有する理
由は明白でないが、恐らく金属組織学的なものと推定さ
れる。Furthermore, although the reason why copper has an additive effect on preventing intergranular corrosion is not clear, it is probably due to metallographic reasons.
本発明は、これら各作用の相乗効果により、放電特性を
劣化させることな（、耐食性のよい亜鉛合金が得られた
ものである。In the present invention, due to the synergistic effect of these respective effects, a zinc alloy with good corrosion resistance is obtained without deteriorating the discharge characteristics.
このように本発明の亜鉛アルカリ電池は、電解液に苛性
カリ、苛性ソーダ等を１：成分と覆るアルカリ水溶液を
用い、負極活物質に１−記し／、：ｄｆ（鉛合金または
汞化した亜鉛合金、正極活物質に二酸化マンガン、酸化
銀、酸素等を用いることによりｊｑられる。As described above, the zinc-alkaline battery of the present invention uses an alkaline aqueous solution containing caustic potash, caustic soda, etc. as a 1: component as an electrolyte, and has a negative electrode active material of 1-, :df (lead alloy or oxidized zinc alloy, This can be achieved by using manganese dioxide, silver oxide, oxygen, etc. as the positive electrode active material.
［実施例のｄ１明］
以下、実施例および比較例に基づいて本発明を具体的に
説明する。[d1 Light of Examples] The present invention will be specifically described below based on Examples and Comparative Examples.
実施例１〜７および比較１０二二［
純度９９．９９７％以上の亜鉛地金を約５００℃で溶融
し、これに第１表に示すごとく鉛、インジウム、アルミ
ニウムをそれぞれ０．０５重石％、０．０２重間％、０
．０５重量％添加して亜鉛合金を作成し、これを高几ア
ルゴンガス（噴出圧５ ｋｇ ／ ａｔ ）を使って５
０〜１５０メツシユの粒度範囲に篩別し、粉体化した。Examples 1 to 7 and Comparison 1022 [Zinc ingot with a purity of 99.997% or more is melted at about 500°C, and as shown in Table 1, 0.05% lead, indium, and aluminum are each added to it. 0.02 weight%, 0
．． 05% by weight was added to create a zinc alloy, and this was heated using high-temperature argon gas (ejection pressure 5 kg/at).
It was sieved to a particle size range of 0 to 150 mesh and powdered.
次に水酸化カリウム１０％のアルカリ性溶液中に、上記
粉末を投入し、２５℃で１０分間予備撹拌を行ない、汞
化率が１．０重量％になるように水銀を細孔より徐々に
滴下しながら２５℃で６０分間撹拌した。次いで水洗を
行ない４５℃で一昼夜乾燥を行なって亜鉛合金粉末（比
較例１）を得た。・また、第１表に示すごとく、下記の
組成でそれぞれ、
１）：鉛０．０５重量％、インジウム０．０２重量％、
アルミニウム０．０５重量％、銅０．０００５重量＝７
−
％（比較例２）
２）：鉛０．０５重量％、インジウｂ ０９０２小絹％
、アルミニウム０．０５ 市１％、銅０．００１＠損％
（実施例１）
３〉：鉛０．０５重量％、インジウム０．０２重量％、
アルミニウム０．０５重量％、銅０．０１重量％（実施
例２）
４）：鉛０．０５重量％、インジウム０．０２重量％、
アルミニウム０．０５重量％、銅０．３重量％（実施例
３）
５）：鉛０．０５重間％、インジウム０．０２重量％、
アルミニウム０．０５重量％、銅０．５重間％（比較例
３）
６）：鉛０．０５Φ石％、インジウム０．０２重品％、
アルミニウム０．０５巾Ｕ％、銅１．０重−％（比較例
４）
７）：インジウム０．１重量％、アルミニウム０．２重
石％（比較例５）
８）：インジウム０．１重量％、アルミニウム０．２重
量％、銅０．１重量％（実施例４）９） ： １） ０
．１ｔｌｉＭ％、イ＞シウム０．０２ ！ｉ１％、ガリ
ウム０．１重量％、アルミニウム０．０５重量％（比較
例６）
１０）：鉛０．１重量％、インジウム０．０２重重閤、
