JPS63285869A - Alkaline battery - Google Patents
Alkaline batteryInfo
- Publication number
- JPS63285869A JPS63285869A JP12226287A JP12226287A JPS63285869A JP S63285869 A JPS63285869 A JP S63285869A JP 12226287 A JP12226287 A JP 12226287A JP 12226287 A JP12226287 A JP 12226287A JP S63285869 A JPS63285869 A JP S63285869A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- boric acid
- zinc
- electrolyte
- discharge
- 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
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 boric acid ions Chemical class 0.000 claims abstract description 16
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 229940063013 borate ion Drugs 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
-
- 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
-
- 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、低水銀化のために負極活物質にアルミニウ
ムを含む亜鉛合金を用いたアルカリ電池に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an alkaline battery using a zinc alloy containing aluminum as a negative electrode active material to reduce mercury.
（従来の技術）
亜鉛の氷化のための水銀は、一種の公害物質であるとこ
ろから、現在では水銀の含有量を低下させるための亜鉛
合金の開発が種々なされている。(Prior Art) Since mercury, which causes zinc to freeze, is a type of pollutant, various zinc alloys are currently being developed to reduce the mercury content.
そのなかで、とりわけアルミニウムを含む亜鉛合金は、
ガスの発生を抑制で、き、低汞化のための有力な材料で
あるとして注目されている。Among them, zinc alloys containing aluminum are particularly
It is attracting attention as a powerful material for suppressing gas generation and reducing carbon dioxide emissions.
（発明が解決しようとする問題点）
しかしながら、アルミニウム含有亜鉛合金を負極活物質
として用いた場合には、ある負荷抵抗で急速に放電性能
が低下することが問題となっている。(Problems to be Solved by the Invention) However, when an aluminum-containing zinc alloy is used as a negative electrode active material, there is a problem in that the discharge performance rapidly deteriorates at a certain load resistance.
この現像は、特に軽負荷放電時で特異的に発現している
が、これら放電性能の低下した電池の内部を分解して調
べた結果、放電反応生成物によって内部短絡を起こして
いることが判明した。This development occurs specifically during light load discharge, but as a result of disassembling and examining the inside of these batteries with degraded discharge performance, it was found that internal short circuits were caused by discharge reaction products. did.
最も確度の高いこととして推定されることは、アルミニ
ウムを含む亜鉛合金が、特定の電流で放電されることに
よって特異な結晶が成長し、該結晶がセパレータを貝通
し、その結果短絡現象を引き起こすのであろうと考えら
れている。The most accurate assumption is that when a zinc alloy containing aluminum is discharged with a specific current, peculiar crystals grow, and these crystals pass through the separator, resulting in a short circuit phenomenon. It is thought that there will be.
従って、この対策どしてまず最初に考えられることは、
セパレータの材質を厚くしたり、１！維を密にすること
によって内部短絡を封することであるが、このような方
法で対処した場合にはゲル状負極亜鉛の充ｖＡ量の減少
による放電容伍の低下や、内部抵抗の増大等の不都合を
生じ、一般的性能を大幅に低下させるものとなる。Therefore, the first thing to consider for this measure is:
Make the material of the separator thicker, 1! The idea is to seal the internal short circuit by making the fibers denser, but if this method is used, the discharge capacity will decrease due to a decrease in the charging capacity of the gelled negative electrode zinc, and the internal resistance will increase. This results in inconveniences and greatly reduces general performance.
そこで本発明者らは、この種の特異な結晶の生成を阻害
する物質について種々検討した結果、ホウ酸またはホウ
酸を含む一アルカリ塩を電解液に添加したところ所定の
効果を得ることを確認した。As a result of various studies on substances that inhibit the formation of this type of unique crystal, the present inventors confirmed that adding boric acid or a monoalkali salt containing boric acid to the electrolytic solution produced the desired effect. did.
