JPS58137963A - Alkaline zinc storage battery - Google Patents
Alkaline zinc storage batteryInfo
- Publication number
- JPS58137963A JPS58137963A JP57019291A JP1929182A JPS58137963A JP S58137963 A JPS58137963 A JP S58137963A JP 57019291 A JP57019291 A JP 57019291A JP 1929182 A JP1929182 A JP 1929182A JP S58137963 A JPS58137963 A JP S58137963A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- cadmium
- oxide
- paste
- hydroxide
- 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
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
- H01M4/24—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】
本発明はニッケルー亜鉛電池、銀一亜鉛電池のように陰
極活物質として亜鉛を用いるアルカリ亜鉛蓄電池に関し
、特に亜鉛陰極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkaline zinc storage batteries that use zinc as a cathode active material, such as nickel-zinc batteries and silver-zinc batteries, and particularly relates to improvements in zinc cathodes.
この植電池において、負極活物質としての亜鉛は、単位
重量当りのエネルギー密度が大きく、貝安価である利点
を有する反面、次のような欠点がある。即ち、亜鉛極の
放電生成物である亜鉛酸イオンが電解液中に遊離し、充
電の際に金属亜鉛が樹枝状あるいは海綿状に電着する形
態をとり、充放電の繰返しにより電着亜鉛が生長してセ
パレータを貫通し、対極に接して内部短絡を引起す。ま
た亜鉛極は通常亜鉛活物質に結着剤を加え、混練したペ
ーストを芯体（集電体）に塗着乾燥して作成されている
が、放電時に亜鉛極表面の亜鉛が亜鉛酸イオンとなウて
溶出するため、充放電を繰返すと亜鉛極表面と亜鉛極内
部とでは、亜鉛濃度に差が生じ、亜鉛極表面の結着剤の
割合か増大して電導性及び含液性が低ドするξとになり
、亜鉛極内部における反応が起り離くなり電池容量が低
下する。In this plant cell, zinc as the negative electrode active material has the advantage of having a high energy density per unit weight and being inexpensive, but has the following drawbacks. That is, zincate ions, which are the discharge products of the zinc electrode, are liberated in the electrolytic solution, and during charging, metallic zinc is electrodeposited in a dendritic or spongy form, and as the charging and discharging are repeated, the electrodeposited zinc is It grows through the separator and contacts the opposite electrode, causing an internal short circuit. Zinc electrodes are usually made by adding a binder to zinc active material and applying the kneaded paste to a core (current collector) and drying it, but during discharge, the zinc on the surface of the zinc electrode turns into zincate ions. As a result, when charging and discharging are repeated, there will be a difference in zinc concentration between the surface of the zinc electrode and the inside of the electrode, and the proportion of binder on the surface of the zinc electrode will increase, resulting in a decrease in electrical conductivity and liquid impregnation. As a result, a reaction occurs inside the zinc electrode and the battery capacity decreases.
仁のような問題に対処するために、亜鉛活物の表面にカ
ドミウム化合物一を形成することが提案されている。こ
の提案によれば、亜鉛活物質層は常時金属カドミウム層
で覆われて電解液と直接に接していないため、放電反応
により生成される亜鉛酸イオンは非常に少なくなる。こ
のため充電反応により生じる樹枝状あるいは海綿状の電
着亜鉛の生成が少なくなると共ｔζ亜鉛活物質表面部に
あける亜鉛濃度の低下が抑制され、サイクル特性が飛躍
的に向上する。To deal with problems such as oxidation, it has been proposed to form cadmium compounds on the surface of zinc active materials. According to this proposal, since the zinc active material layer is always covered with the metal cadmium layer and is not in direct contact with the electrolyte, the amount of zincate ions generated by the discharge reaction is extremely small. Therefore, the formation of dendritic or spongy electrodeposited zinc caused by the charging reaction is reduced, and a decrease in the zinc concentration on the surface of the tζ zinc active material is suppressed, and the cycle characteristics are dramatically improved.
カドミウムは亜鉛より責な酸舶還元電位を持つため、一
度金属カドミウムに充電電析された表面−は亜鉛の充放
電に頒関係に金員状態を保ち亜鉛酸イオンの溶出防止と
いう所期の目的を連する。Since cadmium has a higher acid reduction potential than zinc, once charged and deposited on the surface of metal cadmium, the intended purpose is to maintain a metallic state in relation to the charging and discharging of zinc and to prevent the elution of zincate ions. Continuing.
