JP2889669B2 - Non-sintered nickel positive electrode plate for alkaline storage batteries - Google Patents
Non-sintered nickel positive electrode plate for alkaline storage batteriesInfo
- Publication number
- JP2889669B2 JP2889669B2 JP2212014A JP21201490A JP2889669B2 JP 2889669 B2 JP2889669 B2 JP 2889669B2 JP 2212014 A JP2212014 A JP 2212014A JP 21201490 A JP21201490 A JP 21201490A JP 2889669 B2 JP2889669 B2 JP 2889669B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- electrode plate
- oxyhydroxide
- positive electrode
- cobalt
- 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 - Fee Related
Links
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
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−カドミウム蓄電池、ニッケル−
亜鉛蓄電池あるいはニッケル−水素蓄電池などのアルカ
リ蓄電池に用いられる非焼結式ニッケル正極板に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention relates to a nickel-cadmium storage battery,
The present invention relates to a non-sintered nickel positive electrode plate used for an alkaline storage battery such as a zinc storage battery or a nickel-hydrogen storage battery.
（ロ）従来の技術 従来、ニッケル−カドミウム蓄電池などのニッケル正
極板の代表的なものは焼結式により得られたものであっ
た。この焼結式極板の場合、活物質保持体としての焼結
基板の孔径が小さいので、活物質を粉末状態で直接充填
することができず、活物質塩を含浸し、これを活物質に
転化するなどの煩雑な工程を要した。(B) Conventional technology Conventionally, a typical nickel positive electrode plate such as a nickel-cadmium storage battery has been obtained by a sintering method. In the case of this sintered type electrode plate, since the pore diameter of the sintered substrate as the active material holding member is small, the active material cannot be directly filled in a powder state, and the active material salt is impregnated with the active material salt. A complicated process such as conversion was required.
最近、水酸化ニッケルを主とするペースト状の活物質
混合物を約95％程度の多孔度を有するスポンジ状の金属
ニッケル基板に直接充填するという非焼結式ニッケル正
極板が提案されている。Recently, there has been proposed a non-sintered nickel positive electrode plate in which a paste-like active material mixture mainly composed of nickel hydroxide is directly filled into a sponge-like metal nickel substrate having a porosity of about 95%.
この非焼結式正極板は、従来の焼結式正極板に比べ、
製造が非常に簡単であること、また高容量化、軽量化に
適し研究が進められている。This non-sintered positive electrode plate, compared to the conventional sintered positive electrode plate,
Research is being carried out on the fact that it is very easy to manufacture and suitable for increasing the capacity and weight.
特公昭57−5344号公報では、非焼結式ニッケル正極板
の利用率を向上させるため、コバルト化合物を添加する
方法が提案されている。添加されたコバルト化合物は、
１回目の充電初期に酸化を受け、導電性の高いオキシ水
酸化コバルトに変化し、その結果として、水酸化ニッケ
ル間の導電性が向上し、利用率の向上をもたらすのであ
る。Japanese Patent Publication No. 57-5344 proposes a method of adding a cobalt compound in order to improve the utilization rate of a non-sintered nickel positive electrode plate. The added cobalt compound is
It is oxidized in the early stage of the first charge and changes to cobalt oxyhydroxide having high conductivity. As a result, the conductivity between nickel hydroxide is improved and the utilization factor is improved.
しかし、活物質中に添加されたコバルト化合物を充電
時に完全にオキシ水酸化コバルトへ酸化することは困難
である。このため、コバルト化合物を添加し導電性が向
上する効果を十分に引き出すことができない。However, it is difficult to completely oxidize the cobalt compound added to the active material to cobalt oxyhydroxide during charging. Therefore, the effect of improving the conductivity by adding a cobalt compound cannot be sufficiently brought out.
これに対して、特開昭60−254564号公報では、活物質
中にオキシ水酸化ニッケル粉末を添加することにより、
コバルト化合物の酸化を助長する方法が提案されてい
る。On the other hand, JP-A-60-254564 discloses that by adding nickel oxyhydroxide powder to an active material,
Methods have been proposed to promote the oxidation of cobalt compounds.
しかしながら、オキシ水酸化ニッケルをニッケル極に
添加する場合、粉末の状態で添加すると、局所的な部分
では均一性に欠け、また、コバルト化合物はオキシ水酸
化ニッケルの近傍でオキシ水酸化コバルトに変化するた
め、オキシ水酸化コバルトも均一性に乏しくなり、導電
性の向上効果を充分に得ることができない。However, when adding nickel oxyhydroxide to a nickel electrode, if it is added in the form of a powder, the local portion lacks uniformity, and the cobalt compound changes to cobalt oxyhydroxide near the nickel oxyhydroxide. Therefore, cobalt oxyhydroxide also has poor uniformity, and the effect of improving conductivity cannot be sufficiently obtained.
尚、コバルト化合物を酸化してオキシ水酸化コバルト
とするためには、オキシ水酸化コバルトが３価なのでコ
バルト化合物は２価以下としなければならない。ここ
で、２価以下のコバルト化合物としては、金属コバル
ト、水酸化コバルト等が挙げられる。In order to oxidize the cobalt compound into cobalt oxyhydroxide, the cobalt compound must be divalent or less since cobalt oxyhydroxide is trivalent. Here, examples of the divalent or lower valent cobalt compound include metallic cobalt and cobalt hydroxide.
