JP3089440B2 - Alkaline battery - Google Patents
Alkaline batteryInfo
- Publication number
- JP3089440B2 JP3089440B2 JP03352567A JP35256791A JP3089440B2 JP 3089440 B2 JP3089440 B2 JP 3089440B2 JP 03352567 A JP03352567 A JP 03352567A JP 35256791 A JP35256791 A JP 35256791A JP 3089440 B2 JP3089440 B2 JP 3089440B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- alkaline battery
- alkaline
- indium
- zinc alloy
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/06—Electrodes for primary cells
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルカリ電池の負極活物
質である亜鉛合金粒または無水銀亜鉛合金粒の腐食によ
るガス発生を防止するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to prevent the generation of gas due to corrosion of zinc alloy particles or mercury-free zinc alloy particles which are negative electrode active materials of alkaline batteries.
【０００２】[0002]
【従来の技術】従来、アルカリ電池では、活物質として
の亜鉛合金粒と、アルカリ電解液とをゲル化したゲル状
負極が用いられている。かかるアルカリ電池では、ゲル
状負極中の亜鉛がアルカリ電解液で腐食されると、水素
ガスを発生した内圧が上昇したり、電池容量が低下す
る。この亜鉛の腐食は、主に亜鉛の水素過電圧が低いこ
とが原因である。このため、前記亜鉛の表面を水銀でア
マルガム化する汞化処理を施すことによって、該亜鉛合
金粒の水素過電圧を高めている。2. Description of the Related Art Conventionally, an alkaline battery uses a gelled negative electrode obtained by gelling zinc alloy particles as an active material and an alkaline electrolyte. In such an alkaline battery, when the zinc in the gelled negative electrode is corroded by the alkaline electrolyte, the internal pressure at which hydrogen gas is generated increases, and the battery capacity decreases. This zinc corrosion is mainly caused by the low hydrogen overpotential of zinc. For this reason, the surface of the zinc is subjected to a meroizing treatment for amalgamating with mercury to increase the hydrogen overpotential of the zinc alloy particles.
【０００３】ところが、近年、環境公害問題上の見地か
ら電池内の水銀量の低減化が望まれている。このような
ことから、汞化処理に用いる水銀量が少なくなくても十
分な耐食性を有する負極活物質として、種々の金属元素
（例えば鉛、インジューム、アルミニウム、ガリウム
等）を亜鉛に添加した組成の亜鉛合金粒が用いられるよ
うになってきた。However, in recent years, it has been desired to reduce the amount of mercury in a battery from the viewpoint of environmental pollution. For this reason, as a negative electrode active material having sufficient corrosion resistance even if the amount of mercury used in the calcining process is not small, a composition in which various metal elements (for example, lead, indium, aluminum, gallium, etc.) are added to zinc. Zinc alloy grains have come to be used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記組
成のアルミニウム等との亜鉛合金粒が汞化処理されてい
ない場合には、電解液に対する十分な耐食性を得ること
ができないため、かかる亜鉛合金粒を負極活物質として
用いたアルカリ電池では、貯蔵中に水素ガス発生による
内圧上昇を抑制することができず破裂するという問題点
があった。However, if the zinc alloy particles with aluminum or the like having the above composition are not subjected to the aluminizing treatment, sufficient corrosion resistance to the electrolyte cannot be obtained. The alkaline battery used as the negative electrode active material has a problem that the internal pressure cannot be suppressed due to the generation of hydrogen gas during storage, and the battery ruptures.
【０００５】本発明は、従来の問題点を解決するために
なされたもので、環境汚染のない汞化処理されていない
亜鉛合金粒の腐食を十分に防止したゲル状負極を備え、
貯蔵中の水素ガス発生による内圧上昇を抑制したアルカ
リ電池を提供しようとするものである。SUMMARY OF THE INVENTION The present invention has been made to solve the conventional problems, and has a gelled negative electrode which has sufficiently prevented corrosion of zinc alloy particles which have not been subjected to calorization and have no environmental pollution.
An object of the present invention is to provide an alkaline battery in which an increase in internal pressure due to generation of hydrogen gas during storage is suppressed.