ところが長期にわたる充放電サイクルの繰返しにより、
カドミウム層も一部充放電反応に関惨し、また亜鉛活物
−か徐々に膨張して表面のカドミウム層が徐々にカドミ
ウムと亜鉛との混合物層となってカドミウム単独場にお
ける効果が低下する。However, due to repeated charging and discharging cycles over a long period of time,
A part of the cadmium layer also participates in the charge/discharge reaction, and the active zinc material gradually expands, and the cadmium layer on the surface gradually becomes a mixture layer of cadmium and zinc, reducing the effectiveness of cadmium alone.
即ち亜鉛極の全表面をカドミウム層で被服することがで
きな（なり、亜鉛酸イオンの溶出を防止できなくなって
いた。In other words, the entire surface of the zinc electrode could not be covered with a cadmium layer (and the elution of zincate ions could not be prevented).
本発明はかかる点に鑑み発明されたものにして、亜鉛活
物質−の表面に、アルカリ土類金属の水酸化物あるいは
酸化物を含有するカドミウム化合物層を形成してなる亜
鉛極を備えたアルカリ亜鉛蓄電池を提供せんとするもの
である。The present invention has been devised in view of the above, and provides an alkaline electrode equipped with a zinc electrode formed by forming a cadmium compound layer containing an alkaline earth metal hydroxide or oxide on the surface of a zinc active material. The aim is to provide zinc storage batteries.
以ド本発明の詳細な説明する。The present invention will now be described in detail.
実施例１
酸化亜鉛粉末８０重盪囁、亜鉛１０１ｉ盪％、添加剤と
して鹸化カドミウム５重量％及びフッ素樹脂粉末５重量
哄よりなる混合粉末に水を加え、混練してペースト状と
なす。このペーストを銅又は鉄よりなる集電仮に塗着乾
燥して亜鉛活物質−を形成する。ついで酸化カドミウム
８０重量囁、金属カドミウム１５重量１％、水酸化カル
シウム５重量哄及び７ｙ票樹脂粉末２重１′％よりなる
混合粉末に水を加え、混練してペースト状となす。この
ペーストを前記亜鉛活物質−の表面に塗着し、乾燥させ
てカドミウム化合物の薄層を形成した後、圧着して亜鉛
極とする。このように形成した亜鉛極の断面図を第１図
に示す。この図において、亜鉛極１１１は亜鉛活物質層
（２）と、水酸化カルシウムを含有した表面カドミウム
化合物層（３）からなり、該化合物層の厚みは、亜鉛活
物質１１ｉ１１１２１の厚みの約１７６〜１／１０程度
である。（４）は集電体である。Example 1 Water is added to a mixed powder consisting of 80 kg of zinc oxide powder, 101 % of zinc, 5 wt. % of saponified cadmium as an additive, and 5 wt. of fluororesin powder, and the mixture is kneaded to form a paste. This paste is temporarily applied to a current collector made of copper or iron and dried to form a zinc active material. Next, water was added to a mixed powder consisting of 80 parts by weight of cadmium oxide, 1% by weight of metal cadmium, 5 parts by weight of calcium hydroxide, and 1% by weight of 2 parts by weight of 7Y resin powder, and the mixture was kneaded to form a paste. This paste is applied to the surface of the zinc active material, dried to form a thin layer of cadmium compound, and then pressed to form a zinc electrode. A cross-sectional view of the zinc electrode formed in this manner is shown in FIG. In this figure, the zinc electrode 111 consists of a zinc active material layer (2) and a surface cadmium compound layer (3) containing calcium hydroxide, and the thickness of the compound layer is approximately 176 to 176 times the thickness of the zinc active material 11i11121. It is about 1/10. (4) is a current collector.
