JPS6151760A - Alkaline storage battery - Google Patents
Alkaline storage batteryInfo
- Publication number
- JPS6151760A JPS6151760A JP59171970A JP17197084A JPS6151760A JP S6151760 A JPS6151760 A JP S6151760A JP 59171970 A JP59171970 A JP 59171970A JP 17197084 A JP17197084 A JP 17197084A JP S6151760 A JPS6151760 A JP S6151760A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- equilibrium dissociation
- alloys
- pressure
- hydrogen absorption
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- 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
【発明の詳細な説明】
産業上の利用分野
本発明は、水素を可逆的に吸蔵・放出する水素吸蔵電極
を負極とし、この負極に吸蔵している水素を正極の酸素
と電気化学的に反応させて電気エネルギーを発生するア
ルカリ蓄電池に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention uses a hydrogen storage electrode that reversibly stores and releases hydrogen as a negative electrode, and electrochemically reacts the hydrogen stored in the negative electrode with oxygen at the positive electrode. The present invention relates to an alkaline storage battery that generates electrical energy.
従来例の構成とその問題点
従来の鉛−酸化鉛蓄電池、ニッケルーカドミウム蓄電池
等の電池は、酸化物電極を持つだめに、重量または容積
の単位当たりのエネルギー貯蔵容量が比較的低い。そこ
でエネルギー貯蔵容量の向上を図るために、負極として
可逆的に水素を吸蔵・放出する水素吸蔵合金を用い、吸
蔵した水素を活物質とする電極が提案されている。たと
えば特開昭５１−１３９３４号公報には、水素吸蔵合金
としてＬａＣｏ５ 、 ＬａＮｉ５合金などが提案され
ている。Conventional Structures and Problems Conventional batteries such as lead-lead oxide batteries and nickel-cadmium batteries have relatively low energy storage capacity per unit of weight or volume because they have oxide electrodes. Therefore, in order to improve the energy storage capacity, an electrode has been proposed in which a hydrogen storage alloy that reversibly stores and releases hydrogen is used as a negative electrode, and the stored hydrogen is used as an active material. For example, LaCo5 and LaNi5 alloys are proposed as hydrogen storage alloys in JP-A-51-13934.
これらの水素吸蔵電極は、１種類の水素吸蔵合金からな
っているため、比較的大きな放電容量を有している。し
かし、ニッケル正極と組合せて密閉型のアルカリ蓄電池
を構成した場合、ＬａＣｏ ５合金は水素平衡解離圧力
が低いため、水素が水素吸蔵電極内で比較的安定に存在
し、過充電状態で正極から発生する酸素ガスを水素吸蔵
電極の界面で水素吸蔵合金中の水素と反応して水を生成
する機構が円滑に進行しにくい問題点を有する。一方、
ＬａＮｉ ５合金は水素平衡解離圧力が高いため、合金
の界面で水素ガスと正極から発生する酸素ガスとの反応
性は良いが、とくに高温時において充電しにくい傾向が
あるため放電容量が小さくなる。Since these hydrogen storage electrodes are made of one type of hydrogen storage alloy, they have a relatively large discharge capacity. However, when a sealed alkaline storage battery is configured in combination with a nickel positive electrode, the LaCo 5 alloy has a low hydrogen equilibrium dissociation pressure, so hydrogen exists relatively stably within the hydrogen storage electrode, and hydrogen is generated from the positive electrode in an overcharged state. The problem is that the mechanism in which oxygen gas reacts with hydrogen in the hydrogen storage alloy at the interface of the hydrogen storage electrode to generate water does not proceed smoothly. on the other hand,
Since the LaNi 5 alloy has a high hydrogen equilibrium dissociation pressure, the reactivity between hydrogen gas and oxygen gas generated from the positive electrode at the alloy interface is good, but it tends to be difficult to charge, especially at high temperatures, resulting in a small discharge capacity.
発明の目的
本発明の目的は、上記に鑑み、負極の放電容量が大きく
、しかも過充電時に正極から発生する酸素ガスの吸収能
力向上を図り、高容量かつ電池内圧が低く、安全性の高
いアルカリ蓄電池を提供することである。Purpose of the Invention In view of the above, an object of the present invention is to provide an alkaline battery with a high capacity, low internal pressure, and high safety, which has a large negative electrode discharge capacity and also improves the ability to absorb oxygen gas generated from the positive electrode during overcharging. The aim is to provide storage batteries.