ガリウム０．１重量％、アルミニウム０．０５重量％、
銅０．０５ ｉｍ％（実施例５）
１１）：鉛ｏ、ｉ重量％、インジウム０．０２重量％、
タリウム０．０２重量％、カドミウム０．０２重−％、
ガリウム０．０１重量％、銀０，０５重量％、アルミニ
ウム０．０５重量％（比較例７）
１２）：鉛０，１市ｆｉ１％、イ＞シ’ｙム０，０２
ｉ［１ｉ５ｔ％、タリウム０．０２重量％、カドミウム
０．０２重量％、ガリウム０．０１重量％、銀０．０５
重量％、アルミニウム０．０５重量％、銅０．０５重量
％（実施例６）１３）：鉛０．０２重量％、インジウム
０．０２重量％、タリウム０．０２重石％、カドミウム
０．０２重間％、スズ０．０１重量％、ビスマス０．０
１重量％、ガリウ７４０．０１重量％、銀０．０２重崩
％重量ルミニウム０．０５重重重（比較例８）
１４）：鉛０．０２重量％、インジウム０．０２重量％
、タリウム０．０２小吊％、カドミウム０．０２小量％
、スズ０．０１重間％、ビスマス０．０１車編％、ガリ
ウム０．（１１重量％、銀０．０２重串％、アルミニウ
ム０．０５重量％、銅０，０５重娼％（実施例７）から
なる亜鉛合金をそれぞれ作成し、これを前記と同様な方
法で粉体化し、汞化処理を行なって水銀含有率が１．０
重量％の亜鉛合金粉末（実施例１〜７および比較例２〜
８）を得た。Next, the above powder was put into an alkaline solution of 10% potassium hydroxide, prestirred for 10 minutes at 25°C, and mercury was gradually added dropwise through the pores so that the aqueous conversion rate was 1.0% by weight. The mixture was stirred at 25° C. for 60 minutes. Next, it was washed with water and dried at 45° C. for a day and night to obtain a zinc alloy powder (Comparative Example 1). - Also, as shown in Table 1, each of the following compositions: 1): 0.05% by weight of lead, 0.02% by weight of indium,
Aluminum 0.05% by weight, copper 0.0005% by weight = 7
-% (Comparative Example 2) 2): Lead 0.05% by weight, Injiu B 0902 small silk%
, Aluminum 0.05 City 1%, Copper 0.001@Loss%
(Example 1) 3>: 0.05% by weight of lead, 0.02% by weight of indium,
0.05% by weight of aluminum, 0.01% by weight of copper (Example 2) 4): 0.05% by weight of lead, 0.02% by weight of indium,
0.05% by weight of aluminum, 0.3% by weight of copper (Example 3) 5): 0.05% by weight of lead, 0.02% by weight of indium,
0.05% aluminum, 0.5% copper (comparative example 3) 6): 0.05% lead, 0.02% indium,
Aluminum 0.05 width U%, copper 1.0 weight% (Comparative Example 4) 7): Indium 0.1 weight%, aluminum 0.2 weight% (Comparative Example 5) 8): Indium 0.1 weight% , aluminum 0.2% by weight, copper 0.1% by weight (Example 4) 9): 1) 0
．． 1tliM%, I>Sium 0.02! i1%, gallium 0.1% by weight, aluminum 0.05% by weight (Comparative Example 6) 10): Lead 0.1% by weight, indium 0.02% by weight,
Gallium 0.1% by weight, aluminum 0.05% by weight,
Copper 0.05 im% (Example 5) 11): Lead o, i wt%, indium 0.02 wt%,
Thallium 0.02% by weight, cadmium 0.02% by weight,
Gallium 0.01% by weight, Silver 0.05% by weight, Aluminum 0.05% by weight (Comparative Example 7) 12): Lead 0.1 City fi 1%, I>Sim 0.02