（ハ）発明が解決しようとする課題 本発明は、上述の如き問題点を解決し、極板内に均一
に導電性を向上させ、以って利用率の高いニッケル正極
板を得ようとするものである。(C) Problems to be Solved by the Invention The present invention is intended to solve the above-mentioned problems, to improve the conductivity uniformly in the electrode plate, and to obtain a nickel positive electrode plate having a high utilization factor. Things.
（ニ）課題を解決するための手段 本発明は、表面層がオキシ水酸化ニッケルである水酸
化ニッケル粉末と、２価以下のコバルト化合物粉末とを
含む混合物を活物質保持体に担持させた非焼結式ニッケ
ル正極板にある。(D) Means for Solving the Problems The present invention relates to a non-aqueous substrate comprising a mixture of nickel hydroxide powder whose surface layer is nickel oxyhydroxide and a cobalt compound powder having a valence of 2 or less supported on an active material holder. Sintered nickel positive plate.
（ホ）作用 活物質中に添加されたコバルト化合物は、オキシ水酸
化ニッケルの存在により、アルカリ水溶液中にて、以下
のような反応でオキシ水酸化コバルトに変化する。(E) Action The cobalt compound added to the active material is changed to cobalt oxyhydroxide in an alkaline aqueous solution by the following reaction due to the presence of nickel oxyhydroxide.
１）Co(OH)2→Co錯イオン ２）Co錯イオン＋NiOOH→CoOOH＋Ni(OH)2 つまり、オキシ水酸化コバルトの生成は、オキシ水酸
化ニッケルの近傍にて生じるのである。1) Co (OH) 2 → Co complex ion 2) Co complex ion + NiOOH → CoOOH + Ni (OH) 2 That is, the formation of cobalt oxyhydroxide occurs near nickel oxyhydroxide.
本発明によれば、表面層がオキシ水酸化ニッケルであ
る水酸化ニッケル粉末を用いているので、オキシ水酸化
ニッケル表面層とコバルト化合物とが反応し、水酸化ニ
ッケル粉末を均一に被覆するようにオキシ水酸化コバル
トが生成する。これにより、極板内に均一にオキシ水酸
化コバルトが存在し、導電性が良くなり利用率が向上す
る。According to the present invention, since the surface layer uses nickel hydroxide powder that is nickel oxyhydroxide, the nickel oxyhydroxide surface layer reacts with the cobalt compound to uniformly coat the nickel hydroxide powder. Cobalt oxyhydroxide is formed. Thereby, the cobalt oxyhydroxide is uniformly present in the electrode plate, the conductivity is improved, and the utilization rate is improved.
（ヘ）実施例 粒径５μｍの球状水酸化ニッケルを亜塩素酸ナトリウ
ム2wt％、水酸化ナトリウム20wt％水溶液に５分間浸漬
し、水洗、乾燥して表面層がオキシ水酸化ニッケルであ
る水酸化ニッケルを作製した。オキシ水酸化ニッケルの
量は、水酸化ニッケルに対して約5wt％である。(F) Example Spherical nickel hydroxide having a particle size of 5 μm is immersed in an aqueous solution of 2 wt% of sodium chlorite and 20 wt% of sodium hydroxide for 5 minutes, washed with water and dried, and the surface layer is nickel hydroxide of nickel oxyhydroxide. Was prepared. The amount of nickel oxyhydroxide is about 5% by weight based on nickel hydroxide.
この表面層がオキシ水酸化ニッケルである水酸化ニッ
ケル粉末95wt％と、水酸化コバルト粉末5wt％からなる
活物質粉末に、メチルセルロース0.5wt％水溶液を加え
混合し活物質スラリーを作製した。この活物質スラリー
を発泡ニッケル基体に充填し乾燥後、圧延することによ
り活物質密度2.5g/cc−voidの本発明極板を得た。A 0.5 wt% aqueous solution of methylcellulose was added to and mixed with 95 wt% of nickel hydroxide powder whose surface layer was nickel oxyhydroxide and 5 wt% of cobalt hydroxide powder to prepare an active material slurry. This active material slurry was filled in a foamed nickel substrate, dried, and then rolled to obtain an electrode plate of the present invention having an active material density of 2.5 g / cc-void.
一方、粒径５μｍの球状水酸化ニッケルを亜塩素酸ナ
トリウム2wt％水溶液に１時間浸漬し、完全にオキシ水
酸化ニッケルに変化させた後、水洗、乾燥してオキシ水
酸化ニッケル粉末を作製した。On the other hand, spherical nickel hydroxide having a particle size of 5 μm was immersed in a 2 wt% aqueous solution of sodium chlorite for 1 hour to completely convert it to nickel oxyhydroxide, washed with water and dried to prepare a nickel oxyhydroxide powder.
