JPS63119157A - Zinc electrode - Google Patents
Zinc electrodeInfo
- Publication number
- JPS63119157A JPS63119157A JP26344786A JP26344786A JPS63119157A JP S63119157 A JPS63119157 A JP S63119157A JP 26344786 A JP26344786 A JP 26344786A JP 26344786 A JP26344786 A JP 26344786A JP S63119157 A JPS63119157 A JP S63119157A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- oxide powder
- zinc oxide
- electrode
- 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.)
- Pending
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 abstract description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 239000003792 electrolyte Substances 0.000 description 10
- 239000011149 active material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- -1 zincate ions Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、ニッケルー亜鉛蓄電池や銀−亜鉛蓄電池な
どのアルカリ亜鉛蓄電池に用いられる亜鉛極に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a zinc electrode used in an alkaline zinc storage battery such as a nickel-zinc storage battery or a silver-zinc storage battery.
〈従来の技術〉
上記亜鉛極で活物質として用いられている亜鉛は、エネ
ルキー密度が高く、安価で且つ無公害である等の特長が
あり、従って、この亜鉛極を陰極とするアルカリ亜鉛蓄
電池は高エネルギー密度電池としての期待が大きい。と
ころが、このアルカリ亜鉛蓄電池は長期のサイクル寿命
が得にくいという欠点があり、サイクル寿命を改善して
実用化を図るために多くの研究がなされている。アルカ
リ亜鉛蓄電池のサイクル寿命がこのように短いのは、陰
極として用いる亜鉛極がアルカリ電解液に可溶な電極で
あることに起因している。即ち、この亜鉛極においては
、放電時に亜鉛がアルカリ電解液中に溶出する一方、こ
の溶出により生じた亜鉛酸イオンが充電時には亜鉛極表
面に樹枝状に電析する。そして、充放電の繰返しによっ
てこの電析亜鉛が生長し、セパレータを貫通して対極に
達して内部短絡を引き起こしてしまい、またこれによっ
て亜鉛極の形状変化が大きくなる結果、早期サイクルで
電池特性が劣化し、実用上満足しうるサイクル寿命が得
られないのである。<Prior art> Zinc, which is used as an active material in the above zinc electrode, has the characteristics of high energy density, low cost, and non-pollution. Therefore, an alkaline zinc storage battery using this zinc electrode as a cathode is It has high expectations as a high energy density battery. However, this alkaline zinc storage battery has the disadvantage that it is difficult to obtain a long cycle life, and many studies have been conducted to improve the cycle life and put it into practical use. This short cycle life of alkaline zinc storage batteries is due to the fact that the zinc electrode used as the cathode is soluble in an alkaline electrolyte. That is, in this zinc electrode, zinc is eluted into the alkaline electrolyte during discharge, while zincate ions generated by this elution are deposited in a dendritic form on the surface of the zinc electrode during charging. Through repeated charging and discharging, this deposited zinc grows, penetrates the separator, and reaches the counter electrode, causing an internal short circuit. This also causes a large change in the shape of the zinc electrode, resulting in deterioration of battery characteristics in early cycles. This results in deterioration, and a practically satisfactory cycle life cannot be obtained.
この欠点に対処し、アルカリ亜鉛蓄電池のサイクルか命
を少しでも改善するため、電池内のアルカリ電解液量を
実質的に遊離のものがないように規制する技術が従来よ
り提案されている。In order to address this drawback and improve the cycle life of alkaline zinc storage batteries, techniques have been proposed for regulating the amount of alkaline electrolyte in the battery so that there is virtually no free electrolyte.
このように電解液量を規制することで、上記放電生成物
である亜鉛酸イオンは拡散することなく亜鉛極近傍にと
どまるようになり、次の充電時には電析亜鉛が元の位置
に電着し易くなる。By regulating the amount of electrolyte in this way, the zincate ions, which are the discharge products mentioned above, do not diffuse and remain near the zinc pole, and the next time the battery is charged, the deposited zinc is deposited at its original position. It becomes easier.