i[1i5t%, thallium 0.02% by weight, cadmium 0.02% by weight, gallium 0.01% by weight, silver 0.05
Weight %, aluminum 0.05 weight %, copper 0.05 weight % (Example 6) 13): lead 0.02 weight %, indium 0.02 weight %, thallium 0.02 weight %, cadmium 0.02 weight % %, tin 0.01% by weight, bismuth 0.0
1% by weight, 740.01% by weight of Galium, 0.02% by weight of silver, 0.05% by weight of aluminum (Comparative Example 8) 14): 0.02% by weight of lead, 0.02% by weight of indium
, 0.02% thallium, 0.02% cadmium
, 0.01% tin, 0.01% bismuth, 0.0% gallium. (11% by weight, 0.02% by weight of silver, 0.05% by weight of aluminum, and 0.05% by weight of copper (Example 7), and powdered in the same manner as above. mercury content is 1.0 after
% by weight of zinc alloy powder (Examples 1-7 and Comparative Examples 2-
8) was obtained.
このようにして得られたり１鉛合金粉末を使−】で水素
ガス発生試験を行ない、その結果を第１表に示す。なお
、ガス発生試験は、電解液として濃度４０重量％の水酸
化カリウム水溶液に酸化亜鉛を飽和させたものを５ｘ１
用い、亜鉛合金粉末をＨＩ ０ＪＩＩいて６０℃で３０
日問および６０日間のガス発生ｆｍ（ｘｌ／ａ ）を測
定した。A hydrogen gas generation test was conducted using the lead alloy powder thus obtained and the results are shown in Table 1. In addition, in the gas generation test, a potassium hydroxide aqueous solution with a concentration of 40% by weight was saturated with zinc oxide as an electrolyte.
Zinc alloy powder was heated to HI 0JII at 60℃ for 30 minutes.
Gas production fm (xl/a ) was measured daily and for 60 days.
また、これらの亜鉛合金粉末を負極活物質どして第１図
に示すアルカリマンガン電池を用いて電池性能を評価し
た。第１図のアルカリマンガン電池は、正極缶１、正極
２、負極３、セパレーター４、封口体５、負極底板６、
負極集電体７、キャップ８、熱収縮性樹脂チューブ９、
絶縁リング１０゜１１、外装缶１２で構成されている。Further, battery performance was evaluated using an alkaline manganese battery shown in FIG. 1 using these zinc alloy powders as a negative electrode active material. The alkaline manganese battery shown in FIG. 1 includes a positive electrode can 1, a positive electrode 2, a negative electrode 3, a separator 4, a sealing body 5, a negative electrode bottom plate 6,
negative electrode current collector 7, cap 8, heat-shrinkable resin tube 9,
It consists of an insulating ring 10°11 and an outer can 12.
このアルカリマンガン電池を用いて放電負荷４Ω、２０
℃の放電条Ｆ＋により終止電圧０，９Ｖまでの放電持続
時間を測定し、比較例１の測定値を１００とした指数で
示した。結束を第１表に示す。Using this alkaline manganese battery, the discharge load is 4Ω, 20Ω.
The discharge duration up to the final voltage of 0.9 V was measured using a discharge strip F+ at ℃, and expressed as an index with the measured value of Comparative Example 1 as 100. The binding is shown in Table 1.
