JPS63158749A - Zinc electrode for alkaline storage battery - Google Patents
Zinc electrode for alkaline storage batteryInfo
- Publication number
- JPS63158749A JPS63158749A JP61304405A JP30440586A JPS63158749A JP S63158749 A JPS63158749 A JP S63158749A JP 61304405 A JP61304405 A JP 61304405A JP 30440586 A JP30440586 A JP 30440586A JP S63158749 A JPS63158749 A JP S63158749A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- indium
- metallic
- electrode
- oxide
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 63
- 239000011701 zinc Substances 0.000 title claims abstract description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 150000002472 indium compounds Chemical class 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 5
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 208000028659 discharge Diseases 0.000 abstract 1
- 229940101209 mercuric oxide Drugs 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021515 thallium hydroxide Inorganic materials 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 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
- H01M4/36—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
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
(イ) 産業上の利用分野
本発明はニッケル・亜鉛蓄電池や、銀・亜鉛蓄を池など
に用いられる活物質として亜鉛を使用するアルカリ蓄電
池用亜鉛極に関するものである。[Detailed description of the invention] (a) Field of industrial application The present invention relates to a zinc electrode for an alkaline storage battery using zinc as an active material, which is used in nickel-zinc storage batteries and silver-zinc storage ponds. .
(ロ) 従来の技術
負極活物質として用いられる亜鉛は単位重祉当りのエネ
ルギー密度が大きく、且安価であるという利点があり、
このような亜鉛極を有してなるアルカリ亜鉛蓄電池は高
エネルギー密度で作動電圧が高い等の特徴のある電池と
しての期待が大きい。(b) Conventional technology Zinc, which is used as a negative electrode active material, has the advantage of having a high energy density per unit of energy and being inexpensive.
Alkaline zinc storage batteries having such zinc electrodes have high expectations as batteries with features such as high energy density and high operating voltage.
ところが、この種のアルカリ亜鉛蓄電池では、放電時に
亜鉛がアルカリ電解液中に溶出して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し生長するので
、充放電の繰返しによりこの電析亜鉛がセパレータを貫
通し正極に接触して電池円内部短絡を引き起こしたり、
あるいは亜鉛極表面が高密度化して電池放電容量が低下
する結果、電池のサイクル寿命が非常に短いという欠点
がある。However, in this type of alkaline zinc storage battery, the zincate ions produced when zinc is eluted into the alkaline electrolyte during discharge are deposited and grow in a dendritic form on the surface of the zinc electrode during charging. Electrodeposited zinc may penetrate the separator and come into contact with the positive electrode, causing an internal short circuit in the battery.
Another disadvantage is that the surface of the zinc electrode becomes highly dense and the battery discharge capacity decreases, resulting in a very short cycle life of the battery.
この欠点に対処し、電池のサイクル特性を改善する従来
技術として例えば特開昭59−189562号公報には
タリウムの酸化物または水酸化物と、インジウムの酸化
物または水酸化物を亜鉛活物質に対し総11〜15重量
%添加、含有きせるとサイクル特性の大幅な向上が得ら
れることが開示されている。しかしながら、これらを単
に添加するのみでは樹枝状亜鉛の生長を有効に阻止する
ことができず、その効果を十分に発揮することができな
い。As a conventional technique for addressing this drawback and improving battery cycle characteristics, for example, Japanese Patent Application Laid-Open No. 189562/1989 discloses that thallium oxide or hydroxide and indium oxide or hydroxide are used as zinc active materials. On the other hand, it is disclosed that when 11 to 15% by weight of total additives are added, the cycle characteristics can be significantly improved. However, simply adding these does not effectively inhibit the growth of dendritic zinc, and the effect cannot be fully exhibited.
これは、これらの添加物が還元されて、サイクル数が進
行するに従い金属亜鉛表面を覆うものの、充放電サイク
ルの初期においては、これら添加物が金属亜鉛表面を覆
っておらず、この時に樹枝状亜鉛生成の核となるような
金属亜鉛が一旦出現すると、サイクル数が進行するに従
い前記添加物があったとしても、樹枝状亜鉛生長が有効
に阻止できないためである。また、前記添加物が金属亜
鉛表面を覆うのは、充放電サイクルを数lO回程度繰り
返した後であり、この時点では樹枝状亜鉛生成の核とな
るような金属亜鉛がすでに出現している。更に樹枝状亜
鉛の生成は急速充電時及び過充電時に特に顕著となる。This is because these additives are reduced and cover the metal zinc surface as the number of cycles progresses, but at the beginning of the charge/discharge cycle, these additives do not cover the metal zinc surface, and at this time the dendritic This is because once metallic zinc, which becomes the core of zinc production, appears, the growth of dendritic zinc cannot be effectively inhibited as the number of cycles progresses, even if the additive is present. Further, the additive covers the surface of metallic zinc only after charge/discharge cycles have been repeated several 10 times, and at this point, metallic zinc that will become the nucleus for the formation of dendritic zinc has already appeared. Furthermore, the formation of dendritic zinc becomes particularly noticeable during rapid charging and overcharging.
