JPH05242886A - Nickel sintered type electrode for alkaline storage battery - Google Patents
Nickel sintered type electrode for alkaline storage batteryInfo
- Publication number
- JPH05242886A JPH05242886A JP4076145A JP7614592A JPH05242886A JP H05242886 A JPH05242886 A JP H05242886A JP 4076145 A JP4076145 A JP 4076145A JP 7614592 A JP7614592 A JP 7614592A JP H05242886 A JPH05242886 A JP H05242886A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- nickel
- active material
- sintered
- alkaline storage
- 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
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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケル粉末焼結多孔
体基板に硝酸ニッケルなどの溶融塩を含浸した後、水酸
化ナトリウム水溶液などで水酸化物化することによっ
て、活物質を基板中に充填する焼結式ニッケル電極に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention fills a substrate with an active material by impregnating a nickel powder sintered porous substrate with a molten salt such as nickel nitrate and then converting the hydroxide into an aqueous solution of sodium hydroxide. The present invention relates to a sintered nickel electrode.
【０００２】[0002]
【従来の技術】焼結式ニッケル電極は、穿孔鋼板などの
基板にニッケル粉末を焼結した多孔体を硝酸ニッケルな
どの溶融塩含浸液に浸漬し、多孔体基板中にニッケル塩
を含浸させ、次いで水酸化ナトリウム水溶液などのアル
カリ液中で水酸化ニッケルに変化させる一連の操作によ
って製造されている。これら操作は、所定の充填量が得
られるまで数回繰り返えされる。2. Description of the Related Art Sintered nickel electrodes are manufactured by immersing a porous body obtained by sintering nickel powder on a substrate such as a perforated steel sheet in a molten salt impregnating solution such as nickel nitrate to impregnate the porous substrate with nickel salt. Then, it is manufactured by a series of operations for changing to nickel hydroxide in an alkaline solution such as an aqueous solution of sodium hydroxide. These operations are repeated several times until the predetermined filling amount is obtained.
【０００３】一般に、前記の硝酸ニッケル含浸液に硝酸
カドミウムを添加することによって、少量のカドミウム
が主活物質である水酸化ニッケルに固溶状態で添加され
ている。これは、水酸化ニッケルのみを充填した焼結式
ニッケル電極では、充放電した場合に大きな電極膨潤
（電極厚みの増大）を引き起こすが、少量のカドミウム
を固溶状態で含有させると、そのような電極膨潤が抑制
されるためである。電極膨潤は電池の短絡や寿命の低下
の原因となるため、それを抑制する手段として、カドミ
ウムの固溶体添加は必要不可欠とされている。Generally, a small amount of cadmium is added in a solid solution state to nickel hydroxide, which is the main active material, by adding cadmium nitrate to the nickel nitrate impregnating solution. This is because a sintered nickel electrode filled only with nickel hydroxide causes large electrode swelling (increased electrode thickness) when charged and discharged, but when a small amount of cadmium is contained in a solid solution state, This is because electrode swelling is suppressed. Electrode swelling causes a short circuit and shortens the life of the battery, so addition of a solid solution of cadmium is indispensable as a means for suppressing it.
【０００４】しかしながら、近年の環境問題のクローズ
アップに伴い、有害金属であるカドミウムの含有は問題
視されている。特に、ニッケル金属水素化物電池やニッ
ケル亜鉛電池においては、カドミウムを含有しないこと
が最重要となっており、カドミウムに替わる新たな添加
元素の開発が望まれている。However, with the recent close-up of environmental problems, the inclusion of cadmium, which is a harmful metal, is regarded as a problem. In particular, in nickel metal hydride batteries and nickel zinc batteries, it is of utmost importance not to contain cadmium, and development of new additive elements in place of cadmium is desired.
【０００５】一方、ポータブルエレクトロニクス機器の
小型軽量化に伴い、その電源である電池に対して高エネ
ルギー密度化が求められている。しかしながら、前記の
焼結式ニッケル電極の活物質利用率の上限は約８０％と
低いことが知られており、電池を高容量化する上での問
題点となっている。また、これら機器内で使用される電
池の周囲雰囲気は高温となる場合が多く、高温性能の優
れた電池の開発も望まれている。On the other hand, with the miniaturization and weight reduction of portable electronic equipment, higher energy density is required for the battery which is the power source thereof. However, it is known that the upper limit of the utilization rate of the active material of the sintered nickel electrode is as low as about 80%, which is a problem in increasing the capacity of the battery. Further, the ambient atmosphere of the battery used in these devices often becomes high temperature, and development of a battery excellent in high temperature performance is desired.
