JPH09219214A - Alkaline storage battery - Google Patents
Alkaline storage batteryInfo
- Publication number
- JPH09219214A JPH09219214A JP8023752A JP2375296A JPH09219214A JP H09219214 A JPH09219214 A JP H09219214A JP 8023752 A JP8023752 A JP 8023752A JP 2375296 A JP2375296 A JP 2375296A JP H09219214 A JPH09219214 A JP H09219214A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- ytterbium
- storage battery
- electrolyte
- nickel
- 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
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はニッケル水素化物蓄
電池、ニッケル−カドミウム蓄電池などのアルカリ蓄電
池に関するものである。TECHNICAL FIELD The present invention relates to alkaline storage batteries such as nickel hydride storage batteries and nickel-cadmium storage batteries.
【０００２】[0002]
【従来の技術】ニッケル水酸化物を活物質として用いる
正極は、ニッケル−水素化物電池、ニッケル−カドミウ
ム電池、ニッケル−亜鉛電池、ニッケル−鉄電池などの
アルカリ蓄電池に共通して幅広く用いられている。近年
においては低公害性、高エネルギ−密度などの観点から
特にニッケル−水素化物電池が注目され、ポ−タブル機
器用から電気自動車用まで幅広く研究開発がなされてい
る。2. Description of the Prior Art A positive electrode using nickel hydroxide as an active material is widely used in alkaline storage batteries such as nickel-hydride batteries, nickel-cadmium batteries, nickel-zinc batteries and nickel-iron batteries. . In recent years, nickel-hydride batteries have received particular attention from the viewpoints of low pollution, high energy density, and the like, and research and development have been extensively carried out from portable devices to electric vehicles.
【０００３】これらアルカリ電池はいずれの場合でも、
ポータブル機器や電気自動車等の限られた狭い空間の中
に納められるため、温度上昇し易く、放熱しにくい状況
下に置かれている。このため、正極活物質の高温時の利
用率維持が要求される。この要求を満足するための方法
の一つである正極活物質へのカドミウム添加は、環境的
に問題があり、ニッケル−カドミウム電池からニッケル
水素化物電池へと低公害化してきたことに逆行すること
になってしまう。これらの問題を解決するためにカルシ
ウム化合物などの各種添加剤が報告されているが、電池
性能の改善には不十分であった。In any case, these alkaline batteries are
Since it is housed in a limited narrow space such as a portable device or an electric vehicle, it is placed in a situation where the temperature easily rises and heat is difficult to radiate. Therefore, it is required to maintain the utilization rate of the positive electrode active material at high temperatures. Addition of cadmium to the positive electrode active material, which is one of the methods for satisfying this requirement, is environmentally problematic, and it goes against the fact that the pollution has been reduced from nickel-cadmium batteries to nickel hydride batteries. Become. Various additives such as calcium compounds have been reported to solve these problems, but they were insufficient for improving the battery performance.
【０００４】これに対し従来より、水酸化カリウムを主
成分とする電解液中に水酸化リチウムあるいは水酸化ナ
トリウムを少量添加せしめることにより、高温特性を改
善するという方法が、広く一般的に行われている。しか
しながらリチウムイオンは電池の充放電サイクルを繰り
返すと、正極活物質である水酸化ニッケルの結晶格子中
に取り込まれてしまうため、サイクルを重ねると電解液
中のリチウムイオン濃度が低下してくるという問題点
が、また水酸化ナトリウムは濃度を高くすると電解液が
粘ちょうになるため、その使用量が制限されるという問
題点がそれぞれあった。On the other hand, conventionally, a method of improving high temperature characteristics by adding a small amount of lithium hydroxide or sodium hydroxide to an electrolytic solution containing potassium hydroxide as a main component has been widely and generally performed. ing. However, when the lithium ion is repeatedly charged and discharged in the battery, it is taken into the crystal lattice of nickel hydroxide, which is the positive electrode active material. Therefore, the lithium ion concentration in the electrolytic solution decreases as the cycle is repeated. However, when the concentration of sodium hydroxide is increased, the electrolytic solution becomes viscous, and there is a problem in that the amount used is limited.
【０００５】[0005]
【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時の利
用率を高めたアルカリ蓄電池を提供しようとするもので
ある。The present invention has been made in view of the above problems, and an object of the present invention is to provide an alkaline storage battery in which the utilization rate of the nickel positive electrode at high temperature is increased.