【０００６】[0006]
【課題を解決するための手段】本発明は亜鉛合金粒とゲ
ル化剤とアルカリ電解液とからなるゲル状負極を具備し
たアルカリ電池において、該ゲル状負極に、０．１〜２
０μｍの粒径の酸化インジュームを添加したことを特徴
とするアルカリ電池である。好ましくは酸化インジュー
ムが、Ｉｎ２Ｏ３、ＩｎＯ、Ｉｎ２Ｏであること、添加
量がゲル状負極中に、１０〜３０００ＰＰＭであるこ
と、また亜鉛合金粒が微量または全く水銀汞化されてい
なくてもよい。SUMMARY OF THE INVENTION The present invention relates to an alkaline battery provided with a gelled negative electrode comprising zinc alloy particles, a gelling agent, and an alkaline electrolyte, wherein the gelled negative electrode comprises 0.1 to 2 parts.
An alkaline battery to which an oxidation indium having a particle diameter of 0 μm is added. Preferably, the oxidation indium is In 2 O 3 , InO, In 2 O, the addition amount is 10 to 3000 PPM in the gelled negative electrode, and the zinc alloy particles are slightly or completely mercurized. It is not necessary.
【０００７】[0007]
【作用】本発明はゲル状負極内に分散した酸化インジュ
ームが、亜鉛合金粒表面に近づくと、亜鉛と反応して金
属インジュームになろうとする。金属インジュームにな
ると酸化インジューム中の酸素が発生する。しかしこの
反応は進行せず、酸化インジュームは酸化物のままの状
態を保っている。進行しない理由は、亜鉛合金粒から水
素ガス発生しようとする反応が一方であるため、亜鉛合
金粒に直接接触できないためである。この反応が互にバ
ランスをとっているため、長期貯蔵中反応が進まず、水
素、酸素ガスが発生しなくなる。これは特に水銀無汞化
亜鉛合金粒の防食に効果がある。このためアルカリ電池
の貯蔵特性の向上ができる。According to the present invention, when the indium oxide dispersed in the gelled negative electrode approaches the surface of the zinc alloy particles, it reacts with zinc to form metal indium. When metal indium is formed, oxygen in the oxidation indium is generated. However, this reaction does not proceed, and the oxidation indium remains as an oxide. The reason why it does not proceed is that direct reaction with the zinc alloy particles is not possible because one reaction is to generate hydrogen gas from the zinc alloy particles. Since these reactions balance each other, the reaction does not proceed during long-term storage, and hydrogen and oxygen gas are not generated. This is particularly effective in preventing corrosion of mercury-free and non-melted zinc alloy particles. For this reason, the storage characteristics of the alkaline battery can be improved.
【０００８】[0008]
【実施例】次に本発明の実施例を説明する。まず、負極
に添加する酸化インジュームの添加量と種類とを検討し
た。アルカリ電池の負極として、汞化されていない亜鉛
合金粒３０ｋｇ、ゲル化剤としてポリアクリル酸０．５
ｋｇ、ＫＯＨ電解液１９ｋｇとを混合してなるゲル状亜
鉛を作成した。次に、粒径が０．１〜２０μｍの酸化イ
ンジュームとしてＩｎ２Ｏ３を、０．５ｇ（１０ＰＰ
Ｍ）、１０ｇ（２００ＰＰＭ）、１００ｇ（２０００Ｐ
ＰＭ）、１５０ｇ（３０００ＰＰＭ）、２００ｇ（４０
００ＰＰＭ）とを別々にゲル状亜鉛に添加混合して、ゲ
ル状負極を作成した。Next, embodiments of the present invention will be described. First, the amount and type of oxide indium added to the negative electrode were examined. 30 kg of unmelted zinc alloy particles as a negative electrode of an alkaline battery, 0.5 g of polyacrylic acid as a gelling agent
kg and 19 kg of a KOH electrolyte solution to prepare gelled zinc. Next, 0.5 g (10 PP) of In 2 O 3 was used as an oxidation indium having a particle size of 0.1 to 20 μm.
M), 10 g (200 PPM), 100 g (2000 PPM)
PM), 150 g (3000 PPM), 200 g (40
00PPM) was separately added to and mixed with gelled zinc to form a gelled negative electrode.