この結果、亜鉛の樹枝状電析の生長が抑えられ、また亜
鉛極の変形が緩和されて亜鉛極並びに電池のサイクル寿
命が改善される。As a result, the growth of zinc dendritic deposits is suppressed, and the deformation of the zinc electrode is alleviated, thereby improving the cycle life of the zinc electrode and battery.
〈発明が解決しようとする問題点〉
しかしながら、このように電解液量を制限して電池を構
成した場合、電池の高率放電時に十分な極板容量が得ら
れないという問題がある。<Problems to be Solved by the Invention> However, when a battery is constructed by limiting the amount of electrolyte in this manner, there is a problem that sufficient plate capacity cannot be obtained during high rate discharge of the battery.
これは、電池内の電解液量を上記のように制限した結果
、電池放電時における亜鉛極での電極反応（７ｎ＋２０
Ｈ−→Ｚｎ （Ｏｆ−１＞２ ＋２０−）に必要な水酸
イオンＯＨ−の供給が十分法やかになされず、このため
、高率放電時のように極板の電流密度が大きく、極板の
単位面積当りの水酸イオンの必要量が多くなる場合には
上記電極反応が円滑に行なわれなくなってしまうことに
起因している。そして、このような極板容量の低下によ
って高率放電時の特性が大きく劣化し、サイクル寿命の
低下を招いてしまう。This is due to the electrode reaction (7n+20
The hydroxide ion OH- required for H-→Zn (Of-1>2 +20-) is not supplied properly, and as a result, the current density of the electrode plate is large as in the case of high-rate discharge. This is due to the fact that when the required amount of hydroxide ions per unit area of the electrode plate increases, the electrode reaction cannot be carried out smoothly. Such a decrease in plate capacity significantly deteriorates the characteristics during high rate discharge, leading to a decrease in cycle life.
〈問題点を解決するための手段〉
本発明者は、上記の問題点を解決するように検討した所
、亜鉛極の亜鉛活物質に用いる酸化亜鉛粉末の組成を次
のように規定した時には所期の目的を達成できることを
知得してこの発明を完成した。<Means for Solving the Problems> The inventor of the present invention has studied how to solve the above problems, and found that when the composition of zinc oxide powder used as the zinc active material of the zinc electrode is specified as follows, This invention was completed after realizing that it was possible to achieve the original purpose of the invention.
即ち、この発明の亜鉛極は、０．１〜０．５μｍの粒径
を有する第１の酸化亜鉛粉末２０〜８０重量％と、０．
１μｍ以下の粒径を有する第２の酸化亜鉛粉末８０〜２
０重量％とを混合してなる酸化亜鉛粉末を用いたことを
要旨とする。That is, the zinc electrode of the present invention contains 20 to 80% by weight of the first zinc oxide powder having a particle size of 0.1 to 0.5 μm, and 0.1 to 80% by weight of the first zinc oxide powder having a particle size of 0.1 to 0.5 μm.
Second zinc oxide powder 80-2 having a particle size of 1 μm or less
The gist is that a zinc oxide powder mixed with 0% by weight was used.
〈作 用〉
亜鉛極の亜鉛活物質に使用する酸化亜鉛粉末としては、
従来、粒径が０．１〜０．５μｍの範囲のものが用いら
れている。本発明では従来用いられていたこの範囲の粒
径の酸化亜鉛粉末に、粒径０．１μｍ以下の酸化亜鉛粉
末を混合するようにしたものである。そして、このよう
な微小粒子を含有させることで、亜鉛極中の比表面積が
増大し、放電時における極板の電流密度が小さくなる結
果、高率放電特性が改善される。<Function> Zinc oxide powder used as the zinc active material of zinc electrodes is
Conventionally, particles having a particle size in the range of 0.1 to 0.5 μm have been used. In the present invention, zinc oxide powder having a particle size of 0.1 μm or less is mixed with the conventionally used zinc oxide powder having a particle size within this range. By including such fine particles, the specific surface area of the zinc electrode increases, and the current density of the electrode plate during discharge decreases, resulting in improved high rate discharge characteristics.
