JPH0864204A - Negative electrode active material for air-ga primary battery and air-ga primary battery using it - Google Patents
Negative electrode active material for air-ga primary battery and air-ga primary battery using itInfo
- Publication number
- JPH0864204A JPH0864204A JP22419494A JP22419494A JPH0864204A JP H0864204 A JPH0864204 A JP H0864204A JP 22419494 A JP22419494 A JP 22419494A JP 22419494 A JP22419494 A JP 22419494A JP H0864204 A JPH0864204 A JP H0864204A
- Authority
- JP
- Japan
- Prior art keywords
- air
- negative electrode
- active material
- battery
- primary battery
- 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.)
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Classifications
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- Y02E60/128—
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- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、空気−Ｇａ１次電池に
関し、更に詳しくは負極活物質としてＧａまたはＧａを
主とする合金を主成分として使用することにより高容量
電池として構成した空気−Ｇａ１次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air-Ga1 primary battery, and more particularly to an air-Ga1 primary battery composed of a high capacity battery using Ga or an alloy mainly containing Ga as a negative electrode active material. Regarding the next battery.
【０００２】[0002]
【従来の技術】空気電池は、正極活物質として空気中の
酸素を使用することから、電池内に正極活物質を充填す
る必要がなく、密閉型電池として最もエネルギー密度の
高い電池となる。さらに対エネルギー当りの経済性が高
いことから近年ボタン型の空気電池が補聴器用の電源と
して用いられている。2. Description of the Related Art Since an air battery uses oxygen in the air as a positive electrode active material, it is not necessary to fill the positive electrode active material in the battery, and it becomes a battery having the highest energy density as a sealed battery. In addition, a button type air battery has been used as a power source for hearing aids in recent years because it is highly economical with respect to energy.
【０００３】従来の空気電池は、正極に酸素還元用触媒
を担持した酸素透過膜（空気極）を用い、一方、負極に
は活物質として亜鉛を用いている。現存の空気−Ｚｎ電
池は１次電池であり、充放電の可能な２次電池は未だな
い。A conventional air battery uses an oxygen permeable membrane (air electrode) carrying an oxygen reduction catalyst on the positive electrode, while using zinc as an active material on the negative electrode. The existing air-Zn battery is a primary battery, and there is no secondary battery that can be charged and discharged.
【０００４】[0004]
【発明が解決しようとする課題】しかしながらこのよう
な従来の空気電池においては、正極が膜の形態で、活物
質の酸素が空気中から無限に供給されるために、その電
池容量は負極活物質の理論容量によって上限が決まって
しまう。However, in such a conventional air battery, since the positive electrode is in the form of a film and oxygen of the active material is infinitely supplied from the air, the battery capacity thereof is negative. The upper limit is determined by the theoretical capacity of.
【０００５】空気電池用負極活物質としては一般に亜鉛
が用いられているが、この場合の空気電池の公称電圧は
１．４Ｖ（理論電圧：１．６５Ｖ）であり、電気化学等
量は６５．３９／２＝３２．７，理論エネルギー密度は
１４００Wh/kg である。Zinc is generally used as a negative electrode active material for an air battery. In this case, the air battery has a nominal voltage of 1.4 V (theoretical voltage: 1.65 V) and an electrochemical equivalent of 65. 39/2 = 32.7, theoretical energy density is 1400Wh / kg.
【０００６】したがって亜鉛より高電位で、かつ低化学
等量の活物質の開発が望まれ、今までに、鉄、アルカリ
金属、アルカリ土類金属、アルミニウム等の物質が研究
されているが活物質の不活性化の問題が解決できず、実
用化まで至らないのが実状であった。Therefore, it is desired to develop an active material having a potential higher than that of zinc and a low chemical equivalent amount, and substances such as iron, alkali metals, alkaline earth metals, and aluminum have been studied so far. The problem was that the inactivation problem could not be solved and could not be put to practical use.