発明の構成
本発明は、水素平衡解離圧力の異なる２種類以上の水素
吸蔵合金粉末又はその水素化物粉末からなる水素吸蔵電
極を用いるものである。ここで、上記水素吸蔵合金粉末
の中で水素平衡解離圧力が少なくとも１気圧かまたはそ
れ以下の水素吸蔵合金粉末を１種類以上含有するのが望
ましい。また、上記水素平衡解離圧力の異なる複数の水
素吸蔵合金の混合物粉末において、常温で水素平衡解離
圧力が１〜５気圧の範囲内にある水素吸蔵合金が５重量
係から２０重量％含有していることが望ましい。Structure of the Invention The present invention uses a hydrogen storage electrode made of two or more types of hydrogen storage alloy powders or hydride powders thereof having different hydrogen equilibrium dissociation pressures. Here, it is desirable that the hydrogen storage alloy powder contains at least one type of hydrogen storage alloy powder having a hydrogen equilibrium dissociation pressure of at least 1 atmosphere or less. Further, in the powder mixture of a plurality of hydrogen storage alloys having different hydrogen equilibrium dissociation pressures, the hydrogen storage alloy having a hydrogen equilibrium dissociation pressure within the range of 1 to 5 atm at room temperature is contained in an amount of 5 to 20% by weight. This is desirable.
実施例の説明
実施例１
Ｍ［９９，６％以上ノランタン、ニッケル、コバルト金
属を用いて、元素比でＬｕ：Ｎ工が１：６になる配合組
成混合物、及び元素比でＬａ ：Ｎｉ ：Ｃ。Description of Examples Example 1 M[99.6% or more of noranthane, nickel, and cobalt metals, a composition mixture with an elemental ratio of Lu:N of 1:6, and an elemental ratio of La:Ni:C .
が１：３：２になる配合組成混合物を各々アーク溶解炉
ニテ溶解し、ＬａＮｉ５． ＬａＮｉ、Ｇｏ、、合金を
製造した。この各々の合金試料をアルゴン雰囲気のドラ
イボックス中で粉砕し、篩分けして３００メソシュ通過
の粉末を用意した。ついで、 ＬａＮｉ ５合金粉末Ａ
とＬａＮｉ ３Ｃｏ ２合金粉末Ｂを各種の配合比で混
合し、この混合粉末に結着剤としてボピニルアルコール
の水溶液を用いてペースト状とし、これをニッケルの発
泡多孔体に加圧充填し、約２００ Ｋｇ／ａＡ の圧力
で加圧圧縮後乾燥した。こうして得た電極を負極とし、
公知の焼結式酸化ニッケル正極を用いて、公称２．０人
り程度に和尚する単２型密閉アルカリ蓄電池を２種類ず
つ構成した。LaNi5. LaNi, Go, and alloys were manufactured. Each of the alloy samples was ground in a dry box under an argon atmosphere and sieved to prepare a powder that passed 300 mesh. Next, LaNi 5 alloy powder A
and LaNi 3Co 2 alloy powder B are mixed in various blending ratios, this mixed powder is made into a paste using an aqueous solution of bopinyl alcohol as a binder, and this is pressurized and filled into a nickel foam porous body. It was compressed and dried at a pressure of about 200 Kg/aA. The electrode obtained in this way is used as a negative electrode,
Using a known sintered nickel oxide positive electrode, two types of AA sealed alkaline storage batteries each having a nominal capacity of about 2.0 people were constructed.
すなわち容量測定用は負極律則とし、電池内圧測定用は
正極律則とした。That is, the negative electrode rule was used for capacity measurement, and the positive electrode rule was used for measuring battery internal pressure.
上記容量測定用の電池を４０ ’Ｃの温度において０、
Ｉ Ｃ（１０時間率）で１３０％以上充電した後、０．
２ Ｇ （５時間率）で放電し、ｉ、ｏｖまでの放電容
量を測定した。また温度２０℃における充電電流レー）
０．１０から１Ｃまでの過充電特性を電圧上昇変化で調
べた。各種負極試料は第１表に示す通りである。The above battery for capacity measurement was heated at 40'C.
After charging more than 130% with IC (10 hour rate), 0.
It was discharged at 2 G (5 hour rate) and the discharge capacity up to i, ov was measured. Also, the charging current at a temperature of 20℃)
The overcharge characteristics from 0.10 to 1C were investigated by changing the voltage rise. Various negative electrode samples are shown in Table 1.
第２表に各種負極試料の放電容量試験結果と過充電時の
電池内圧を示す。電池内圧は１６０％充電した時、各充
電率毎に示したものである。Table 2 shows the discharge capacity test results of various negative electrode samples and the battery internal pressure during overcharging. The internal pressure of the battery is shown for each charging rate when the battery is charged to 160%.
