JP3632866B2 - Nickel hydride storage battery - Google Patents
Nickel hydride storage battery Download PDFInfo
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- JP3632866B2 JP3632866B2 JP25098695A JP25098695A JP3632866B2 JP 3632866 B2 JP3632866 B2 JP 3632866B2 JP 25098695 A JP25098695 A JP 25098695A JP 25098695 A JP25098695 A JP 25098695A JP 3632866 B2 JP3632866 B2 JP 3632866B2
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- Prior art keywords
- nickel
- storage battery
- hydride storage
- ytterbium
- nickel hydride
- 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.)
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- 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
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Description
【０００１】
【発明の属する技術分野】
本発明はニッケル水酸化物および水素吸蔵合金を用いたニッケル水素化物蓄電池に関するものである。
【０００２】
【従来の技術】
昨今の環境保護の気運に乗り、低公害性のニッケル水素化物蓄電池は、従来のカドミウムを負極に用いるニッケルカドミウム蓄電池に代わる電源としてポータブル機器などに用いられ、研究開発が盛んに行われている。
【０００３】
ところで、従来のニッケルカドミウム蓄電池においては、ニッケル正極の高温における利用率を維持するためカドミウムの添加が不可欠であった。低公害性を最大の特徴とするニッケル水素物蓄電池においては、環境破壊物質であるカドミウムを使用することができないという問題があった。これを解決する手段として、特開平５−２９０８７９公報等にみられるように、カルシウム化合物などの各種添加剤を添加する方法が報告されている。しかしながらニッケル水素化物蓄電池においては、以下に述べるように、ニッケル正極の高温における利用率が低いという問題があり、これら従来添加物では、電池性能改善には不十分であった。一方、水素吸蔵合金は強アルカリ中では合金構成成分である希土類が溶け出し、絶縁性の水酸化物として析出する腐蝕現象を起こすため、寿命が短くなるという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明は上記問題点に鑑みてなされたものであり、ニッケル正極の高温における利用率を高め、水素吸蔵合金負極の合金腐食をおさえ、サイクル寿命を高めたニッケル水素化物蓄電池を完成したものである。
【０００５】
【課題を解決するための手段】
本発明では、ニッケル水素化物蓄電池中のニッケル水酸化物正極にイッテルビウム又はイッテルビウム化合物を混合添加することで、上記問題点を解決した。
【０００６】
イッテルビウムおよびイッテルビウム化合物は強アルカリ中でわずかに溶け、安定な水酸化物として析出する。イッテルビウム水酸化物は酸素発生過電圧を引き上げる効果を持ち、電解液の分解を防止するためニッケル正極の高温における利用率を高める。また溶解したイッテルビウムおよびイッテルビウム化合物は、水素吸蔵合金負極表面に安定な水酸化物として析出する際に被膜を形成し、これが合金成分の腐食を防ぐため、負極の寿命を長くする。
【０００７】
【発明の実施の形態】
以下に実施例に基づき本発明を説明する。
（実施例１）
例えばカドミウムを含まない市販の水酸化ニッケルを準備して、水酸化ニッケル粉末に対し、 導電剤として金属Ｃｏを重量％で６ｗｔ％、ＣｏＯを重量％で４ｗｔ％となるようにそれぞれ加え、例えばＹｂ２ Ｏ３ を重量％で２．５ ％十分に混合した。これに水および増粘剤を加えペ−スト状にし、例えば、ニッケル繊維基板に充填、乾燥後プレスして本発明ニッケル正極と成し、通常の水素吸蔵合金電極を相手極としアルカリ電解液を用いて、本発明ニッケル水素化物蓄電池を作成した。
【０００８】
一方、比較のため上記と同様の組成の水酸化ニッケル粉末に従来添加物として、Ｃａ（ＯＨ）2を添加したもの、および、添加剤を使用しない従来の正極を作製し、同様に通常の水素吸蔵合金電極を相手極としアルカリ電解液を用いて、比較用ニッケル水素化物蓄電池を作製した。この比較用電池は、Ｙｂ2Ｏ3を前記水酸化ニッケル粉末に混合添加してない以外は本発明ニッケル水素化物蓄電池と全く同じ物である。
【０００９】
このようにして作成した本発明ニッケル水素化物蓄電池と比較用ニッケル水素化物蓄電池を用いて、充放電を行った。その結果を図１に、またこれらの電池の酸素発生過電圧を表１それぞれ示す。
【００１０】
【表１】
図１中で放電利用率は正極合剤中のＮｉ（ＯＨ）２ の理論容量を１グラム当たり２９０ｍＡｈとしたときの実際の放電容量を理論容量で割ったものに１００ をかけたものである。図１から明かなとおり、本発明ニッケル水素化物蓄電池は高温においても十分な容量を維持していることがわかる。また、表１から明らかな通り本発明の酸素過電圧は従来例に比べて高く、これにより電解液の分解が抑えられ、電池の容量低下を防止できる。
【００１２】
更に、サイクル試験を行った後の電池を解体し、負極から水素吸蔵合金を取り出して、Ｘ先回折を行った結果を図２に示す。図２より明らかなように本発明である水酸化ニッケル粉末にＹｂ2Ｏ3を混合添加したものは、２シータ２９度付近の希土類水酸化物のピークが小さく、合金腐蝕が抑えられていることが分かる。
【００１３】
（実施例２）
例えば実施例１と同様に水酸化ニッケル粉末に対し、 導電剤として金属Ｃｏを重量％で６ｗｔ％、ＣｏＯを重量％で４ｗｔ％となるようにそれぞれ加え、種々の量のＹｂ２ Ｏ３ を加え、さらに水および増粘剤を加えペ−スト状にし、例えば、ニッケル繊維基板に充填、乾燥後プレスして水酸化ニッケル正極を作成した。Ｙｂ２ Ｏ３ の添加量は表２にまとめて示す。
【００１４】
【表２】
この水酸化ニッケル正極に通常の水素吸蔵合金電極を相手極とし、アルカリ電解液を用いて、ニッケル水素化物蓄電池を作製した。この電池を用いて、充放電を行った。その結果を図３に示す。図３から明らかなとおり、Ｙｂ2Ｏ3を混合添加することにより高温性能が改善されていることが分かる。但し、５％以上の添加では常温での利用率が悪くなり、０．５％以下の添加では高温での効果が弱くなるため、重量％で０．５から５．０％の混合添加が望ましい。
【００１６】
【発明の効果】
上記のように、本発明のニッケル水素化物蓄電池では、水酸化ニッケルを主成分とする活物質粉末にイッテルビウムおよびイッテルビウム化合物を混合添加することにより、ニッケル正極の高温における利用率を高め、水素吸蔵合金負極の合金腐蝕をおさえ、サイクル寿命を高めたニッケル水素化物蓄電池を完成するという極めて優れた効果が得られる。
【図面の簡単な説明】
【図１】サイクル数と放電利用率の関係を示した図である。
【図２】負極から取り出した水素吸蔵合金のＸ線回折を示した図である。
【図３】Ｙｂ２ Ｏ３ 添加量と放電利用率の関係を示した図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a nickel hydride storage battery using nickel hydroxide and a hydrogen storage alloy.
[0002]
[Prior art]
In light of recent environmental protection, low-pollution nickel hydride storage batteries are used in portable devices and the like as power sources to replace conventional nickel cadmium storage batteries that use cadmium as a negative electrode, and research and development are actively conducted.
[0003]
By the way, in the conventional nickel cadmium storage battery, the addition of cadmium was indispensable in order to maintain the utilization rate of the nickel positive electrode at a high temperature. The nickel hydride storage battery, which is characterized by low pollution, has a problem that cadmium, which is an environmentally destructive substance, cannot be used. As means for solving this, a method of adding various additives such as a calcium compound has been reported as disclosed in JP-A-5-290879. However, the nickel hydride storage battery has a problem that the utilization rate of the nickel positive electrode at a high temperature is low as described below, and these conventional additives are insufficient for improving the battery performance. On the other hand, the hydrogen storage alloy has a problem that the life is shortened because the rare earth element, which is an alloy constituent, dissolves in a strong alkali and causes a corrosion phenomenon that precipitates as an insulating hydroxide.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems, and has completed a nickel hydride storage battery that has improved utilization at a high temperature of a nickel positive electrode, suppressed alloy corrosion of a hydrogen storage alloy negative electrode, and has improved cycle life. .
[0005]
[Means for Solving the Problems]
In this invention, the said problem was solved by mixing and adding a ytterbium or a ytterbium compound to the nickel hydroxide positive electrode in a nickel hydride storage battery.
[0006]
Ytterbium and ytterbium compounds dissolve slightly in strong alkalis and precipitate as stable hydroxides. Ytterbium hydroxide has the effect of raising the oxygen generation overvoltage, and increases the utilization rate of the nickel positive electrode at high temperatures in order to prevent decomposition of the electrolyte. The dissolved ytterbium and the ytterbium compound form a film when it is deposited as a stable hydroxide on the surface of the hydrogen storage alloy negative electrode, and this prevents corrosion of the alloy components, thereby extending the life of the negative electrode.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below based on examples.
(Example 1)
For example, a commercially available nickel hydroxide containing no cadmium is prepared, and the metal Co is added to the nickel hydroxide powder as a conductive agent in an amount of 6 wt% by weight and CoO to 4 wt% by weight, for example, Yb 2 O 3 was thoroughly mixed by 2.5% by weight. Water and a thickener are added to this to make a paste, for example, filled into a nickel fiber substrate, dried and pressed to form a nickel positive electrode of the present invention, and an alkaline electrolyte with an ordinary hydrogen storage alloy electrode as a counter electrode. The nickel hydride storage battery of the present invention was prepared.
[0008]
On the other hand, as a conventional additive nickel hydroxide powder having the same composition as the purpose of comparison, that the addition of Ca (OH) 2, and, prior do not use additives positive electrode and work made, likewise normal the hydrogen absorbing alloy electrode using an alkaline electrolyte and mating pole was manufactured create a comparative nickel hydride storage battery. This comparative battery is exactly the same as the nickel hydride storage battery of the present invention except that Yb 2 O 3 is not mixed and added to the nickel hydroxide powder .
[0009]
Charging / discharging was performed using the nickel hydride storage battery of the present invention and the comparative nickel hydride storage battery thus prepared. The results are shown in FIG. 1, and the oxygen generation overvoltages of these batteries are shown in Table 1, respectively.
[0010]
[Table 1]
In FIG. 1, the discharge utilization is 100 times the actual discharge capacity divided by the theoretical capacity when the theoretical capacity of Ni (OH) 2 in the positive electrode mixture is 290 mAh per gram. As can be seen from FIG. 1, the nickel hydride storage battery of the present invention maintains a sufficient capacity even at high temperatures. Further, as is apparent from Table 1, the oxygen overvoltage of the present invention is higher than that of the conventional example, whereby the decomposition of the electrolytic solution can be suppressed and the battery capacity can be prevented from decreasing.
[0012]
Further, the battery after the cycle test was disassembled, the hydrogen storage alloy was taken out from the negative electrode, and the result of X-first diffraction is shown in FIG. As is clear from FIG. 2, when the nickel hydroxide powder of the present invention is mixed with Yb 2 O 3 , the peak of rare earth hydroxide near 2
[0013]
(Example 2)
For example, in the same manner as in Example 1, to the nickel hydroxide powder, as a conductive agent, metal Co was added in an amount of 6 wt% and CoO was added in an amount of 4 wt%, and various amounts of Yb 2 O 3 were added. Further, water and a thickener were added to make a paste, for example, filled in a nickel fiber substrate, dried and pressed to prepare a nickel hydroxide positive electrode. The amount of Yb 2 O 3 added is summarized in Table 2.
[0014]
[Table 2]
A nickel hydride storage battery was fabricated using this nickel hydroxide positive electrode with a normal hydrogen storage alloy electrode as the counter electrode and an alkaline electrolyte. Charging / discharging was performed using this battery. The result is shown in FIG. As is apparent from FIG. 3, it can be seen that the high temperature performance is improved by mixing and adding Yb 2 O 3 . However, worsens utilization at ordinary temperature by the addition of more than 5%, it becomes weak effect at high temperatures by the addition of 0.5% or less is preferable admixed 5.0% from 0.5% by weight .
[0016]
【The invention's effect】
As described above, in the nickel hydride storage battery of the present invention, the ytterbium and ytterbium compounds are mixed and added to the active material powder containing nickel hydroxide as a main component , thereby increasing the utilization rate of the nickel positive electrode at a high temperature. An extremely excellent effect is obtained in that a nickel hydride storage battery having an improved cycle life is completed by suppressing the alloy corrosion of the negative electrode.
[Brief description of the drawings]
FIG. 1 is a diagram showing a relationship between the number of cycles and a discharge utilization rate.
FIG. 2 is a diagram showing X-ray diffraction of a hydrogen storage alloy taken out from a negative electrode.
FIG. 3 is a graph showing the relationship between the amount of Yb 2 O 3 added and the discharge utilization rate.
Claims (3)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25098695A JP3632866B2 (en) | 1995-09-28 | 1995-09-28 | Nickel hydride storage battery |
| EP96931980A EP0794584A4 (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode, and alkaline storage battery |
| US08/849,103 US6136473A (en) | 1995-09-28 | 1996-09-25 | Hydrogen absorbing electrode, nickel electrode and alkaline storage battery |
| PCT/JP1996/002761 WO1997012408A1 (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode, and alkaline storage battery |
| CNB961915048A CN1205679C (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode, and alkaline storage battery |
| CNB2004100317501A CN1244964C (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode and alkaline storage battery |
| CNB2004100317520A CN1253954C (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode and alkaline storage battery |
| KR1019970703538A KR100416428B1 (en) | 1995-09-28 | 1996-09-25 | A hydrogen occlusion electrode, a nickel electrode, and an alkaline storage battery |
| CNA2004100317516A CN1536691A (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode and alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25098695A JP3632866B2 (en) | 1995-09-28 | 1995-09-28 | Nickel hydride storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0992279A JPH0992279A (en) | 1997-04-04 |
| JP3632866B2 true JP3632866B2 (en) | 2005-03-23 |
Family
ID=17215978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25098695A Expired - Lifetime JP3632866B2 (en) | 1995-09-28 | 1995-09-28 | Nickel hydride storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3632866B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4474722B2 (en) | 2000-03-21 | 2010-06-09 | パナソニック株式会社 | Alkaline storage battery and positive electrode for alkaline storage battery used therefor |
| US20010026891A1 (en) | 2000-03-28 | 2001-10-04 | Yoshitaka Dansui | Nickel positive electrode active material and nickel metal hydride storage battery |
| EP1311017B1 (en) * | 2001-11-12 | 2008-10-15 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
-
1995
- 1995-09-28 JP JP25098695A patent/JP3632866B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0992279A (en) | 1997-04-04 |
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