本発明は以上の知見に基づきなされたもので、その目的
とするところは、アルミニウムを含む低氷化亜鉛合金を
使用したアルカリ電池において、放電性の内部短絡を防
止し、放電性能を高い水準に維持するようにしたアルカ
リ電池を提供するものである。The present invention was made based on the above knowledge, and its purpose is to prevent internal short circuits in the discharge property and to improve the discharge performance to a high level in alkaline batteries using a low-icing zinc alloy containing aluminum. To provide an alkaline battery that maintains
（問題点を解決するための手段）
前記目的を達成するため、この発明は、負極活物質とし
てアルミニウムを含む亜鉛合金を用いたアルカリ電池に
おいて、該負極活物質を含むゲル状亜鉛負極の電解液と
してホウ酸イオンを含む電解液を用いたことを要旨とす
る。(Means for Solving the Problems) In order to achieve the above object, the present invention provides an electrolyte solution for a gelled zinc negative electrode containing the negative electrode active material in an alkaline battery using a zinc alloy containing aluminum as a negative electrode active material. The gist is that an electrolytic solution containing borate ions was used.
すなわち、本発明のアルカリ電池は、負極を構成する材
料として、前記アルミニウム含有の亜鉛合金からなる負
極活物質と、ゲル状アルカリ電解液との混合物を用い、
前記ゲル状アルカリ電解液中にホウ酸、またはホウ酸の
アルカリ塩形態でホウ酸イオンを添加したものである。That is, the alkaline battery of the present invention uses a mixture of the negative electrode active material made of the aluminum-containing zinc alloy and a gelled alkaline electrolyte as the material constituting the negative electrode,
Boric acid ions in the form of boric acid or an alkali salt of boric acid are added to the gel-like alkaline electrolyte.
そして、該ホウ酸イオンは、負極活物質中に含まれるア
ルミニウムが特定の放電条件下で亜鉛の特異な結晶の生
成を妨害するイオンとして含有され、その添加量は、亜
鉛負極に対して重量比で１０〜１１００ｐｐの割合で電
解液中に含有されていることが望ましい。The borate ions are contained as ions that prevent the aluminum contained in the negative electrode active material from forming specific crystals of zinc under specific discharge conditions, and the amount added is determined by weight ratio to the zinc negative electrode. It is desirable that the electrolytic solution contains 10 to 1100 pp of oxide.
なお、その含有量が１０ｐｐｍを下回ると結晶生成の阻
害物質としての絶対量が少なく、また、１１００ｐｐ以
上を越えて添加したとしても効果の増加が余り期待でき
ない割りには、添加但増大に伴い、開路電圧の低下を招
くなどの不都合を生ずるので、上記の範囲内の添加量と
する。In addition, when the content is less than 10 ppm, the absolute amount as an inhibitor of crystal formation is small, and even if it is added in excess of 1100 ppm, no increase in effect can be expected. Since this may cause inconveniences such as a decrease in open circuit voltage, the amount added should be within the above range.
（作 用）
ホウ酸イオンの添加によって、特定の負荷抵抗での放電
性能の低下は見られなくなった。またこの事実に対する
作用機序は明らかでないが、ホウ酸イオンの存在によっ
て特異な結晶の生成が阻害され、結晶による内部短絡現
象がなくなるからであると推定される。(Effect) With the addition of borate ions, no deterioration in discharge performance was observed at a specific load resistance. Although the mechanism behind this fact is not clear, it is presumed that the presence of borate ions inhibits the formation of specific crystals and eliminates the internal short-circuit phenomenon caused by the crystals.
（実 施 例） 以下、実施例によってこの発明の詳細な説明する。(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.
まず、この発明の実施に用いたＬＲＯａ形電池の構造は
、図に示す一般的構造となっている。First, the structure of the LROa type battery used to implement the present invention is a general structure shown in the figure.
図における電池は、正極缶を兼ねた有底円筒型の電池ケ
ース１の上部開口の内周部を負極端子板２の周縁フラン
ジ部に封口ガスケット３を介して絞り加工、カール加工
などによってカシメ付け、電池内部を密封している。In the battery shown in the figure, the inner periphery of the upper opening of a bottomed cylindrical battery case 1 that also serves as a positive electrode can is caulked to the peripheral flange of a negative electrode terminal plate 2 through a sealing gasket 3 by drawing, curling, etc. , the inside of the battery is sealed.