【０００７】上述のように従来の亜鉛に代る新規な空気
電池用負極活物質を用いて、高容量電池として知られる
従来の空気−亜鉛電池を上回る容量の空気電池の開発が
望まれていた。As described above, it has been desired to develop an air battery having a capacity higher than that of a conventional air-zinc battery known as a high capacity battery, by using a novel negative electrode active material for an air battery which replaces conventional zinc. .
【０００８】[0008]
【課題を解決するための手段】本発明者等は斯かる課題
を解決するために鋭意研究したところ、周期表第３１番
元素であるＧａが、原子量６９．７２、価数変化３、電
気化学当量２３．２４と亜鉛に対して有利な性質を有
し、かつ空気電池用負極活物質となり得ることを見いだ
し、本発明を提供することができた。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve such problems. As a result, Ga, which is the 31st element of the periodic table, has an atomic weight of 69.72, a valence change of 3, and an electrochemical property. The present invention was able to be provided by finding out that it has an equivalent property of 23.24 and zinc, and can be a negative electrode active material for an air battery.
【０００９】すなわち本発明の第１は、ＧａまたはＧａ
を主成分とする合金を用いた新規な空気−Ｇａ１次電池
用負極活物質を開発したことであり、第２は、正極とし
て空気極を、負極としてＧａまたはＧａを主とする合金
を主成分としてなる負極活物質を負極体の中に充填した
ものを用いてなることを特徴とする空気−Ｇａ１次電池
を開発したことである。That is, the first aspect of the present invention is Ga or Ga.
Is to develop a new negative electrode active material for an air-Ga primary battery using an alloy containing as a main component. Secondly, a main component is an air electrode as a positive electrode and Ga or an alloy mainly containing Ga as a negative electrode. The present invention is to develop an air-Ga primary battery characterized by using a negative electrode body filled with the following negative electrode active material.
【００１０】[0010]
【作用】本発明において使用するＧａは、周期表中Ｚｎ
の隣に位置し、化学的にも似た性質をもつ元素であり、
酸・アルカリのどちらにも溶解する両性元素である。特
にアルカリ性水溶液中においては、ＧａＯ3 3-やＨＧａ
Ｏ3 2-などのイオンとなり、あるいはＧａ2 Ｏ3 、Ｇａ
（ＯＨ）3 、ＧａＯＯＨ等の酸化物や水酸化物となって
０から３価の価数変化を起こす。そこでこれらの反応を
電極反応として利用することでＺｎと同様、Ｇａを空気
−Ｇａ１次電池用活物質として用い得ることを予測して
研究を進め、本発明に到達した。In the present invention, Ga is Zn in the periodic table.
Is an element that is located next to and has similar chemical properties,
It is an amphoteric element that dissolves in both acids and alkalis. Especially in an alkaline aqueous solution, GaO 3 3- and HGa
It becomes an ion such as O 3 2− , or Ga 2 O 3 , Ga
It becomes an oxide or hydroxide of (OH) 3 , GaOOH, etc. and changes the valence from 0 to trivalent. Therefore, by utilizing these reactions as an electrode reaction, it was predicted that Ga, like Zn, could be used as an active material for an air-Ga primary battery, and research was advanced to reach the present invention.
【００１１】Ｇａが有する重要な特性として、低融点金
属（融点２９．８℃）であることが挙げられるが、Ｇａ
の液体状態、固体状態の違いは電池特性に大きな影響を
及ぼさない。さらにＩｎ、Ｚｎ、Ｓｎ、Ｐｂ，Ｂｉ、Ｔ
ｌ等の金属と適当な比率で合金化することによって融点
をさらに下げることができる。さらにＧａは従来の活物
質であるＨｇのように環境上問題とされるような毒性を
有していない。このような特性を有しているため、Ｇａ
は空気−Ｇａ１次電池用負極活物質として有用であるこ
とが確認された。An important characteristic of Ga is that it has a low melting point metal (melting point 29.8 ° C.).
The difference between the liquid state and the solid state does not significantly affect the battery characteristics. Furthermore, In, Zn, Sn, Pb, Bi, T
The melting point can be further lowered by alloying with a metal such as 1 at an appropriate ratio. Further, Ga does not have the toxicity which is an environmental problem like Hg which is a conventional active material. Since it has such characteristics, Ga
Was confirmed to be useful as a negative electrode active material for air-Ga primary batteries.