（：ｆｌ；ｉｌ ’ｉｉ ｔｉど−１ど′、３６５１ｂ
ノ第１表に示されるごとく、亜鉛に鉛、インジウム、タ
リウム、カドミウム、スズ、ヒ゛スマス、力′リウム、
銀より選ばれる１紳以Ｉ−どアルミニウム＼に加えて銅
を特定範囲の間添加して汞化さｉ！ｌ、：汞化亜鉛合金
粉末を負極活物質に用いた実施例１〜７は、銅を無添加
、もしくは上記範囲から外れで銅を添加した汞化亜鉛合
金粉末を負極活物質に用いた比較例１〜８に比べて、特
に長期高温保存にお【プる水素ガス発生が抑制され、ま
た放電性能においては、上記範囲においては銅の添加に
起因する悪影響は見られず、高い放電性能を示している
。(:fl;il 'ii ti-1-do', 3651b
As shown in Table 1, zinc contains lead, indium, thallium, cadmium, tin, hesmuth, thallium,
In addition to the aluminum selected from silver, copper is added within a specific range to form a chemical compound. l.: Examples 1 to 7 in which zinc chloride alloy powder was used as the negative electrode active material were compared with examples 1 to 7 in which copper was not added or zinc chloride alloy powder to which copper was added outside the above range was used as the negative electrode active material. Compared to Examples 1 to 8, the generation of hydrogen gas during long-term high-temperature storage was suppressed, and in terms of discharge performance, no adverse effects due to the addition of copper were observed within the above range, and high discharge performance was achieved. It shows.
［発明の効果］
以上説明のごとく、鉛、インジウム、タリウム、カドミ
ウム、スズ、ビスマス、ガリウム、銀より選ばれる１種
以上とアルミニウムと銅を特定範囲で含有した亜鉛合金
をそのまま、もしくは汞化して負極活物質として用いた
本ブで明の亜鉛アルカリ電池は、特に長期高温保存に、
１月」る水素ガス発生率を抑制しつつ、電池性能を向１
−さｌることが可能であり、また水銀が低含有率もしく
は含有しｌ−。[Effects of the invention] As explained above, a zinc alloy containing one or more selected from lead, indium, thallium, cadmium, tin, bismuth, gallium, and silver, and aluminum and copper within a specific range is used as it is or after being made into a The zinc-alkaline battery used as the negative electrode active material is particularly suitable for long-term high-temperature storage.
Improving battery performance while suppressing hydrogen gas generation rate
- It is possible to reduce the amount of mercury and contain low or low mercury content.
いことから、ネ１会的ニーズにも沿ったものである。As such, it is in line with the needs of the community.
従って、本発明の亜鉛アルカリ電池は広範な用途に使用
可能である。Therefore, the zinc-alkaline battery of the present invention can be used in a wide range of applications.
第１図は本発明に係わるアルカリマンガン電池の側断面
図を示す。
１：正極缶、 ２：正極、 ３：負極、４：セパレ
ーター、５：封口体、６：負極底板、７：負極集電体、
８：キャップ、
９：熱収縮性樹脂チューブ、
ｉｏ、１ｉ：絶縁リング、１２：外装缶。FIG. 1 shows a side sectional view of an alkaline manganese battery according to the present invention. 1: positive electrode can, 2: positive electrode, 3: negative electrode, 4: separator, 5: sealing body, 6: negative electrode bottom plate, 7: negative electrode current collector,
8: Cap, 9: Heat-shrinkable resin tube, io, 1i: Insulating ring, 12: Exterior can.
Claims (1)
スマス、ガリウム、銀より選ばれる１種以上の合計量を
０．００５〜０．５重量％、アルミニウムを０．００５
〜０．５重量％、銅を０．００１〜０．３重量％含有す
る亜鉛合金を負極活物質として用いたことを特徴とする
亜鉛アルカリ電池。 ２、前記亜鉛合金が汞化されている前記特許請求の範囲
第１項記載の亜鉛アルカリ電池。[Claims] 1. The total amount of one or more selected from lead, indium, thallium, cadmium, tin, bismuth, gallium, and silver is 0.005 to 0.5% by weight, and aluminum is 0.005% by weight.