〈実施例〉
０．１〜０．５μｍの粒径の酸化亜鉛粉末に、粒径が０
．１μｍ以下の酸化亜鉛粉末を種々な割合で混合して種
々の酸化亜鉛粉末を作った。この酸化亜鉛粉末８５重量
％に金属亜鉛粉末１０重量％並びに酸化カドミウム粉末
５重量％を加えてなる混合粉末に、水とＰ丁ＦＥを添加
し混練して活物質ペーストを作り、この活物質ペースト
をニッケルメツシュの両面に圧着するなどして種々の亜
鉛極を作製した。<Example> Zinc oxide powder with a particle size of 0.1 to 0.5 μm was
．． Various zinc oxide powders were prepared by mixing zinc oxide powders of 1 μm or less in various proportions. A mixed powder made by adding 10% by weight of metal zinc powder and 5% by weight of cadmium oxide powder to 85% by weight of this zinc oxide powder is mixed with water and PTFE to make an active material paste. Various zinc electrodes were made by crimping the nickel mesh onto both sides of a nickel mesh.
このようにして作った亜鉛極を陰極とし、これに公知の
焼結式ニッケル極を陽極として組合せ、種々の密閉型ニ
ッケルー亜鉛蓄電池を構成した。尚、電解液には、酸化
亜鉛を飽和させた３０重量％ＫＯＨ水溶液を用いた。ま
たセパレータには、微孔性フィルムに含液材として不織
布を重ね合わせた多層構造のものを使用した。The zinc electrode thus produced was used as a cathode, and a known sintered nickel electrode was combined with this as an anode to construct various sealed nickel-zinc storage batteries. Note that a 30% by weight KOH aqueous solution saturated with zinc oxide was used as the electrolytic solution. Furthermore, the separator used had a multilayer structure in which a nonwoven fabric as a liquid-containing material was superimposed on a microporous film.
更に、アルカリ電解液の注液量は、これらセパレータと
陽陰極が均一に濡れ、且つ遊離の電解液が実質的に存在
しない程度とした。Further, the amount of alkaline electrolyte injected was such that the separator and the anode and cathode were uniformly wetted, and there was substantially no free electrolyte.
これらのニッケルー亜鉛蓄電池について、４時間率の電
流で５時間充電した後に１時間率の電流で電池電圧が１
．３Ｖになるまで放電するという一連の充放電サイクル
を繰返して各電池のサイクル寿命（回）を測定した。尚
、放電時において１．３Ｖの電池電圧を４２分間維持で
きなくなった時点、つまり電池放電容量が公称容量（初
期容＠）の７０％以下となったところを電池サイクル寿
命とした。For these nickel-zinc storage batteries, after 5 hours of charging at a 4-hour rate of current, the battery voltage drops to 1 at a 1-hour rate of current.
．． The cycle life (times) of each battery was measured by repeating a series of charging and discharging cycles in which the battery was discharged to 3V. The battery cycle life was defined as the point at which the battery voltage of 1.3 V could not be maintained for 42 minutes during discharge, that is, the point at which the battery discharge capacity became 70% or less of the nominal capacity (initial capacity).
縦軸にサイクル寿命（回）を、また横軸には粒径が０．
１μｍ以下の酸化亜鉛の割合（重量％）をとって上記結
果をプロットした所、添付図面に示したようなグラフを
得た。このグラフより、微小粒子からなるこの酸化亜鉛
粉末を２０〜８０１４％混合して用いた場合のザイクル
特性が格段に優れていることがわかる。これにより、亜
鉛極に用いる酸化亜鉛粉末として、０．１〜０．５μｍ
の粒径の酸化亜鉛粉末２０〜８０重量％と０．１μｍ以
下の粒径の酸化亜鉛粉末８０〜２０重量％との混合粉末
を用いた時に高率放電時におけるザイクル特性の著しい
向上が図れることがわかった。The vertical axis shows the cycle life (times), and the horizontal axis shows the particle size of 0.