電池内部には、上端を前記封口ガスケット３の中心を０
通して前記負極端子板２に電気的接続した集電棒４と、
該集電棒４の外周を取巻くようにして負極５、セパレー
タ６、及び二酸化マンガンを主体とする正極合剤７が同
心状に充填され、発電要素を構成している。Inside the battery, place the upper end with the center of the sealing gasket 3 at 0.
a current collector rod 4 electrically connected to the negative terminal plate 2 through the
A negative electrode 5, a separator 6, and a positive electrode mixture 7 mainly composed of manganese dioxide are filled concentrically around the outer periphery of the current collector rod 4 to constitute a power generation element.
前記負極５はアルミニウム含有の亜鉛合金からなる負極
活物質と、ゲル状アルカリ電解液との混合物であり、本
発明では前記ゲル状アルカリ電解液中にホウ酸、または
ホウ酸アルカリ塩形態で１１＼つ酸イオンが含まれてい
る。The negative electrode 5 is a mixture of a negative electrode active material made of an aluminum-containing zinc alloy and a gel-like alkaline electrolyte, and in the present invention, boric acid or boric acid alkali salt form 11\ Contains oxalic acid ions.
以上の構成の電池において、ホウ酸イオンを会まない従
来電池では、例えば３００Ω軽負荷で連続放電した場合
に氷化率１．５％以下の低氷化亜鉛負極を用いると放電
性能が低下しやすい。In a battery with the above configuration, in a conventional battery that does not contain borate ions, if a low icing zinc negative electrode with a icing rate of 1.5% or less is used during continuous discharge under a light load of 300Ω, for example, the discharge performance will decrease. Cheap.
そこで、電解液中にホウ酸を負極亜鉛に対して１ｍ比で
１０〜２００＋）ｌ）ｍ添加した本発明サンプル（イ）
〜（ニ）を用意し、それぞれの放電性能を比較した所、
以下の表に示す結果を得た。Therefore, the present invention sample (A) in which boric acid was added to the electrolytic solution at a ratio of 10 to 200+)l)m to the negative electrode zinc
~(d) were prepared and the discharge performance of each was compared.
The results shown in the table below were obtained.
なお、亜鉛ｆＪ極は前記アルミニウムを６００ｐｐｍ含
むほかに鉛５００ｐｐｍ、インジウム２００ｐｐｍ含む
亜鉛合金で水化率は１．０％のものを用い、従来電池も
同一の亜鉛合金で氷化率は１゜０％であるものを用いた
。The zinc fJ electrode used was a zinc alloy containing 600 ppm of aluminum, 500 ppm of lead, and 200 ppm of indium, with a hydration rate of 1.0%, and the conventional battery was also made of the same zinc alloy with a icing rate of 1.0%. % was used.
また、比較例では鉛５００ｐｐｍ、インジウム２ｏｏｐ
ｐｍのみでアルミニウムを含まない合金を用いた。In addition, in the comparative example, lead was 500 ppm and indium was 2 oop.
An alloy containing only pm and no aluminum was used.
表
以上の表に示す結果から明らかなように、本発明では電
解液中にホウ酸イオンを含まないアルミニウム含有亜鉛
合金を用いた従来の電池に比べて何意差が明らかに生じ
ている。また、比較例で示したアルミニウムを含まない
亜鉛合金を用いた電池は、放電特性としては良好な状態
を示しているが、ガス発生抑制の面で不利であり、総合
的な評価としては前記実施例で得た電池が上回るものと
なる。As is clear from the results shown in the tables above, the present invention clearly shows some difference compared to the conventional battery using an aluminum-containing zinc alloy that does not contain borate ions in the electrolyte. In addition, the battery using a zinc alloy that does not contain aluminum shown in the comparative example shows good discharge characteristics, but is disadvantageous in terms of suppressing gas generation. The battery obtained in the example will be better.
また、（ニ）のホウ酸の添加量が１ｏｏｐｐｍを上回っ
たものについては効果の向上が見られないばかりか、開
路電圧の面で不利になるので、本発明ではホウ酸イオン
の下限を１０ｐｐｍ、上限を２ｏｏｐｐｍとすることで
、最良の結果を得ることができる。Furthermore, if the amount of boric acid (d) added exceeds 1 ooppm, not only will the effect not be improved, but it will also be disadvantageous in terms of open circuit voltage. The best results can be obtained by setting the upper limit to 2ooppm.