【０００６】[0006]
【発明が解決しようとする問題点】本発明は、前記の課
題に鑑みてなされたものであり、有害金属であるカドミ
ウムを含有することなく、電極膨潤を防止し、高温性能
に優れ、活物質利用率の高い完全無公害な焼結式ニッケ
ル電極を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and prevents swelling of electrodes, is excellent in high-temperature performance, and does not contain an active material without containing cadmium which is a harmful metal. It is intended to provide a completely pollution-free sintered nickel electrode having a high utilization rate.
【０００７】[0007]
【問題点を解決するための手段】本発明の焼結式ニッケ
ル電極は、主活物質である水酸化ニッケルに２族元素
（亜鉛、マグネシウム、バリウム）およびコバルトをそ
れぞれ２重量％以上に範囲で固溶状態で含有させ、且
つ、α−Ｃｏ（ＯＨ）2 を遊離状態で含有させたことを
特徴とするものである。In the sintered nickel electrode of the present invention, the main active material, nickel hydroxide, contains Group 2 elements (zinc, magnesium, barium) and cobalt in an amount of 2% by weight or more, respectively. It is characterized in that it is contained in a solid solution state and α-Co (OH) 2 is contained in a free state.
【０００８】[0008]
【作用】本発明者らは、前記に記載の亜鉛、マグネシウ
ム又はバリウムを水酸化ニッケルに固溶状態で含有させ
ることによって、カドミウムと同様に電極膨潤を抑制す
る効果のあることを見出した。その抑制効果は、それら
元素の含有量に比例して増大し、２重量％以上の範囲で
有効であることがわかった。また、これら元素の添加
は、ニッケル電極の酸素発生電位を貴にシフトさせ、コ
バルトの添加は酸化電位を卑にシフトさせる作用をそれ
ぞれ持つことから、ニッケル電極の酸素過電圧（酸素発
生電位と酸化電位の電位差）が増大し、高温での充電効
率の優れた電極となる。The present inventors have found that the inclusion of zinc, magnesium or barium described above in nickel hydroxide in a solid solution state has the effect of suppressing electrode swelling, similar to cadmium. It was found that the suppressing effect increases in proportion to the contents of those elements and is effective in the range of 2% by weight or more. In addition, since the addition of these elements has the effect of shifting the oxygen generation potential of the nickel electrode to noble, and the addition of cobalt has the effect of shifting the oxidation potential to the base, the oxygen overvoltage (oxygen generation potential and oxidation potential of the nickel electrode). Potential difference) increases, and the electrode has excellent charging efficiency at high temperatures.
【０００９】また、前記の水酸化ニッケル粒子と遊離の
状態で混在するα−Ｃｏ（ＯＨ）2には、活物質利用率
を向上させる効果のあることを見出した。該電極をアル
カリ電解液に浸漬すると、α−Ｃｏ（ＯＨ）2 は活性な
β−Ｃｏ（ＯＨ）2 に変化し、速やかに溶解してＨＣｏ
Ｏ2 - 錯イオンを形成した後、Ｃｏ（ＯＨ）2 として再
析出して電極全体に均一に分散する。即ち、α−Ｃｏ
（ＯＨ）2 は空気中で安定であり、アルカリ水溶液と接
触した時のみ活性なβ−Ｃｏ（ＯＨ）2 に変化する。一
方、β−Ｃｏ（ＯＨ）2 は空気中で不安定であり、難溶
解なＣｏＯＨ2 を表面に形成し、速やかな溶解が妨げら
れる。このように、α−Ｃｏ（ＯＨ）2 は、活性なβ−
Ｃｏ（ＯＨ）2 を電解液と接触した時にのみ生成するこ
とから、これまでβ−Ｃｏ（ＯＨ）2 を用いた場合の問
題点であったＣｏＨＯ2 被膜形成を回避することが可能
となった。このようにして電極全体に均一に分散したβ
−Ｃｏ（ＯＨ）2 は、初充電により導電性のＣｏＯＯＨ
に不可逆的に変化し、水酸化ニッケル粒子間を導電性の
ＣｏＯＯＨで接続することで、活物質利用率を向上させ
たものと考えられる。It has also been found that α-Co (OH) 2 mixed with the nickel hydroxide particles in a free state has an effect of improving the utilization rate of the active material. When the electrode is dipped in an alkaline electrolyte, α-Co (OH) 2 changes to active β-Co (OH) 2 and quickly dissolves to form HCo.
O 2 - after the formation of the complex ion, is dispersed evenly throughout and reprecipitated electrode as Co (OH) 2. That is, α-Co
(OH) 2 is stable in air and changes to β-Co (OH) 2 which is active only when contacted with an alkaline aqueous solution. On the other hand, β-Co (OH) 2 is unstable in air and forms CoOH 2 which is difficult to dissolve on the surface, which hinders its rapid dissolution. Thus, α-Co (OH) 2 is active β-Co (OH) 2.