【０００９】また、酸化インジュームはＩｎ２Ｏ３の他
に、ＩｎＯ、Ｉｎ２Ｏについても各々１０ｇ（２００Ｐ
ＰＭ）添加混合して同様に作成した。これらの上記ゲル
状負極を各々用いて、ＬＲ６型アルカリ乾電池を製造
し、６０℃に３０日間貯蔵し、添加量と添加物別に発生
したガスの量を測定して表１に示した。Further, in addition to indium oxide is In 2 O 3, InO, each also In 2 O 10g (200P
PM) was prepared in the same manner by adding and mixing. Using these gelled negative electrodes, an LR6 type alkaline dry battery was manufactured, stored at 60 ° C. for 30 days, and the amount of addition and the amount of gas generated for each additive were measured.
【００１０】[0010]
【表１】 [Table 1]
【００１１】次に、酸化インジュームＩｎ２Ｏ３の粒径
の影響を検討した。粒径０．１μｍ、１μｍ、２０μ
ｍ、３０μｍのＩｎ２Ｏ３を入手して、２００ＰＰＭ添
加したゲル状負極を作成し、前記同様にＬＲ６型アルカ
リ乾電池を製造し、同様試験で粒径別に発生したガス量
を測定し、表２に示した。Next, the influence of the particle size of the indium oxide In 2 O 3 was examined. Particle size 0.1μm, 1μm, 20μ
m and 30 μm of In 2 O 3 were obtained, a gelled negative electrode to which 200 PPM was added was prepared, an LR6-type alkaline dry battery was produced in the same manner as described above, and the amount of gas generated for each particle size was measured in the same test. It was shown to.
【００１２】[0012]
【表２】 [Table 2]
【００１３】本発明は表１に示されたように、Ｉｎ２Ｏ
３が１０〜３０００ＰＰＭ（０．５〜１５０ｇ）の添加
量において、ガス発生量が特に少なく良好である。しか
し無添加及び２００ｇ（４０００ＰＰＭ）については好
ましいくない。さらに表１から、Ｉｎ２Ｏ３の他に、Ｉ
ｎＯ、Ｉｎ２Ｏであっても同様に良好な効果が得ること
ができる。As shown in Table 1, the present invention relates to In 2 O
3, when the amount of addition is 10 to 3000 PPM (0.5 to 150 g), the amount of generated gas is particularly small and is good. However, no addition and 200 g (4000 PPM) are not preferred. Further, from Table 1, in addition to In 2 O 3 , I
Even with nO or In 2 O, a good effect can be obtained similarly.
【００１４】次に表２から、Ｉｎ２Ｏ３の粒径の影響を
検討した結果、粒径０．１μｍ〜２０μｍの範囲で良好
な結果が得られた。３０μｍ以上は若干ガス発生が多く
なった。Next, from Table 2, as a result of examining the influence of the particle size of In 2 O 3 , good results were obtained in the particle size range of 0.1 μm to 20 μm. Gas generation slightly increased at 30 μm or more.
【００１５】本発明は好ましくは、Ｉｎ２Ｏ３、Ｉｎ
Ｏ、Ｉｎ２Ｏである。また粒径が０．１〜２０μｍを用
いる理由は、ゲル状負極へ亜鉛粒の分散性が優れている
ためである。亜鉛合金粒の表面に付着し易すくするた
め、特に粒径を限定して用いる必要がある。酸化インジ
ュームの粒径が２０μｍを越えると、分散性が悪くな
り、効果が片寄りバラッキの原因となる。また、０．１
μｍ未満では、まず微粉を製造するのが困難であること
と分散性もよくない。The present invention preferably employs In 2 O 3 , In
O and In 2 O. The reason why the particle diameter is 0.1 to 20 μm is that zinc particles are excellent in dispersibility in the gelled negative electrode. In order to make it easy to adhere to the surface of the zinc alloy particles, it is necessary to use the particles with a limited particle size. If the particle size of the oxidized indium exceeds 20 μm, the dispersibility will be poor, and the effect will be uneven and cause unevenness. Also, 0.1
If it is less than μm, it is difficult to first produce fine powder and dispersibility is not good.
【００１６】なお、本発明は水銀０％に限定されること
なく、微量の水銀を添加した亜鉛合金粒においても、同
様の効果が得られる。また、酸化インジュームは、０．
１〜２０μｍの粒径の微粉に粉砕できれば、Ｉｎ２Ｏ３
・ｎＨ２Ｏを添加してもよい。The present invention is not limited to 0% mercury, and a similar effect can be obtained even with zinc alloy particles containing a small amount of mercury. Further, the oxidation indium is 0.1%.