【０００６】[0006]
【課題を解決するための手段】本発明の第１は、アルカ
リ電解液中にイッテルビウムまたはイッテルビウム化合
物を溶解せしめたアルカリ蓄電池である。本発明の第２
は、前記電解液が水酸化カリウムを主成分とすると共
に、水酸化ナトリウムまたは水酸化リチウムを含有して
おり、且つ電解液中にイッテルビウムまたはイッテルビ
ウム化合物を溶解せしめたアルカリ蓄電池である。The first aspect of the present invention is an alkaline storage battery in which ytterbium or a ytterbium compound is dissolved in an alkaline electrolyte. Second of the present invention
Is an alkaline storage battery in which the electrolytic solution contains potassium hydroxide as a main component and also contains sodium hydroxide or lithium hydroxide, and ytterbium or a ytterbium compound is dissolved in the electrolytic solution.
【０００７】アルカリ水溶液中のイッテルビウムまたは
イッテルビウム化合物のイオンは溶液の酸素ガス発生過
電圧を引き上げる効果を持ち、充電末期における正極側
からの酸素ガス発生を抑制するため、正極活物質たる水
酸化ニッケルの充電受け入れを改善し、充放電効率およ
び高温時における利用率を高めることができる。The ions of ytterbium or the ytterbium compound in the alkaline aqueous solution have the effect of raising the oxygen gas generation overvoltage of the solution, and in order to suppress the oxygen gas generation from the positive electrode side at the end of charging, charge nickel hydroxide as the positive electrode active material. The acceptance can be improved, and the charge / discharge efficiency and the utilization rate at high temperature can be increased.
【０００８】[0008]
【実施例】以下、実施例に基づき本発明を説明する。正
極活物質として高密度の水酸化ニッケル粉末をを準備
し、一酸化コバルト（ＣｏＯ）１０重量％と充分混合
し、これに増粘剤を加えペースト状にし、３次元多孔体
ニッケル基板に充填、乾燥後プレスして正極板を得た。
この様にして作製した正極と、公知の水素吸蔵合金を用
い正極容量より過剰の容量となるように設計した負極
と、耐アルカリ性を有するセパレータとで正極容量規制
となるように試験電池を作製した。この後、各種の組成
の電解液を各電池に注入し、本発明電池１及び２とし
た。また、比較例としてイッテルビウムまたはイッテル
ビウム化合物のイオンを含まない電解液を注入したこと
以外は本発明電池１及び２と同じである比較電池３及び
４をそれぞれ作製した。表１に各電池の電解液組成を示
した。EXAMPLES The present invention will be described below based on examples. A high density nickel hydroxide powder was prepared as a positive electrode active material, thoroughly mixed with 10% by weight of cobalt monoxide (CoO), and a thickener was added thereto to form a paste, which was filled in a three-dimensional porous nickel substrate, After drying, it was pressed to obtain a positive electrode plate.
A test battery was manufactured so that the positive electrode capacity was regulated by the positive electrode manufactured in this manner, a negative electrode designed to have an excess capacity than the positive electrode capacity using a known hydrogen storage alloy, and a separator having alkali resistance. . After that, electrolytic solutions of various compositions were injected into each battery to obtain batteries 1 and 2 of the invention. Further, as Comparative Examples, Comparative Batteries 3 and 4 which were the same as the Batteries 1 and 2 of the present invention, respectively, were prepared except that an electrolyte solution containing no ytterbium or ytterbium compound ions was injected. Table 1 shows the electrolyte composition of each battery.
【０００９】[0009]
【表１】 [Table 1]
【００１０】これらの電池を参照極として酸化水銀電極
を用いて開放、液過剰条件で充放電試験を行った。図１
に各温度における利用率を示す。本発明電極１及び２
は、イッテルビウムイオンが電解液中に含まれない比較
電極３に比べて利用率が高く、５０℃および４０℃の高
温においてはその差が顕著に現れた。また、電解液中に
水酸化リチウム及び水酸化ナトリウムを含有せしめた比
較電極４に比べ、本発明電極２は優れた高い利用率を示
した。A charging / discharging test was conducted under the conditions of liquid excess, using these batteries as reference electrodes and using a mercury oxide electrode. FIG.
Shows the utilization rate at each temperature. Inventive Electrodes 1 and 2
Has a higher utilization factor than the comparative electrode 3 in which the ytterbium ion is not contained in the electrolytic solution, and the difference appears remarkably at high temperatures of 50 ° C. and 40 ° C. Further, the electrode 2 of the present invention showed an excellent high utilization rate as compared with the comparative electrode 4 in which the electrolyte solution contained lithium hydroxide and sodium hydroxide.
【００１１】図２に本発明電池１と比較電池３の２０℃
および４０℃の充電曲線を示す。２０℃においては酸素
ガス発生過電圧は同程度であるが、４０℃においては比
較電池３は充電末期においても酸素過電圧の立ち上がり
はなく、充電受け入れが低下していることが窺われる。
一方、本発明電池１においては酸素過電圧の立ち上がり
が見られ、４０℃においても高い利用率を示した。高温
時の利用率維持についてはイッテルビウムイオンおよび
水酸化リチウムを複合添加した比較電池２についても同
様であった。これは、電解液中のイッテルビウムおよび
イッテルビウム化合物のイオンの酸素ガス発生過電圧上
昇効果によるものである。FIG. 2 shows the battery 1 of the present invention and the comparative battery 3 at 20 ° C.