Since Co (OH) 2 is produced only when it comes into contact with the electrolytic solution, it has become possible to avoid the formation of a CoHO 2 film, which has been a problem when using β-Co (OH) 2 so far. .. In this way, β distributed uniformly over the electrode
-Co (OH) 2 is conductive CoOOH after the first charge.
It is considered that the utilization rate of the active material was improved by connecting the nickel hydroxide particles with each other by conductive CoOOH.
【００１０】このような作用は、例えばβ−Ｃｏ（Ｏ
Ｈ）2 にもあることが知られているが、本発明のα−Ｃ
ｏ（ＯＨ）2 に比較して、前述の理由で溶解速度が遅
く、分散性も不均一であるために、活物質利用率を向上
させる作用は小さい。Such an action has, for example, β-Co (O
H) 2 is also known, but α-C of the present invention
Compared with o (OH) 2 , the dissolution rate is slow and the dispersibility is non-uniform for the reasons described above, and therefore the effect of improving the utilization rate of the active material is small.
【００１１】[0011]
【実施例】ニッケル粉末を焼結して得られた多孔度約８
０％のニッケル焼結式基板を、８０℃、比重１．８の硝
酸ニッケル水溶液に硝酸亜鉛およびコバルトを各種比率
で加えた含浸液に３０分間浸漬し、乾燥後、８０℃、比
重１．３の水酸化ナトリウム水溶液中にて活物質化する
一連の工程を繰り返して所定の充填量とし、各種電極を
作製した。Example: Porosity of about 8 obtained by sintering nickel powder
A 0% nickel-sintered substrate was immersed in an impregnating solution prepared by adding zinc nitrate and cobalt at various ratios to a nickel nitrate aqueous solution having a specific gravity of 1.8 at 80 ° C. for 30 minutes, and after drying, it was dried at 80 ° C. and a specific gravity of 1.3. Various electrodes were prepared by repeating a series of steps of forming an active material in the aqueous sodium hydroxide solution to give a predetermined filling amount.
【００１２】次いで、前記の電極を比重１．２の硝酸コ
バルト水溶液に浸漬して乾燥後、ｐＨ１０〜１２の希ア
ルカリ水溶液に浸漬して遊離状態のα−Ｃｏ（ＯＨ）2
を生成させて、本発明電極（Ａ）を作製した。また、ｐ
Ｈ１４以上の高濃度アルカリ水溶液で同様の処理を行
い、遊離状態のβ−Ｃｏ（ＯＨ）2 を生成させた電極
（Ｄ）も作成した。比較電極（Ｃ）として、水酸化ニッ
ケルのみを充填した焼結式電極も作成した。このように
して作成した各種電極を、セパレータを介してカドミウ
ム負極と対向させ、比重１．２４の水酸化カリウム水溶
液を電解液とし、開放系にて充放電し性能評価した。Next, the above electrode is immersed in an aqueous cobalt nitrate solution having a specific gravity of 1.2 and dried, and then immersed in a dilute alkaline aqueous solution having a pH of 10 to 12 to form a free α-Co (OH) 2
To produce the electrode (A) of the present invention. Also, p
The same treatment was performed with a high-concentration alkaline aqueous solution of H14 or higher, and an electrode (D) in which free β-Co (OH) 2 was produced was also prepared. As a comparative electrode (C), a sintered electrode filled only with nickel hydroxide was also prepared. The various electrodes thus prepared were opposed to the cadmium negative electrode via the separator, and an aqueous solution of potassium hydroxide having a specific gravity of 1.24 was used as an electrolytic solution to charge and discharge in an open system to evaluate the performance.
【００１３】次表は、水酸化ニッケルに亜鉛５重量％お
よびコバルト５重量％を固溶体添加し、遊離状態のα−
Ｃｏ（ＯＨ）2 を生成させていない焼結式の比較電極
（Ｂ）と、本発明の電極（Ａ）と比較電極（Ｄ）、およ
び比較電極（Ｃ）を、０．１Ｃで１５０％充電し、０．
２Ｃで０Ｖ（対Ｈｇ／ＨｇＯ参照電極）まで放電したと
きのニッケル酸化値を示した。The following table shows that a solid solution containing 5% by weight of zinc and 5% by weight of cobalt was added to nickel hydroxide to obtain α-
The sintering type reference electrode (B) not producing Co (OH) 2 , the electrode (A) and the reference electrode (D) of the present invention, and the reference electrode (C) were charged at 0.1 C by 150%. , And 0.
The nickel oxidation value when discharged to 0 V (vs. Hg / HgO reference electrode) at 2C is shown.