If it can be pulverized into fine powder having a particle size of 1 to 20 μm, In 2 O 3
- the nH 2 O may be added.
【００１７】[0017]
【発明の効果】本発明はアルカリ電池のゲル状負極に粒
径が０．１〜２０μｍの酸化インジュームを１０〜３０
００ＰＰＭ存在させることにより、ガス発生を防止でき
た。ゲル状負極の汞化量は当初は１０重量％であった
が、現在では０．１５重量％まで低下している。しか
し、本発明は水銀０％においても、酸化インジュームを
上記微量添加することにより、ガス発生を防止し、地球
環境にやさしいアルカリ電池を提供できるようになっ
た。According to the present invention, an indium oxide having a particle size of 0.1 to 20 μm is added to a gelled negative electrode of an alkaline battery for 10 to 30 minutes.
Gas generation could be prevented by the presence of 00 PPM. The amount of calorification of the gelled negative electrode was 10% by weight at the beginning, but has now decreased to 0.15% by weight. However, according to the present invention, even in the case of 0% mercury, gas generation is prevented by adding the above-mentioned trace amount of indium oxide, and an alkaline battery friendly to the global environment can be provided.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−111441（ＪＰ，Ａ) 特開 平３−280356（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/62 H01M 4/06 ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-111441 (JP, A) JP-A-3-280356 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/62 H01M 4/06 JICST file (JOIS)
Claims (3)
とからなるゲル状負極を具備したアルカリ電池におい
て、 該ゲル状負極に、０．１〜２０μｍの粒径の酸化インジ
ュームを添加したことを特徴とするアルカリ電池。1. An alkaline battery provided with a gelled negative electrode comprising zinc alloy particles, a gelling agent and an alkaline electrolyte, wherein an oxide indium having a particle size of 0.1 to 20 μm is added to the gelled negative electrode. An alkaline battery, characterized in that:
ｎＯ、Ｉｎ２Ｏであることを特徴とする請求項１記載の
アルカリ電池。2. The method according to claim 1, wherein the oxidation indium is In 2 O 3 , I
nO, alkaline batteries according to claim 1, wherein it is an In 2 O.
ＰＰＭゲル状負極に添加されていることを特徴とする請
求項１、２記載のアルカリ電池。3. The method according to claim 1, wherein the oxidation indium is 10 to 3000.
3. The alkaline battery according to claim 1, wherein the alkaline battery is added to a PPM gelled negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03352567A JP3089440B2 (en) | 1991-11-13 | 1991-11-13 | Alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03352567A JP3089440B2 (en) | 1991-11-13 | 1991-11-13 | Alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05135770A JPH05135770A (en) | 1993-06-01 |
| JP3089440B2 true JP3089440B2 (en) | 2000-09-18 |
Family
ID=18424943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03352567A Expired - Lifetime JP3089440B2 (en) | 1991-11-13 | 1991-11-13 | Alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3089440B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009060A1 (en) * | 2004-07-16 | 2006-01-26 | Fdk Energy Co., Ltd. | Cylindrical alkaline battery |
| KR200489538Y1 (en) * | 2016-12-01 | 2019-07-02 | 주식회사 엘지생활건강 | Cosmetic Device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4083482B2 (en) * | 2001-08-09 | 2008-04-30 | 三洋化成工業株式会社 | Gelling agent for alkaline battery and alkaline battery |
| US7579115B2 (en) | 2004-07-08 | 2009-08-25 | Sanyo Chemical Industries, Ltd. | Gelling agent for alkaline battery and alkaline battery |
| WO2006028095A1 (en) | 2004-09-09 | 2006-03-16 | Sanyo Chemical Industries, Ltd. | Thickener for alkaline battery and alkaline battery |
| CN109075314B (en) * | 2016-10-03 | 2021-04-27 | 松下知识产权经营株式会社 | Alkaline dry cell |
-
1991
- 1991-11-13 JP JP03352567A patent/JP3089440B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009060A1 (en) * | 2004-07-16 | 2006-01-26 | Fdk Energy Co., Ltd. | Cylindrical alkaline battery |
| JP2006032152A (en) * | 2004-07-16 | 2006-02-02 | Fdk Energy Co Ltd | Cylindrical alkaline battery |
| KR200489538Y1 (en) * | 2016-12-01 | 2019-07-02 | 주식회사 엘지생활건강 | Cosmetic Device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05135770A (en) | 1993-06-01 |
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