【００１２】Ｇａの使用形態としては、Ｇａ単独でも合
金でもよく、また粉末状でも固体状でも構わないが、粉
末状で用いる場合には電解液中に浸漬して用いるとよい
ことを見いだした。The Ga may be used in the form of Ga alone or an alloy, and may be in the form of powder or solid, but it has been found that when it is used in the form of powder, it may be used by dipping it in an electrolytic solution.
【００１３】一方、空気極は触媒のＰｔを含むアセチレ
ンブラックに結着剤や撥水剤の作用を持つＰＴＦＥ（ポ
リテトラフルオロエチレン）を加えて混合し、次いで該
混合粉を適当な大きさに圧延して集電体のＮｉ網に圧着
して空気極を構成した。On the other hand, for the air electrode, acetylene black containing Pt as a catalyst is mixed with PTFE (polytetrafluoroethylene) having the action of a binder and a water repellent, and then the mixed powder is made to have an appropriate size. It was rolled and pressure-bonded to the Ni net of the current collector to form an air electrode.
【００１４】以下、実施例をもって詳細に説明するが、
本発明の範囲はこれらに限定されるものではない。A detailed description will be given below with reference to examples.
The scope of the present invention is not limited to these.
【００１５】[0015]
【実施例１】図１に示すような正極１として空気極を、
負極２としてＰｔ線（−極）３を挿入したＧａＩｎ合金
１０からなる負極を用いた電池を構成し、放電試験を行
った。この場合の負極活物質としてはＧａ（同和鉱業製
純度６Ｎ）９５wt% とＩｎ（同和鉱業製純度６Ｎ）５wt
% とからなるＧａＩｎ合金３ｇを用いた。空気極として
は触媒のＰｔを含むアセチレンブラックに、結着剤や撥
水剤の作用を持つＰＴＦＥを適量加えて混合し、次いで
この混合粉を適当な大きさに圧延し、集電体のＮｉ網に
圧着して電極としたものを用いた。Example 1 An air electrode was used as the positive electrode 1 as shown in FIG.
A battery using a negative electrode made of a GaIn alloy 10 having a Pt wire (-electrode) 3 inserted as the negative electrode 2 was constructed and a discharge test was conducted. In this case, as the negative electrode active material, Ga (purity 6N manufactured by Dowa Mining Co., Ltd.) 95 wt% and In (purity 6N manufactured by Dowa Mining Co., Ltd.) 5 wt%
3 g of a GaIn alloy consisting of 1% and 3% was used. As an air electrode, acetylene black containing Pt as a catalyst is mixed with an appropriate amount of PTFE having a binding agent and a water repellent effect, and then the mixed powder is rolled into an appropriate size to obtain Ni as a current collector. An electrode was used which was crimped to a net.
【００１６】電解液４には、３０wt% 水酸化カリウム水
溶液を用い、温度２５℃で５mAの放電試験を行った。試
験の結果は図２に示すように放電電圧は１．４３Ｖで非
常に平坦な放電挙動を示した。A 30 wt% potassium hydroxide aqueous solution was used as the electrolytic solution 4, and a discharge test of 5 mA was conducted at a temperature of 25 ° C. As a result of the test, as shown in FIG. 2, the discharge voltage was 1.43 V and showed a very flat discharge behavior.
【００１７】負極活物質であるＧａＩｎ合金は測定温度
２５℃で液体であるが、測定温度を１５℃に変えて固体
状態で放電試験を行った場合も、上記とほぼ同様な放電
挙動を示した。The GaIn alloy, which is the negative electrode active material, is a liquid at a measurement temperature of 25 ° C., but when the measurement temperature was changed to 15 ° C. and a discharge test was conducted in the solid state, the same discharge behavior as above was exhibited. .