(ハ)発明が解決しようとする問題点
本発明は前記問題点に鑑みなされたものであって、亜鉛
極における充放電サイクル初期の金属亜鉛粒子からの樹
枝状亜鉛発生を抑制し、サイクル特性のすぐれたアルカ
リ蓄電池を提供しようとするものである。(c) Problems to be Solved by the Invention The present invention has been made in view of the above-mentioned problems, and it suppresses the generation of dendritic zinc from metal zinc particles at the beginning of the charge/discharge cycle in the zinc electrode, thereby improving the cycle characteristics. The aim is to provide an excellent alkaline storage battery.
(ニ)問題点を解決するための手段
本発明は、酸化亜鉛と金属亜鉛とを主活物質とする亜鉛
極において、前記金属亜鉛をインジウムあるいはインジ
ウム化合物で覆ったことを要旨とするものである。(d) Means for solving the problem The gist of the present invention is that in a zinc electrode whose main active materials are zinc oxide and metallic zinc, the metallic zinc is covered with indium or an indium compound. .
(ホ)作用
急速充電時あるいは過充電時の亜鉛極の電極電位は通常
の充電時よりも卑側にシフトし、亜鉛酸イオンが還元さ
れて金属亜鉛上に電着する反応がおこりやすくなる。す
なわち急速充電時あるいは過充電時の亜鉛極における電
極反応は、酸化亜鉛が還元される反応と、亜鉛酸イオン
が還元されて金属亜鉛上に電着する反応との競争反応と
なる。(E) Effect During rapid charging or overcharging, the electrode potential of the zinc electrode shifts to the more base side than during normal charging, and a reaction in which zincate ions are reduced and electrodeposited on metal zinc becomes more likely to occur. That is, the electrode reaction at the zinc electrode during rapid charging or overcharging is a competitive reaction between a reaction in which zinc oxide is reduced and a reaction in which zincate ions are reduced and electrodeposited on metal zinc.
ところが金属亜鉛表面をインジウムあるいはインジウム
化合物で覆っておくと電着反応の過電圧が増大し、酸化
亜鉛の還元だけが優先的におこるようになる。したがっ
1サイクル初期に急速充電や過充電を行っても、亜鉛極
からの樹枝状亜鉛生長を有効に阻止でき電池円内部短絡
を抑制しうる。However, when the surface of metallic zinc is covered with indium or an indium compound, the overvoltage of the electrodeposition reaction increases, and only the reduction of zinc oxide occurs preferentially. Therefore, even if rapid charging or overcharging is performed at the beginning of one cycle, the growth of dendritic zinc from the zinc electrode can be effectively prevented, and short circuits within the battery circle can be suppressed.
〈へ)実施例
3規定の水酸化ナトリウム水溶液1!に亜鉛粉末500
gを添加し、30分間浸漬し、亜鉛粉末の表面に形成き
れている酸化亜鉛被膜を溶解させた。(To) Example 3 Specified sodium hydroxide aqueous solution 1! zinc powder 500
g was added and immersed for 30 minutes to dissolve the zinc oxide film that had formed on the surface of the zinc powder.
次にこの溶液に水酸化インジウム1.0gを添加し、1
0分間攪拌した後、この溶液をろ過し、500m2の純
水で10回水洗し、70℃で乾燥させてインジウムによ
り表面を覆われた金属亜鉛を作成した。Next, 1.0 g of indium hydroxide was added to this solution, and 1.0 g of indium hydroxide was added to the solution.
After stirring for 0 minutes, this solution was filtered, washed 10 times with 500 m2 of pure water, and dried at 70°C to produce metallic zinc whose surface was covered with indium.
尚、この時のインジウム被膜の重量は金属亜鉛に対して
1重量%であった0次にこの金属亜鉛151i量部と酸
化亜鉛100重量部、及び水素過電圧を上げるための酸
化水銀2重量部とを粉体混合した後、水とポリテトラフ
ルオロエチレン(PTFE)を添加、混練し、ペースト
を得、集電体上に圧着して亜鉛極とした。この本発明亜
鉛極と焼結式ニッケル極とを組み合わせて、円筒密閉型
の公称容1i700mAhの本発明に係るニッケルー亜
鉛電池Aを10セル作成した。The weight of the indium coating at this time was 1% by weight based on the metal zinc.Next, 151 parts of this metal zinc, 100 parts by weight of zinc oxide, and 2 parts by weight of mercury oxide to increase the hydrogen overvoltage were added. After powder mixing, water and polytetrafluoroethylene (PTFE) were added and kneaded to obtain a paste, which was pressed onto a current collector to form a zinc electrode. By combining the zinc electrode of the present invention and the sintered nickel electrode, 10 cells of a cylindrical sealed nickel-zinc battery A according to the present invention having a nominal capacity of 1i700 mAh were fabricated.
また比較用電池として、金属亜鉛表面をインジウム処理
していない金属亜鉛を用い水酸化インジウムを2重量部
添加した以外は、本発明亜鉛極と同様の亜鉛極を得、比
較電池Bを同様にして10セル作成した。In addition, as a comparison battery, a zinc electrode similar to the zinc electrode of the present invention was obtained, except that metal zinc whose surface was not indium-treated was used and 2 parts by weight of indium hydroxide was added, and a comparison battery B was prepared in the same manner. 10 cells were created.