第１表
なおＬａＮｉ５合金は温度２５℃で水素平衡解離圧力は
２気圧であり、平衡解離圧力の高い合金である。Table 1 Note that the LaNi5 alloy has a hydrogen equilibrium dissociation pressure of 2 atm at a temperature of 25° C., and is an alloy with a high equilibrium dissociation pressure.
一方、ＬａＮｉ ５００２合金は０．３気圧であり、平
衡解離圧力の低い合金である。On the other hand, LaNi 5002 alloy has a low equilibrium dissociation pressure of 0.3 atm.
第２表かられかる様に、従来型の合金単体を負極とした
電池層１は、水素平衡解離圧力の低い材料のみを用いて
いるため、容量は大きいが、電池内圧は０．１〜１．０
Ｇにおいて、３．７〜８．２ Ｋｇ／Ｃ＋Ｊと非常に
高い値を示す。一方、電池層２は水素平衡解離圧力の高
い材料のみを用いているため、同じ範囲で電池内圧は１
．５〜４．５Ｋｇ〜 と低い反面、電池容量が小さい。As can be seen from Table 2, the battery layer 1 using a conventional alloy as a negative electrode has a large capacity because only materials with low hydrogen equilibrium dissociation pressure are used, but the internal pressure of the battery is 0.1 to 1. .0
In G, it shows a very high value of 3.7 to 8.2 Kg/C+J. On the other hand, since battery layer 2 uses only materials with high hydrogen equilibrium dissociation pressure, the battery internal pressure is 1 in the same range.
．． Although it is low at 5 to 4.5 kg, the battery capacity is small.
実用的に電池容量と電池内圧の両方を比較的満足する電
池はＡ３〜５である。Batteries that relatively satisfy both battery capacity and battery internal pressure in practical terms are A3 to A5.
水素平衡解離圧力の異なる合金を混合することによって
、単体よりは実用範囲の拡大ができると共に、とぐに水
素平衡解離圧力の高い合金の割合は５〜２０重量％が実
用上優れている。By mixing alloys with different hydrogen equilibrium dissociation pressures, the practical range can be expanded compared to single alloys, and a ratio of 5 to 20% by weight of alloys with high hydrogen equilibrium dissociation pressures is practically excellent.
実施例２
純１ｉ９９．５％以上の、ミソシュメタル（Ｍｍ；希土
類元素の混合物）、ランタン、カルシウム、ニッケル金
属を用いて、元素比でＭｍ：Ｃａ：Ｎｉが０．５：Ｏ，
５： Ｓになる配合組成混合物、及び元素比でＬｚ：Ｃ
ａ：Ｎｉが０．５ ： ｏ、ｔｓ ； ｓ になる配合
組成混合物を各々高周波溶解炉にて溶解し、Ｍｍ ｏ、
５Ｃａ、５Ｎｉ５ 、 Ｌａｏ５Ｃａｏ５Ｎｉ５合
金を製造した。Example 2 Using miso metal (Mm; a mixture of rare earth elements), lanthanum, calcium, and nickel metals with a purity of 99.5% or more, the elemental ratio of Mm:Ca:Ni was 0.5:O,
5: A composition mixture that becomes S and an element ratio of Lz:C
a: The composition mixtures in which Ni is 0.5: o, ts; s are each melted in a high frequency melting furnace, and Mmo,
5Ca, 5Ni5, Lao5Cao5Ni5 alloys were produced.
Ｍｍｏ５Ｃａｏ５Ｎｉ、合金は水素平衡解離圧力の高い
材料であり、Ｌａ０５Ｃａｏ５Ｎ工５合金は低い材料で
ある。The Mmo5Cao5Ni alloy is a material with a high hydrogen equilibrium dissociation pressure, and the La05Cao5N engineering 5 alloy is a material with a low hydrogen equilibrium dissociation pressure.
これらの合金を第３表に示すような割合で混合した負極
を用いて、実施例１と同様にして電池を構成し、同じ条
件で放電容量と電池内圧を測定した。A battery was constructed in the same manner as in Example 1 using a negative electrode in which these alloys were mixed in the proportions shown in Table 3, and the discharge capacity and battery internal pressure were measured under the same conditions.
その結果を第４表に示す。The results are shown in Table 4.
第３表
第４表
第４表からもわかる様に、実施例１の結果と同じ傾向に
ｓｂ、水素平衡解離圧力の相対的々差異を利用すること
によって、電池容量と充電時の電池内圧の改善を図るこ
とができる。As can be seen from Table 3 and Table 4, by utilizing the relative differences in sb and hydrogen equilibrium dissociation pressure, the battery capacity and battery internal pressure during charging can be adjusted in the same manner as the results of Example 1. Improvements can be made.