また、前記実施例ではホウ酸形態でホウ酸イオンを含有
させているが、ホウ酸ナトリウム、ホウ酸カリウム等ホ
ウ酸のアルカリ塩類であっても同様の効果を達成するこ
とを確認している。Furthermore, although borate ions are contained in the form of boric acid in the above examples, it has been confirmed that similar effects can be achieved using alkali salts of boric acid such as sodium borate and potassium borate.
（効 果）
以上の説明から明らかなように、本発明にあっては、ホ
ウ酸イオンの添加によって特定の負荷抵抗での放電性能
の低下はなく、またこのことはホウ酸イオンの存在によ
って特異な結晶の生成が阻害され、内部短絡が防止でき
た結果であると推定される。(Effects) As is clear from the above explanation, in the present invention, the addition of borate ions does not reduce the discharge performance at a specific load resistance, and this is caused by the presence of borate ions. This is presumed to be the result of inhibiting the formation of crystals and preventing internal short circuits.
したがって、以上の組成の負極を用いた場合には低氷化
材料であるアルミニウム含有によるガス発生の抑制効果
とともに、これの欠点であった特定の負荷抵抗下での内
部短絡を防止できることになり、低水銀化材料として有
用である。Therefore, when using a negative electrode with the above composition, it is possible to suppress gas generation due to the inclusion of aluminum, which is a low-icing material, and also to prevent internal short circuits under a certain load resistance, which was a drawback of this method. It is useful as a low mercury material.
図は本発明に係るアルカリマンガン電池の断面図である
。
１・・・正極ｒｆ′ｉ２・・・負極端子板３・・・封口
ガスケット ４・・・集電棒５・・・負極
６・・・ヒバレータ７・・・正極合剤The figure is a sectional view of an alkaline manganese battery according to the present invention. 1... Positive electrode rf'i2... Negative electrode terminal plate 3... Sealing gasket 4... Current collector rod 5... Negative electrode
6...Hiberator 7...Positive electrode mixture
Claims (3)
用いたアルカリ電池において、該負極活物質を含むゲル
状亜鉛負極の電解液としてホウ酸イオンを含む電解液を
用いたことを特徴とするアルカリ電池。(1) An alkaline battery using a zinc alloy containing aluminum as a negative electrode active material, characterized in that an electrolyte containing borate ions is used as an electrolyte for a gelled zinc negative electrode containing the negative electrode active material. .
カリ塩であることを特徴とする特許請求の範囲第１項に
記載のアルカリ電池。(2) The alkaline battery according to claim 1, wherein the boric acid ion is boric acid or an alkali salt of boric acid.
０〜１００ｐｐｍの割合で電解液中に含有されているこ
とを特徴とする特許請求の範囲第１項または第２項に記
載のアルカリ電池。(3) The borate ion has a weight ratio of 1 to the negative electrode zinc.
The alkaline battery according to claim 1 or 2, wherein the alkaline battery is contained in the electrolytic solution in a proportion of 0 to 100 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12226287A JP2563109B2 (en) | 1987-05-19 | 1987-05-19 | Alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12226287A JP2563109B2 (en) | 1987-05-19 | 1987-05-19 | Alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63285869A true JPS63285869A (en) | 1988-11-22 |
| JP2563109B2 JP2563109B2 (en) | 1996-12-11 |
Family
ID=14831601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12226287A Expired - Fee Related JP2563109B2 (en) | 1987-05-19 | 1987-05-19 | Alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2563109B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5721072A (en) * | 1995-07-21 | 1998-02-24 | Matsushita Electric Industrial Co., Ltd. | Alkaline battery |
| EP0945906A2 (en) * | 1998-03-27 | 1999-09-29 | Matsushita Electronics Corporation | Manganese dry batteries |
-
1987
- 1987-05-19 JP JP12226287A patent/JP2563109B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5721072A (en) * | 1995-07-21 | 1998-02-24 | Matsushita Electric Industrial Co., Ltd. | Alkaline battery |
| EP0945906A2 (en) * | 1998-03-27 | 1999-09-29 | Matsushita Electronics Corporation | Manganese dry batteries |
| EP0945906A3 (en) * | 1998-03-27 | 1999-10-06 | Matsushita Electronics Corporation | Manganese dry batteries |
| US6500584B1 (en) | 1998-03-27 | 2002-12-31 | Matsushita Electric Industrial Co., Ltd. | Manganese dry batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2563109B2 (en) | 1996-12-11 |
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