これらの電池を用い、充電を1cの1流で150%、放
電を1cの電流で100%行い、電池容量が500mA
h(終止電圧1.OV)以下になったところを電池寿命
とするサイクル条件にて、充放電サイクルテストを行っ
た。この結果を図に示す。Using these batteries, charging 150% with a single current of 1c and discharging 100% with a current of 1c, the battery capacity was 500mA.
A charge/discharge cycle test was conducted under cycle conditions in which the battery life is defined as the point at which the battery life drops below h (final voltage 1.OV). The results are shown in the figure.
図の結果より、本発明電池Aが優れていることがわかる
。これは、樹枝状亜鉛発生の核となる金属亜鉛粒子表面
をインジウムにより覆っているので、サイクル数が進行
しても、樹枝状亜鉛の生長を有効に抑制していることに
基づくものである。From the results shown in the figure, it can be seen that the battery A of the present invention is superior. This is because the surface of the metallic zinc particles, which serve as the nucleus for the generation of dendritic zinc, is covered with indium, so that even as the number of cycles progresses, the growth of dendritic zinc is effectively suppressed.
尚、インジウムの添加量としては金属亜鉛重量に対して
0.5〜2.0重量%とするのが好ましいことが本発明
者によって知得諮れた。The inventor has discovered that the amount of indium added is preferably 0.5 to 2.0% by weight based on the weight of metal zinc.
また実施例においては金属亜鉛粒子表面を金属インジウ
ムで覆うものを開示したが、酸化インジウムなどのイン
ジウム化合物で覆っても同様の効果がある。Further, in the examples, the surface of metal zinc particles is covered with metal indium, but the same effect can be obtained even if the surface is covered with an indium compound such as indium oxide.
(ト)発明の効果
本発明のアルカリ蓄電池用亜鉛極は、添加せる金属亜鉛
粒子の表面をインジウムあるいはインジウム化合物で覆
うことにより効果的に樹枝状亜鉛生長を抑制しろるので
、かかる亜鉛極を用いたアルカリ蓄電池はサイクル特性
においてきわめて優れたものであり、その工業的価値は
大きい。(G) Effects of the Invention The zinc electrode for alkaline storage batteries of the present invention can effectively suppress the growth of dendritic zinc by covering the surface of the metal zinc particles to be added with indium or an indium compound. The alkaline storage batteries used in this study have extremely excellent cycle characteristics and are of great industrial value.
図は電池のサイクル特性比較図である。 A・・・未発明電池、B・・・比較!池。 The figure is a comparison diagram of cycle characteristics of batteries. A... Uninvented battery, B... Comparison! pond.
Claims (1)
のにおいて、前記金属亜鉛をインジウムあるいはインジ
ウム化合物で覆ったことを特徴とするアルカリ蓄電池用
亜鉛極。(1) A zinc electrode for an alkaline storage battery using zinc oxide and metallic zinc as main active materials, characterized in that the metallic zinc is covered with indium or an indium compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61304405A JPH079806B2 (en) | 1986-12-19 | 1986-12-19 | Zinc electrode for alkaline storage battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61304405A JPH079806B2 (en) | 1986-12-19 | 1986-12-19 | Zinc electrode for alkaline storage battery |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63158749A true JPS63158749A (en) | 1988-07-01 |
JPH079806B2 JPH079806B2 (en) | 1995-02-01 |
Family
ID=17932614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61304405A Expired - Lifetime JPH079806B2 (en) | 1986-12-19 | 1986-12-19 | Zinc electrode for alkaline storage battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH079806B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0224963A (en) * | 1988-07-13 | 1990-01-26 | Sanyo Electric Co Ltd | Alkaline storage battery and its zinc electrode |
JPH04206266A (en) * | 1990-11-29 | 1992-07-28 | Matsushita Electric Ind Co Ltd | Zinc alloy for zinc alkaline battery, its manufacture and relative zinc alkaline battery |
CN112290007A (en) * | 2020-10-27 | 2021-01-29 | 燕山大学 | Preparation method of zinc-copper alloy cathode with self-supporting structure |
-
1986
- 1986-12-19 JP JP61304405A patent/JPH079806B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0224963A (en) * | 1988-07-13 | 1990-01-26 | Sanyo Electric Co Ltd | Alkaline storage battery and its zinc electrode |
JPH04206266A (en) * | 1990-11-29 | 1992-07-28 | Matsushita Electric Ind Co Ltd | Zinc alloy for zinc alkaline battery, its manufacture and relative zinc alkaline battery |
JPH07109762B2 (en) * | 1990-11-29 | 1995-11-22 | 松下電器産業株式会社 | Method for producing zinc alloy for zinc alkaline battery and zinc alkaline battery using the same |
CN112290007A (en) * | 2020-10-27 | 2021-01-29 | 燕山大学 | Preparation method of zinc-copper alloy cathode with self-supporting structure |
Also Published As
Publication number | Publication date |
---|---|
JPH079806B2 (en) | 1995-02-01 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term |