実施例で示したように、水素平衡解離圧力が１気圧又は
それ以下の水素吸蔵合金を１種類以上含有すると電池性
能がよくなることがわかる。また、常温で水素平衡解離
圧力が１〜５気圧の範囲内にある水素吸蔵合金が５〜２
０重量％含有していると、とくに実用上の電池性能が優
れている。水素平衡解離圧力が常温で１０気圧以上ある
合金材料は、高温時の充電が殆んどできなくて、ガス吸
収能も十分発揮しなくなる。１から５気圧の範囲内にあ
る合金がとくに実用上望ましい。実施例では２種類の混
合物を用いたが、さらに他の合金系を用いてもよい。ま
た、水素平衡解離圧力の異なる３種以上を用いても同じ
効果が期待できる。As shown in the examples, it can be seen that the battery performance is improved when one or more types of hydrogen storage alloys having a hydrogen equilibrium dissociation pressure of 1 atm or less are contained. In addition, a hydrogen storage alloy whose hydrogen equilibrium dissociation pressure is within the range of 1 to 5 atm at room temperature is 5 to 2 atm.
When it is contained in an amount of 0% by weight, the practical battery performance is particularly excellent. An alloy material with a hydrogen equilibrium dissociation pressure of 10 atm or more at room temperature will hardly be able to be charged at high temperatures and will not exhibit sufficient gas absorption ability. Alloys in the range of 1 to 5 atmospheres are particularly desirable for practical purposes. Although a mixture of two types was used in the example, other alloy systems may also be used. Moreover, the same effect can be expected even if three or more types having different hydrogen equilibrium dissociation pressures are used.
実施例では、水素吸蔵合金を出発材料として負極を構成
したが、この負極の充電時には合金は大半が水素化物に
変化するので、前もって水素化物の型で負極を製造し、
電池を構成することもできる。In the example, the negative electrode was constructed using a hydrogen storage alloy as a starting material, but when this negative electrode is charged, most of the alloy changes to a hydride, so the negative electrode was manufactured in advance in the form of a hydride.
It can also constitute a battery.
発明の効果
以上のように、本発明のアルカリ蓄電池は、放電容量も
比較的大きく、密閉型電池においては１、充放電時のガ
ス発生も少なく、電池内圧の上昇を抑制することができ
る。Effects of the Invention As described above, the alkaline storage battery of the present invention has a relatively large discharge capacity, and for a sealed battery, 1, gas generation during charging and discharging is small, and an increase in battery internal pressure can be suppressed.
Claims (3)
たはその水素化物からなる水素吸蔵電極を用いたアルカ
リ蓄電池。(1) An alkaline storage battery using a hydrogen storage electrode made of a plurality of hydrogen storage alloys or hydrides thereof having different hydrogen equilibrium dissociation pressures.
衡解離圧力を有する水素吸蔵合金を少なくとも１種含有
する特許請求の範囲第１項記載のアルカリ蓄電池。(2) The alkaline storage battery according to claim 1, wherein the hydrogen storage electrode contains at least one hydrogen storage alloy having a hydrogen equilibrium dissociation pressure of 1 atmosphere or less.
て、常温で水素平衡解離圧力が１〜５気圧の範囲内にあ
る水素吸蔵合金またはその水素化物の比率が５重量％か
ら２０重量％である特許請求の範囲第１項記載のアルカ
リ蓄電池。(3) A patent for a hydrogen storage alloy or a mixture of its hydrides whose hydrogen equilibrium dissociation pressure is within the range of 1 to 5 atm at room temperature, or whose hydride has a proportion of 5% to 20% by weight. The alkaline storage battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59171970A JPS6151760A (en) | 1984-08-18 | 1984-08-18 | Alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59171970A JPS6151760A (en) | 1984-08-18 | 1984-08-18 | Alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6151760A true JPS6151760A (en) | 1986-03-14 |
| JPH0564420B2 JPH0564420B2 (en) | 1993-09-14 |
Family
ID=15933126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59171970A Granted JPS6151760A (en) | 1984-08-18 | 1984-08-18 | Alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6151760A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554456A (en) * | 1994-06-14 | 1996-09-10 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries containing heterogeneous powder particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5338631U (en) * | 1976-09-07 | 1978-04-04 |
-
1984
- 1984-08-18 JP JP59171970A patent/JPS6151760A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5338631U (en) * | 1976-09-07 | 1978-04-04 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554456A (en) * | 1994-06-14 | 1996-09-10 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries containing heterogeneous powder particles |
| WO1996036083A1 (en) * | 1995-05-08 | 1996-11-14 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries containing heterogeneous powder particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0564420B2 (en) | 1993-09-14 |
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