【００１８】また上記ＧａＩｎ合金に代え、純Ｇａある
いはＺｎ、Ｓｎ、Ｐｂとの合金を用いた場合でも同様な
結果が得られ、Ｇａを主成分とする本発明の負極活物質
がいずれも充分に有用であることが確認できた。用いた
合金はそれぞれＺｎ５wt% 、Ｓｎ５wt% 、Ｐｂ５wt% を
含むＧａ−Ｚｎ、Ｇａ−Ｓｎ、Ｇａ−Ｐｂ合金であっ
た。Similar results are obtained when pure Ga or an alloy with Zn, Sn, or Pb is used in place of the GaIn alloy, and the negative electrode active material of the present invention containing Ga as a main component is sufficiently used. It was confirmed to be useful. The alloys used were Ga-Zn, Ga-Sn, and Ga-Pb alloys containing Zn5wt%, Sn5wt%, and Pb5wt%, respectively.
【００１９】[0019]
【比較例１】実施例１との比較のため負極活物質として
亜鉛を用いた空気−Ｚｎ１次電池を構成し、放電試験を
行った。この場合、亜鉛（同和鉱業製純度４Ｎ）３ｇを
圧延により板状にして負極材とした他は、実施例１と同
一条件で放電試験を行った。その結果は図２中に別の曲
線で示した。Comparative Example 1 For comparison with Example 1, an air-Zn primary battery using zinc as a negative electrode active material was constructed and a discharge test was conducted. In this case, the discharge test was conducted under the same conditions as in Example 1 except that 3 g of zinc (purity: 4N manufactured by Dowa Mining Co., Ltd.) was rolled into a plate shape to obtain a negative electrode material. The result is shown by another curve in FIG.
【００２０】図２に見るように、放電電圧１．３４Ｖの
平坦な電位が得られたが、実施例１のＧａＩｎ合金の負
極材を用いた場合に比較して負極活物質質量当りの容量
は少ないことが判明した。As shown in FIG. 2, a flat potential of a discharge voltage of 1.34 V was obtained, but the capacity per mass of the negative electrode active material was higher than that of the case where the GaIn alloy negative electrode material of Example 1 was used. It turned out to be few.
【００２１】[0021]
【実施例２】図３に示すように電解液にＧａ粉（粒径２
００μｍアンダー）を負極活物質として充填して、（Ｇ
ａ粉＋電解液）１１とした空気電池を構成した。この場
合、Ｇａ粉はまず純度４ＮのＧａを液体窒素中で冷却し
固体にした後、液体窒素温度に近い極低温の状態で粉砕
し、この粉が液体にならない温度（１５℃程度）の水中
でふるいにかけ、２００μｍアンダーのＧａ粉を得た。Example 2 As shown in FIG. 3, Ga powder (particle size 2
00 μm under) as a negative electrode active material, and (G
An air battery constituted by a powder + electrolyte solution 11 was constructed. In this case, the Ga powder is first made into a solid by cooling Ga having a purity of 4N in liquid nitrogen, and then pulverized in an extremely low temperature state close to the temperature of liquid nitrogen, and the powder is cooled in water at a temperature (about 15 ° C) And sieved to obtain Ga powder of 200 μm under.
【００２２】次いでこのＧａ粉にポリアクリル酸ナトリ
ウムを１wt% 溶解させた３０wt% 水酸化カリウムを適量
混ぜ、これを負極に充填した後、セパレーター８、空気
極としての正極１（＋極リード線６）を取り付けて測定
セルとした。Next, an appropriate amount of 30 wt% potassium hydroxide in which 1 wt% of sodium polyacrylate was dissolved was mixed with this Ga powder, and this was filled in the negative electrode. Then, the separator 8 and the positive electrode 1 (+ electrode lead wire 6 as the air electrode 6) were mixed. ) Was attached to make a measuring cell.
【００２３】実施例１と同様に温度２５℃、５mAの条件
で放電試験を行ったところ、放電電圧は１．２８Ｖであ
り、実施例１よりも若干低いものの充分に空気電池とし
て利用できることが確認できた。When a discharge test was conducted under the conditions of a temperature of 25 ° C. and 5 mA in the same manner as in Example 1, the discharge voltage was 1.28 V, which was slightly lower than that of Example 1, but was confirmed to be sufficiently usable as an air battery. did it.