このオキシ水酸化ニッケル粉末5wt％と、水酸化ニッ
ケル粉末90wt％及び水酸化コバルト粉末5wt％からなる
活物質粉末を用い、上記と同様にして活物質密度2.5g/c
c−voidの比較極板を得た。Using this nickel oxyhydroxide powder 5 wt%, the nickel hydroxide powder 90 wt% and the cobalt hydroxide powder 5 wt% active material powder, the active material density was 2.5 g / c in the same manner as above.
A comparison electrode of c-void was obtained.
この本発明極板及び比較極板各々１枚と焼結式負極板
２枚とをセパレータを介し、組み合わせた極板群をナイ
ロン袋に入れ、これを両側より構成圧を加え、KOH−NaO
H−LiOHの三成分からなる電解液を注液し、２種類の簡
易セルを作製した。A pair of electrode plates obtained by combining one electrode plate of the present invention and one comparative electrode plate and two sintered negative electrode plates via a separator is placed in a nylon bag, and the resultant is subjected to constituent pressure from both sides by KOH-NaO.
An electrolyte composed of three components of H-LiOH was injected to produce two types of simple cells.
この簡易セルを用い、0.1Cの電流で理論容量に対して
160％まで充電を行い、電圧が0.8Vに達するまで0.3Cの
電流で放電し、利用率を測定した結果を図に示す。図よ
り本発明極板を用いた簡易セルａは、比較極板を用いた
簡易セルｂに比べ高い利用率を示す。Using this simple cell, with 0.1C current to theoretical capacity
The figure shows the results of charging up to 160%, discharging at a current of 0.3C until the voltage reaches 0.8V, and measuring the utilization. From the figure, the simple cell a using the electrode plate of the present invention shows a higher utilization rate than the simple cell b using the comparative electrode plate.
（ト）発明の効果 上述した如く、本発明による非焼結式ニッケル正極板
は、表面層がオキシ水酸化ニッケルである水酸化ニッケ
ル粉末と、２価以下のコバルト化合物粉末とを含むもの
であり、オキシ水酸化ニッケルとの反応により水酸化ニ
ッケル粉末の表面層が均一にオキシ水酸化コバルトにて
被覆され、極板内の導電性が向上して高い利用率を得る
ことができるものでありその工業的価値は極めて大であ
る。(G) Effect of the Invention As described above, the non-sintered nickel positive electrode plate according to the present invention includes a nickel hydroxide powder whose surface layer is nickel oxyhydroxide and a cobalt compound powder having a valence of 2 or less. The surface layer of the nickel hydroxide powder is uniformly coated with cobalt oxyhydroxide by the reaction with nickel oxyhydroxide, and the conductivity in the electrode plate can be improved to obtain a high utilization rate. The industrial value is extremely large.
図は、本発明極板を用いた簡易セルａと、比較極板を用
いた簡易セルｂのサイクルに伴う利用率の変化を示す図
である。The figure shows a change in the utilization rate of the simple cell a using the electrode plate of the present invention and the simple cell b using the comparison electrode plate with the cycle.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/24 H01M 4/52 H01M 4/62 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 4/24 H01M 4/52 H01M 4/62
Claims (1)
化ニッケル粉末と、２価以下のコバルト化合物粉末とを
含む混合物を活物質保持体に担持させたことを特徴とす
るアルカリ蓄電池用非焼結式ニッケル正極板。1. A non-sintered alkaline storage battery comprising: a mixture containing nickel hydroxide powder whose surface layer is nickel oxyhydroxide and a cobalt compound powder having a valence of 2 or less. Bonded nickel positive plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2212014A JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2212014A JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0494058A JPH0494058A (en) | 1992-03-26 |
| JP2889669B2 true JP2889669B2 (en) | 1999-05-10 |
Family
ID=16615455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2212014A Expired - Fee Related JP2889669B2 (en) | 1990-08-09 | 1990-08-09 | Non-sintered nickel positive electrode plate for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2889669B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2581362B2 (en) * | 1991-11-25 | 1997-02-12 | 新神戸電機株式会社 | Electrodes for alkaline storage batteries |
| US5356732A (en) * | 1992-05-29 | 1994-10-18 | Sanyo Electric Co., Ltd. | Alkaline storage cell activation method |
| US5405714A (en) * | 1992-07-31 | 1995-04-11 | Sanyo Electric Co., Ltd. | Method for activating an alkaline storage cell employing a non-sintered type nickel positive electrode |
| DE69626495T2 (en) * | 1995-11-22 | 2003-12-24 | Matsushita Electric Industrial Co., Ltd. | ELECTRODE WITH ACTIVE MATERIAL FOR POSITIVE PLATE OF A BATTERY |
| EP1195824B1 (en) * | 1996-09-20 | 2011-10-05 | Panasonic Corporation | Positive electrode active material for alkaline storage batteries |
| JP3489960B2 (en) * | 1997-04-01 | 2004-01-26 | 松下電器産業株式会社 | Alkaline storage battery |
| MX241166B (en) * | 2001-06-29 | 2006-10-16 | Ovonic Battery Co | Hydrogen storage battery; positive nickel electrode; positive electrode active material and methods for making. |
-
1990
- 1990-08-09 JP JP2212014A patent/JP2889669B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0494058A (en) | 1992-03-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |