JPH0992279A - Alkaline storage battery - Google Patents
Alkaline storage batteryInfo
- Publication number
- JPH0992279A JPH0992279A JP7250986A JP25098695A JPH0992279A JP H0992279 A JPH0992279 A JP H0992279A JP 7250986 A JP7250986 A JP 7250986A JP 25098695 A JP25098695 A JP 25098695A JP H0992279 A JPH0992279 A JP H0992279A
- Authority
- JP
- Japan
- Prior art keywords
- ytterbium
- storage battery
- positive electrode
- nickel
- 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
-
- 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)
Abstract
Description
【０００１】[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。TECHNICAL FIELD The present invention relates to a nickel hydride storage battery using a nickel hydroxide and a hydrogen storage alloy.
【０００２】[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。2. Description of the Related Art With the recent trend of environmental protection, low-pollution nickel hydride storage batteries are being used in portable equipment and the like as a power source to replace conventional nickel-cadmium storage batteries that use cadmium as a negative electrode, and research and development have been actively conducted. Has been done.
【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化物蓄電池において
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な問題があり、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食現象を起
こすため、寿命が短くなるという問題があった。By the way, in the conventional nickel-cadmium storage battery, addition of cadmium was indispensable in order to maintain the utilization rate of the nickel positive electrode at high temperature. In the nickel hydride storage battery, which is most characterized by low pollution, there is a problem that cadmium, which is an environmentally destructive substance, cannot be used. As a means for solving this, a method of adding various additives such as a calcium compound has been reported as seen in JP-A-5-290879. However, nickel hydride storage batteries have the following problems, and these conventional additives have not been sufficient for improving battery performance. On the other hand, the hydrogen storage alloy has a problem that the life is shortened because a rare earth element, which is an alloy constituent, is dissolved out in a strong alkali to cause a corrosion phenomenon in which it is deposited as an insulating hydroxide.
【０００４】[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。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and it has been proposed to improve the utilization rate of a nickel positive electrode at high temperature, suppress the alloy corrosion of a hydrogen storage alloy negative electrode, and extend the cycle life of nickel. This is a completed hydride storage battery.
【０００５】[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添加することで、上記問
題点を解決した。In the present invention, the above problems have been solved by adding ytterbium or a ytterbium compound to the nickel hydroxide positive electrode in a nickel hydride storage battery.
【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。Ytterbium and the ytterbium compound are slightly dissolved in a strong alkali and precipitate as a stable hydroxide. 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 electrolytic solution. Further, the dissolved ytterbium and the ytterbium compound form a film when deposited as a stable hydroxide on the surface of the hydrogen storage alloy negative electrode, and this prevents corrosion of the alloy components, thereby prolonging the life of the negative electrode.
【０００７】[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 Ｏ
3 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。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on Examples. (Example 1) For example, a commercially available nickel hydroxide containing no cadmium was prepared, and 6% by weight of metal Co and 6% by weight of CoO were used as a conductive agent with respect to the nickel hydroxide powder.
Added in an amount of 4 wt%, for example Yb 2 O
2.5% by weight of 3 was thoroughly mixed. To this, water and a thickener are added to form a paste, for example, a nickel fiber substrate is filled, dried and pressed to form the nickel positive electrode of the present invention,
A nickel hydride storage battery of the present invention was prepared by using an ordinary hydrogen storage alloy electrode as a counter electrode and an alkaline electrolyte.
【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
作成し、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
を作成した。この比較用電池はＹｂ2 Ｏ3 を正極中に含
ま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。On the other hand, for comparison, a nickel hydroxide powder having the same composition as that described above to which Ca (OH) 2 was added as a conventional additive, and a conventional positive electrode containing no additive were prepared. A nickel hydride storage battery for comparison was prepared by using the hydrogen storage alloy electrode of No. 2 as a counter electrode and an alkaline electrolyte. 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 contained in the positive electrode.
【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。The nickel hydride storage battery of the present invention thus prepared and the nickel hydride storage battery for comparison were used for charging and discharging. The results are shown in FIG. 1, and the oxygen generation overvoltage of these batteries is shown in Table 1.
【００１０】[0010]
【表１】 [Table 1]
【００１１】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。In FIG. 1, the discharge utilization factor is Ni in the positive electrode mixture.
When the theoretical capacity of (OH) 2 is 290 mAh per gram, the actual discharge capacity is divided by the theoretical capacity and multiplied by 100. As is clear from FIG. 1, the nickel hydride storage battery of the present invention maintains a sufficient capacity even at high temperatures. Further, as is clear from Table 1, the oxygen overvoltage of the present invention is higher than that of the conventional example, which suppresses the decomposition of the electrolytic solution and prevents the battery capacity from decreasing.
【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線回折を
行った結果を図２に示す。図２よりあきらかなように本
発明であるＹｂ2 Ｏ3 を添加したものは、２シータ29度
付近の希土類水酸化物のピークが小さく、合金腐食が抑
えられていることが分かる。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-ray diffraction is shown in FIG. As is apparent from FIG. 2, it is clear that the alloy of the present invention to which Yb 2 O 3 is added has a small peak of the rare earth hydroxide near 2 theta of 29 ° and alloy corrosion is suppressed.
【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。(Embodiment 2) For example, in the same manner as in Embodiment 1, with respect to nickel hydroxide powder, metal Co is used as a weight% as a conductive agent.
At 6 wt% and CoO at 4 wt% by weight, various amounts of Yb 2 O 3 are added, and water and a thickener are further added to form a paste, for example, a nickel fiber substrate is filled. Then, it was dried and pressed to prepare a nickel hydroxide positive electrode. The amount of Yb 2 O 3 added is summarized in Table 2.
【００１４】[0014]
【表２】 [Table 2]
【００１５】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から明かな
とおり、Ｙｂ2 Ｏ3 を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 ％の添
加が望ましい。A nickel hydride storage battery was produced by using this nickel hydroxide positive electrode as a counter electrode for a normal hydrogen storage alloy electrode and using an alkaline electrolyte. Using this battery, charging / discharging was performed. The result is shown in FIG. As is clear from FIG. 3, the high temperature performance is improved by adding Yb 2 O 3 . However, if it is added in an amount of 5% or more, the utilization factor at room temperature becomes poor, and if it is added in an amount of 0.5% or less, the effect at a high temperature becomes weak.
【００１６】[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、水酸化ニッケル正極中にイッテルビウム
およびイッテルビウム化合物を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するという極めて優れた効果が
得られる。As described above, in the nickel hydride storage battery of the present invention, by adding ytterbium and the ytterbium compound in the nickel hydroxide positive electrode, the utilization rate of the nickel positive electrode at high temperature is increased and the hydrogen storage alloy negative electrode An extremely excellent effect of suppressing alloy corrosion and completing a nickel hydride storage battery having an improved cycle life can be obtained.
【図１】サイクル数と放電利用率の関係を示した図であ
る。FIG. 1 is a diagram showing a relationship between the number of cycles and a discharge utilization rate.
【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。FIG. 2 is a diagram showing X-ray diffraction of a hydrogen storage alloy taken out from a negative electrode.
【図３】Ｙｂ2 Ｏ3 添加量と放電利用率の関係を示した
図である。FIG. 3 is a diagram showing the relationship between the amount of Yb 2 O 3 added and the discharge utilization rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 押谷 政彦 大阪府高槻市城西町６番６号 株式会社ユ アサコーポレーション内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiko Oshiya 6-6 Josai-cho, Takatsuki-shi, Osaka Inside Yuasa Corporation
Claims (3)
にイッテルビウム又はイッテルビウム化合物を添加して
なる正極を備えたことを特徴とするアルカリ蓄電池。1. An alkaline storage battery comprising a positive electrode formed by adding ytterbium or a ytterbium compound to an active material containing nickel hydroxide as a main component.
ビウム又はイッテルビウム化合物が、ニッケル水酸化物
を主成分とする活物質と遊離状態で存在している請求項
１記載のアルカリ蓄電池。2. The alkaline storage battery according to claim 1, wherein in the alkaline storage battery, ytterbium or a ytterbium compound exists in a free state with an active material containing nickel hydroxide as a main component.
ビウム又はイッテルビウム化合物が、酸化物あるいは水
酸化物の状態で上記正極中に存在している請求項１記載
のアルカリ蓄電池。3. The alkaline storage battery according to claim 1, wherein in the alkaline storage battery, ytterbium or a ytterbium compound is present in the positive electrode in a state of an oxide or a hydroxide.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25098695A JP3632866B2 (en) | 1995-09-28 | 1995-09-28 | Nickel hydride storage battery |
| PCT/JP1996/002761 WO1997012408A1 (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 |
| US08/849,103 US6136473A (en) | 1995-09-28 | 1996-09-25 | Hydrogen absorbing electrode, nickel electrode and alkaline storage battery |
| EP96931980A EP0794584A4 (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 |
| 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 |
| CNB961915048A CN1205679C (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 true JPH0992279A (en) | 1997-04-04 |
| JP3632866B2 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6489059B2 (en) | 2000-03-21 | 2002-12-03 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and positive electrode used for the alkaline storage battery |
| US7056621B2 (en) * | 2001-11-12 | 2006-06-06 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
| US7147676B2 (en) | 2000-03-28 | 2006-12-12 | Matsushita Electric Industrial Co., Ltd. | Method of preparing a nickel positive electrode active material |
-
1995
- 1995-09-28 JP JP25098695A patent/JP3632866B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6489059B2 (en) | 2000-03-21 | 2002-12-03 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and positive electrode used for the alkaline storage battery |
| US7147676B2 (en) | 2000-03-28 | 2006-12-12 | Matsushita Electric Industrial Co., Ltd. | Method of preparing a nickel positive electrode active material |
| US7056621B2 (en) * | 2001-11-12 | 2006-06-06 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3632866B2 (en) | 2005-03-23 |
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