When the above results were plotted based on the ratio (wt%) of zinc oxide having a diameter of 1 μm or less, a graph as shown in the attached drawing was obtained. From this graph, it can be seen that the cycle characteristics are significantly superior when this zinc oxide powder consisting of fine particles is used in a mixture of 20 to 8014%. As a result, zinc oxide powder used for zinc electrodes has a particle size of 0.1 to 0.5 μm.
When using a mixed powder of 20 to 80% by weight of zinc oxide powder with a particle size of I understand.
上記の割合で混合した酸化亜鉛粉末を用いた場合の特性
がよいのは、前述の如く、微小粉末を混合することによ
って亜鉛極の比表面積が増大し、これによって極板の電
流密度が小さくなったことに依る。そして、この微小粉
末の混合量が８０重量％より大きくなると特性が低下す
るのは、このような微小粉末は通常凝集状態で極板中に
存在しており、この凝集した粒子間には電解液が浸透し
にくいことから、微小粉末をあまりに多く使用すると酸
化亜鉛粉末における電解液の濡れが悪くなり、この結果
、亜鉛極において活物質の利用率が低下する度合が著し
くなるためと思われる。また、混合量が２０重量％より
少ない場合の特性が悪いのは、上記の比表面積の増大に
よる電流密度の減少の程度が不十分であることに依ると
考えられる。The reason why the zinc oxide powder mixed in the above ratio has good properties is that, as mentioned above, by mixing fine powder, the specific surface area of the zinc electrode increases, which reduces the current density of the electrode plate. It depends. When the amount of this fine powder mixed exceeds 80% by weight, the characteristics deteriorate because such fine powder is usually present in the electrode plate in an agglomerated state, and there is an electrolyte between these agglomerated particles. This is thought to be due to the fact that it is difficult to penetrate the zinc oxide powder, so if too much fine powder is used, the wetting of the electrolyte to the zinc oxide powder becomes poor, and as a result, the degree of decrease in the utilization rate of the active material in the zinc electrode becomes significant. Furthermore, the reason why the properties are poor when the amount of the mixture is less than 20% by weight is considered to be due to the insufficient reduction in current density due to the increase in the specific surface area.
〈発明の効果〉
以上のように構成されるこの発明の亜鉛極によれば、亜
鉛極にお（プる比表面積の増大によって極板の電流密度
が小さくなる結果、この亜鉛極並びにこれを用いた電池
の高率放電特性向上を図ることができる。<Effects of the Invention> According to the zinc electrode of the present invention constructed as described above, the current density of the electrode plate decreases due to the increase in the specific surface area of the zinc electrode. It is possible to improve the high rate discharge characteristics of a battery that has been used for a long time.
添付図面は亜鉛極に用いる粒径が０．１μｍ以下の酸化
亜鉛粉末の割合と電池ザイクル寿命との関係を示したグ
ラフである。The attached drawing is a graph showing the relationship between the proportion of zinc oxide powder with a particle size of 0.1 μm or less used in the zinc electrode and battery cycle life.
Claims (1)
粉末２０〜８０重量％と、０．１μｍ以下の粒径を有す
る第２の酸化亜鉛粉末８０〜 ２０重量％とを混合してなる酸化亜鉛粉末を用いたこと
を特徴とする亜鉛極。1. Mixing 20-80% by weight of a first zinc oxide powder having a particle size of 0.1-0.5 μm and 80-20% by weight of a second zinc oxide powder having a particle size of 0.1 μm or less. A zinc electrode characterized by using zinc oxide powder made of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26344786A JPS63119157A (en) | 1986-11-05 | 1986-11-05 | Zinc electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26344786A JPS63119157A (en) | 1986-11-05 | 1986-11-05 | Zinc electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63119157A true JPS63119157A (en) | 1988-05-23 |
Family
ID=17389636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26344786A Pending JPS63119157A (en) | 1986-11-05 | 1986-11-05 | Zinc electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63119157A (en) |
-
1986
- 1986-11-05 JP JP26344786A patent/JPS63119157A/en active Pending
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