A zinc-alkaline battery characterized in that a zinc alloy containing -0.5% by weight and 0.001-0.3% by weight of copper is used as a negative electrode active material. 2. The zinc-alkaline battery according to claim 1, wherein the zinc alloy is made of aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60262495A JPH0622122B2 (en) | 1985-11-25 | 1985-11-25 | Zinc alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60262495A JPH0622122B2 (en) | 1985-11-25 | 1985-11-25 | Zinc alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62123658A true JPS62123658A (en) | 1987-06-04 |
| JPH0622122B2 JPH0622122B2 (en) | 1994-03-23 |
Family
ID=17376588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60262495A Expired - Lifetime JPH0622122B2 (en) | 1985-11-25 | 1985-11-25 | Zinc alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0622122B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0500313A2 (en) * | 1991-02-19 | 1992-08-26 | Mitsui Mining & Smelting Co., Ltd. | Zinc alloy powder for alkaline cell and method to produce the same |
| US5240793A (en) * | 1988-12-07 | 1993-08-31 | Grillo-Werke Ag | Alkaline batteries containing a zinc powder with indium and bismuth |
| US6284410B1 (en) | 1997-08-01 | 2001-09-04 | Duracell Inc. | Zinc electrode particle form |
| US7875390B2 (en) * | 2005-11-22 | 2011-01-25 | Panasonic Corporation | Alkaline battery and method for producing the same |
| KR20210058905A (en) | 2018-10-22 | 2021-05-24 | 닛폰세이테츠 가부시키가이샤 | Casting method of cast steel |
-
1985
- 1985-11-25 JP JP60262495A patent/JPH0622122B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5240793A (en) * | 1988-12-07 | 1993-08-31 | Grillo-Werke Ag | Alkaline batteries containing a zinc powder with indium and bismuth |
| EP0500313A2 (en) * | 1991-02-19 | 1992-08-26 | Mitsui Mining & Smelting Co., Ltd. | Zinc alloy powder for alkaline cell and method to produce the same |
| US6284410B1 (en) | 1997-08-01 | 2001-09-04 | Duracell Inc. | Zinc electrode particle form |
| US7875390B2 (en) * | 2005-11-22 | 2011-01-25 | Panasonic Corporation | Alkaline battery and method for producing the same |
| KR20210058905A (en) | 2018-10-22 | 2021-05-24 | 닛폰세이테츠 가부시키가이샤 | Casting method of cast steel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0622122B2 (en) | 1994-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0371737B2 (en) | ||
| JPS62123658A (en) | Zinc-alkaline battery | |
| JPH0421310B2 (en) | ||
| JPS61153950A (en) | Zinc alkaline storage battery | |
| JPS6177257A (en) | Zinc alkaline battery | |
| JPH0375985B2 (en) | ||
| JPS6240161A (en) | Zinc alkaline battery | |
| JPS61193362A (en) | Zinc alkaline battery | |
| JPS61153952A (en) | Zinc alkaline storage battery | |
| JPH0375983B2 (en) | ||
| JPS6240157A (en) | Zinc alkaline battery | |
| JPS61153951A (en) | Zinc alkaline storage battery | |
| JPH01279564A (en) | Manufacture of amalgamated zinc alloy powder | |
| JPS61290652A (en) | Zinc alkaline battery | |
| JPS62123657A (en) | Zinc-alkaline battery | |
| JPS6240159A (en) | Zinc alkaline battery | |
| JPS61290655A (en) | Zinc alkaline battery | |
| JPH0375984B2 (en) | ||
| JPS6240158A (en) | Zinc alkaline battery | |
| JPS61290654A (en) | Zinc alkaline battery | |
| JPS6240163A (en) | Zinc alkaline battery | |
| JPS6240160A (en) | Zinc alkaline battery | |
| JPS61290653A (en) | Zinc alkaline battery | |
| JPH0418672B2 (en) | ||
| JPS61290651A (en) | Zinc alkaline battery |