第２図は亜鉛極１１）と公知のニッケル極を組合せて形
成したニッケルー亜鉛蓄電池（Ａ）の断面図である。こ
の図面において、（５Ｉはニッケル極、（６１はセパレ
ータ、（７）は保液層、（８）は電槽、（９）は電槽蓋
、ｕｌＪＩＩｌｌは正負極端子である。FIG. 2 is a sectional view of a nickel-zinc storage battery (A) formed by combining a zinc electrode 11) and a known nickel electrode. In this drawing, (5I is a nickel electrode, (61 is a separator, (7) is a liquid retaining layer, (8) is a container, (9) is a container lid, and ulJIIll is a positive and negative electrode terminal.
実施例２
実施例１において、水酸化カルシウムに代えて水酸化？
グネシウムを使用し、他は同一条件でアルカリ亜鉛蓄電
池ｊｉｌｌを作成した。Example 2 In Example 1, hydroxide was used instead of calcium hydroxide?
An alkaline zinc storage battery jill was created using gnesium and under the same conditions.
実施例３
実施例１において、水酸化カルシウムに代えて本酸化バ
リウムを使用し、他は同一条件でアルカリ亜鉛蓄電池Ｉ
Ｃ）を作成した。Example 3 In Example 1, barium oxide was used instead of calcium hydroxide, and an alkaline zinc storage battery I was prepared under the same conditions as above.
C) was created.
実施例４
実施例１において、水酸化カルシウムに代えて酸化カル
シウムを使用し、他は同一条件でアルカリ亜鉛蓄電池（
Ｄ）を作成した。Example 4 In Example 1, calcium oxide was used instead of calcium hydroxide, and an alkaline zinc storage battery (
D) was created.
また比較のため表面カドミウム−として酸化カドミウム
８０重ＩＮＧ、金属カドミウム１８重量哄及びフッ素樹
脂粉末２重量％からなる亜鉛極を用い、他の点は実施例
１と同一条件の比較電池（Ｅ）を作成した。For comparison, a comparison battery (E) was prepared under the same conditions as Example 1 except that a zinc electrode consisting of 80% cadmium oxide, 18% metal cadmium, and 2% fluororesin powder was used as the surface cadmium. Created.
第３図はこれら蓄電池のサイクル特性比較図であり、特
性（＾）乃至（＆）は同一符号を付した蓄電池のサイク
ル特性である。充放電条件は、容置８００ｍＡＨの蓄電
池を、１５０ａＩ＾で６時間充電した後、１５０ｍＡ
で放電し、電池電圧が１．Ｏｖに達するとき放電停止を
するものである。このサイクル特性比較図から明らかな
ように、本発明による蓄電池（Ａ） 、 （８１、ＩＣ
）又４ｔｉＤ）ｌｔ比較１１ｆ池！ｌｃ比１．、サイク
ル特性が飛躍的に向上する。FIG. 3 is a comparison diagram of the cycle characteristics of these storage batteries, and characteristics (^) to (&) are the cycle characteristics of the storage batteries with the same symbols. The charging and discharging conditions are as follows: After charging a storage battery with a capacity of 800mAH at 150aI^ for 6 hours,
When the battery voltage reaches 1. When reaching Ov, the discharge is stopped. As is clear from this cycle characteristic comparison diagram, the storage battery (A) according to the present invention (81, IC
) Also 4tiD) lt comparison 11f pond! lc ratio 1. , cycle characteristics are dramatically improved.
この理由を考察するに、長期にわたる充放電サイクルに
より、亜鉛酸イオンの溶出を防止できな（なった表面の
金員カドミウムに代わり、アルカリ土類金属の水酸化物
あるいは酸化物が亜鉛と反ルして電解液に不溶な生成物
（実施例１ではＣａＺｎ（ＯＨ）４）として亜鉛酸イオ
ンを有効に固定しているためと考えられる。The reason for this is that the elution of zincate ions cannot be prevented due to long-term charge/discharge cycles. This is considered to be because the zincate ions are effectively fixed as a product (CaZn(OH)4 in Example 1) that is insoluble in the electrolytic solution.