【００１４】 [0014]
【００１５】本発明電極の活物質利用率は９０％と向上
され、最も放電深度が深くなっている。即ち、α−Ｃｏ
（ＯＨ）2 は水酸化ニッケルの放電深度を深くする作用
があり、その効果はβ−Ｃｏ（ＯＨ）2 より大きいこと
がわかる。比較電極（Ｃ）では電極膨潤の原因であるγ
−ＮｉＯＯＨの生成が認められ、充電末期の酸化値が高
くなっている。亜鉛を含有した本発明電極（Ａ）と電極
（Ｂ）では、γ−ＮｉＯＯＨの生成は認められず、電極
膨潤は防止されていた。電極膨潤は、亜鉛の含有量が２
重量％以上の範囲で効果的に防止された。The utilization factor of the active material of the electrode of the present invention was improved to 90%, and the depth of discharge was deepest. That is, α-Co
(OH) 2 has a function of deep discharge depth of the nickel hydroxide, the effect is seen to be greater than the beta-Co (OH) 2. In the comparative electrode (C), γ which is the cause of electrode swelling
-The production of NiOOH is recognized, and the oxidation value at the end of charging is high. In the electrodes (A) and (B) of the present invention containing zinc, generation of γ-NiOOH was not observed, and electrode swelling was prevented. Electrode swelling has a zinc content of 2
It was effectively prevented in the range of more than wt%.
【００１６】図１は、５℃〜４５℃の温度範囲での充電
効率を、本発明電極（Ａ）と比較電極（Ｃ）について示
したものである。本発明電極（Ａ）の高温での充電効率
が良好なことがわかる。高温時の充電効率の向上には、
コバルトを２重量％以上の範囲で水酸化ニッケルに固溶
体添加する必要があった。FIG. 1 shows the charging efficiency in the temperature range of 5 ° C. to 45 ° C. for the electrode (A) of the present invention and the comparative electrode (C). It can be seen that the electrode (A) of the present invention has good charging efficiency at high temperatures. To improve charging efficiency at high temperatures,
It was necessary to add cobalt as a solid solution to nickel hydroxide in the range of 2% by weight or more.
【００１７】[0017]
【発明の効果】以上のように、本発明によれば電極膨潤
が防止され、高温時の充電効率の優れた高容量な、且つ
完全無公害性のニッケル焼結式電極が提供でき、その工
業的価値は極めて大きい。Industrial Applicability As described above, according to the present invention, it is possible to provide a nickel-sintered nickel electrode of high capacity which is prevented from electrode swelling, has excellent charging efficiency at high temperature, and is completely pollution-free. The target value is extremely large.
【図１】充電時の温度を変えた時の各種ニッケル焼結式
電極の充電効率を示す。FIG. 1 shows the charging efficiency of various nickel sintered electrodes when the temperature during charging was changed.
Ａ 本発明電極 Ｃ 比較電極 A Inventive electrode C Comparative electrode
Claims (2)
物質が充填されたニッケル電極において、主活物質であ
る水酸化ニッケルに２族元素およびコバルトを固溶状態
で含有させ、かつ、α−Ｃｏ（ＯＨ）2 を遊離状態で含
有させたことを特徴とするアルカリ蓄電池用焼結式ニッ
ケル電極。1. A nickel electrode in which an active material is filled in a porous substrate obtained by sintering nickel powder, wherein the main active material, nickel hydroxide, contains a Group 2 element and cobalt in a solid solution state, and α A sintered nickel electrode for alkaline storage batteries, characterized in that it contains Co (OH) 2 in a free state.
又はバリウムであり、その含有量が２重量％以上であ
り、かつ、コバルトの含有量が２重量％以上である請求
項１記載のアルカリ蓄電池用焼結式ニッケル電極。2. The alkali according to claim 1, wherein the Group 2 element is zinc, magnesium or barium, the content of which is 2% by weight or more, and the content of cobalt is 2% by weight or more. Sintered nickel electrode for storage batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07614592A JP3292204B2 (en) | 1992-02-26 | 1992-02-26 | Nickel sintered electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07614592A JP3292204B2 (en) | 1992-02-26 | 1992-02-26 | Nickel sintered electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05242886A true JPH05242886A (en) | 1993-09-21 |
| JP3292204B2 JP3292204B2 (en) | 2002-06-17 |
Family
ID=13596839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07614592A Expired - Lifetime JP3292204B2 (en) | 1992-02-26 | 1992-02-26 | Nickel sintered electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3292204B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620549B2 (en) | 1998-06-16 | 2003-09-16 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
-
1992
- 1992-02-26 JP JP07614592A patent/JP3292204B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620549B2 (en) | 1998-06-16 | 2003-09-16 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3292204B2 (en) | 2002-06-17 |
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