And 40 ° C. charge curve. At 20 ° C., the oxygen gas generation overvoltage is about the same, but at 40 ° C., the oxygen overvoltage does not rise in the comparative battery 3 even at the end of charging, which suggests that the charge acceptance is lowered.
On the other hand, in Battery 1 of the present invention, a rise in oxygen overvoltage was observed, and a high utilization factor was exhibited even at 40 ° C. The maintenance of the utilization factor at high temperature was the same for the comparative battery 2 to which ytterbium ions and lithium hydroxide were added in combination. This is due to the oxygen gas generation overvoltage increasing effect of the ions of ytterbium and the ytterbium compound in the electrolytic solution.
【００１２】[0012]
【発明の効果】上記のように、本発明のアルカリ蓄電池
では、電解液中へのイッテルビウム又はその化合物の添
加により、ニッケル正極の利用率を高め、高温下での利
用率の低下を抑制するという極めて優れた効果が得られ
る。As described above, in the alkaline storage battery of the present invention, by adding ytterbium or its compound to the electrolytic solution, it is possible to increase the utilization rate of the nickel positive electrode and suppress the reduction of the utilization rate at high temperature. An extremely excellent effect can be obtained.
【図１】試験温度と利用率の関係を示した図である。FIG. 1 is a diagram showing a relationship between a test temperature and a utilization rate.
【図２】２０℃および４０℃における充電曲線を示した
図である。FIG. 2 is a diagram showing charge curves at 20 ° C. and 40 ° C.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松村 勇一 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichi Matsumura 6-6 Josaimachi, Takatsuki City, Osaka Prefecture Yuasa Corporation
Claims (2)
る正極と、アルカリ電解液から構成されるアルカリ蓄電
池において、電解液中にイッテルビウムまたはイッテル
ビウム化合物を溶解せしめたことを特徴とするアルカリ
蓄電池。1. An alkaline storage battery comprising a negative electrode, a positive electrode containing nickel hydroxide as a main component, and an alkaline electrolyte, wherein ytterbium or a ytterbium compound is dissolved in the electrolyte. .
すると共に、水酸化ナトリウムまたは水酸化リチウムを
含有しており、且つ該電解液中にイッテルビウムまたは
イッテルビウム化合物を溶解せしめた請求項１記載のア
ルカリ蓄電池。2. The electrolytic solution containing potassium hydroxide as a main component and also containing sodium hydroxide or lithium hydroxide, and ytterbium or a ytterbium compound is dissolved in the electrolytic solution. Alkaline storage battery.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8023752A JPH09219214A (en) | 1996-02-09 | 1996-02-09 | Alkaline storage battery |
| EP96931980A EP0794584A4 (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode, and alkaline storage battery |
| CNA2004100317516A CN1536691A (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 |
| CNB961915048A CN1205679C (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 |
| CNB2004100317501A CN1244964C (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage 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 |
| CNB2004100317520A CN1253954C (en) | 1995-09-28 | 1996-09-25 | Hydrogen storage electrode, nickel electrode and alkaline storage battery |
| TW085112495A TW335564B (en) | 1996-02-09 | 1996-10-11 | An occlusion hydrogen electrode, nickel electrode and alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8023752A JPH09219214A (en) | 1996-02-09 | 1996-02-09 | Alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09219214A true JPH09219214A (en) | 1997-08-19 |
Family
ID=12119057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8023752A Pending JPH09219214A (en) | 1995-09-28 | 1996-02-09 | Alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09219214A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001332257A (en) * | 1999-10-08 | 2001-11-30 | Hitachi Maxell Ltd | Non-baking type positive electrode for alkaline battery, its manufacturing method and the alkaline battery using the non-baking type positive electrode |
| WO2015015825A1 (en) * | 2013-07-31 | 2015-02-05 | プライムアースＥｖエナジー 株式会社 | Nickel-metal hydride storage battery |
-
1996
- 1996-02-09 JP JP8023752A patent/JPH09219214A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001332257A (en) * | 1999-10-08 | 2001-11-30 | Hitachi Maxell Ltd | Non-baking type positive electrode for alkaline battery, its manufacturing method and the alkaline battery using the non-baking type positive electrode |
| WO2015015825A1 (en) * | 2013-07-31 | 2015-02-05 | プライムアースＥｖエナジー 株式会社 | Nickel-metal hydride storage battery |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051027 |
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