アルカリ土類金属の水酸化物あるいは酸化物の含有割合
は、１重量ｓ以下ではほとんど効ＩＩがな（、また２５
重量％以上の含有は、表面カドミウム層中のカドミウム
量の割合を減少させて、金属カドミウム層により亜鉛酸
イオンの溶出を防止するという初期の目的を達成するこ
とができなくなると共に表面カドミウム場の抵抗を増大
させることになる。このためアルカリ土類金属の水酸化
物あるいは酸化物の含有量１〜２５重量哄がよく、より
好ましくは２〜１０重量哄である。The content of alkaline earth metal hydroxides or oxides has almost no effect when the content is less than 1 weight s (also 25
If the content is more than % by weight, it will reduce the proportion of cadmium in the surface cadmium layer, making it impossible to achieve the initial purpose of preventing the elution of zincate ions by the metal cadmium layer, and increasing the resistance of the surface cadmium field. This will increase the Therefore, the content of alkaline earth metal hydroxide or oxide is preferably 1 to 25 kg, more preferably 2 to 10 kg.
以−ｔの如（、本発明はアルカリ土類金属の水酸化物あ
るいは酸化物を含有したカドミウム化合物−を亜鉛活物
質層の表面に形成した亜鉛極を用いたから、アルカリ亜
鉛蓄電池のサイクル特性を従来のものに比・ム改善する
ことができ、その工業的価１直大なるものである。As described above, since the present invention uses a zinc electrode in which a cadmium compound containing an alkaline earth metal hydroxide or oxide is formed on the surface of a zinc active material layer, the cycle characteristics of an alkaline zinc storage battery can be improved. It can be improved in comparison with the conventional method, and its industrial value is directly significant.
１！１図は本発明による亜鉛極の断面図、第２図は同亜
鉛極を用いたニッケルー亜鉛蓄電池の断面図でめつ、第
３図は本発明による蓄電池と比較電池のサイクル特性比
較図である。
（２）・・・亜鉛活物質層、（３）・・カドミウム化合
ＩＩｅＩＪＪｉＩＩ。
は）・・・亜鉛極。1! Figure 1 is a cross-sectional view of a zinc electrode according to the present invention, Figure 2 is a cross-sectional view of a nickel-zinc storage battery using the same zinc electrode, and Figure 3 is a comparison diagram of cycle characteristics of a storage battery according to the present invention and a comparative battery. It is. (2)...Zinc active material layer, (3)...Cadmium compound IIeIJJiII. )...Zinc electrode.
Claims (1)
水酸化物あるいは酸化物を含有するカドミウム化合物−
を形成してなる亜鉛極をーえたアルカリ亜鉛蓄電池。 （２｝ 前記アルカリ土類金属の水酸化物あるいは酸
化物の含有割合が１乃至２５重量哄である特許請求の範
囲第１項記載のアルカリ亜鉛蓄電池。[Claims] II) A cadmium compound containing an alkaline earth metal hydroxide or oxide on the surface of the zinc active material layer.
An alkaline zinc storage battery with a zinc electrode formed by (2) The alkaline zinc storage battery according to claim 1, wherein the content of the hydroxide or oxide of the alkaline earth metal is 1 to 25 kg by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57019291A JPS58137963A (en) | 1982-02-08 | 1982-02-08 | Alkaline zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57019291A JPS58137963A (en) | 1982-02-08 | 1982-02-08 | Alkaline zinc storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58137963A true JPS58137963A (en) | 1983-08-16 |
Family
ID=11995327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57019291A Pending JPS58137963A (en) | 1982-02-08 | 1982-02-08 | Alkaline zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58137963A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697746A1 (en) * | 1994-08-18 | 1996-02-21 | Energy Research Corporation | Sealed zinc secondary battery and zinc electrode therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339978A (en) * | 1976-09-24 | 1978-04-12 | Sumitomo Chem Co Ltd | Preparation of microcapsule having wall of semipermeable membrane |
| JPS5626108A (en) * | 1979-08-08 | 1981-03-13 | Takemi Momo | Greening block and its manufacture |
-
1982
- 1982-02-08 JP JP57019291A patent/JPS58137963A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339978A (en) * | 1976-09-24 | 1978-04-12 | Sumitomo Chem Co Ltd | Preparation of microcapsule having wall of semipermeable membrane |
| JPS5626108A (en) * | 1979-08-08 | 1981-03-13 | Takemi Momo | Greening block and its manufacture |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697746A1 (en) * | 1994-08-18 | 1996-02-21 | Energy Research Corporation | Sealed zinc secondary battery and zinc electrode therefor |
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