【００２４】[0024]
【発明の効果】上述のように本発明は、主成分として金
属ＧａまたはＧａ合金を負極活物質として用いた空気−
Ｇａ１次電池を提供するものである。本発明の空気−Ｇ
ａ１次電池は従来の空気−Ｚｎ１次電池より高容量化を
図れるものである。INDUSTRIAL APPLICABILITY As described above, according to the present invention, air containing metal Ga or Ga alloy as a main component as a negative electrode active material is used.
A Ga primary battery is provided. Air-G of the present invention
The a primary battery has a higher capacity than the conventional air-Zn primary battery.
【図１】実施例１における測定用セルの構造図。FIG. 1 is a structural diagram of a measuring cell according to a first embodiment.
【図２】実施例１および比較例１における放電特性図。FIG. 2 is a discharge characteristic diagram in Example 1 and Comparative Example 1.
【図３】実施例２における測定用セルの構造図。FIG. 3 is a structural diagram of a measuring cell in Example 2.
１ 正極 ２ 負極 ３ Ｐｔ線（−極） ４ 電解液 ５ ＰＰセル ６ ＋極リード線 ７ フタ ８ セパレーター ９ Ｐｔ板 １０ Ｇａ／Ｉｎ合金 １１ Ｇａ粉＋電解液 1 Positive electrode 2 Negative electrode 3 Pt wire (-electrode) 4 Electrolyte solution 5 PP cell 6 + Electrode lead wire 7 Lid 8 Separator 9 Pt plate 10 Ga / In alloy 11 Ga powder + Electrolyte solution
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石田 典也 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 (72)発明者 坂本 陵 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 (72)発明者 柳沢 真樹子 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Noriya Ishida 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Within Dowa Mining Co., Ltd. (72) Inventor Ryo Sakamoto 1-2-8 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (72) Inventor Makiko Yanagisawa 1-2-8 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd.
Claims (2)
としてなることを特徴とする空気−Ｇａ１次電池用負極
活物質。1. A negative electrode active material for an air-Ga primary battery, which is mainly composed of Ga or an alloy mainly composed of Ga.
とする合金を主成分としてなる負極活物質を負極体の中
に充填したものを負極として成ることを特徴とする空気
−Ｇａ１次電池。2. An air-Ga primary battery comprising an air electrode as a positive electrode and a negative electrode body filled with a negative electrode active material containing Ga or an alloy mainly containing Ga as a main component. .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22419494A JP3587213B2 (en) | 1994-08-25 | 1994-08-25 | Negative electrode active material for air-Ga primary battery and air-Ga primary battery using the same |
| US08/340,725 US5462821A (en) | 1993-11-19 | 1994-11-16 | Gallium based active material for the negative electrode, a negative electrode using the same, and batteries using said negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22419494A JP3587213B2 (en) | 1994-08-25 | 1994-08-25 | Negative electrode active material for air-Ga primary battery and air-Ga primary battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0864204A true JPH0864204A (en) | 1996-03-08 |
| JP3587213B2 JP3587213B2 (en) | 2004-11-10 |
Family
ID=16809999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22419494A Expired - Fee Related JP3587213B2 (en) | 1993-11-19 | 1994-08-25 | Negative electrode active material for air-Ga primary battery and air-Ga primary battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3587213B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100660949B1 (en) * | 2005-03-09 | 2006-12-26 | 재단법인서울대학교산학협력재단 | Self-healing gallium alloy electrode, lithium secondary battery using thereof and manufacturing method of gallium alloy electrode |
-
1994
- 1994-08-25 JP JP22419494A patent/JP3587213B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100660949B1 (en) * | 2005-03-09 | 2006-12-26 | 재단법인서울대학교산학협력재단 | Self-healing gallium alloy electrode, lithium secondary battery using thereof and manufacturing method of gallium alloy electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3587213B2 (en) | 2004-11-10 |
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