JPH0582025B2 - - Google Patents
Info
- Publication number
- JPH0582025B2 JPH0582025B2 JP59138753A JP13875384A JPH0582025B2 JP H0582025 B2 JPH0582025 B2 JP H0582025B2 JP 59138753 A JP59138753 A JP 59138753A JP 13875384 A JP13875384 A JP 13875384A JP H0582025 B2 JPH0582025 B2 JP H0582025B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- hydrogen
- powder
- batteries
- laxni
- 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.)
- Expired - Lifetime
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
- C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
(イ) 産業上の利用分野
本発明は蓄電池の負極として用いられる水素吸
蔵電極に関し、特に高容量を長期にわたつて維持
するように改良された水素吸蔵電極に関する。
(ロ) 従来の技術
従来からよく用いられる蓄電池としては、鉛電
池及びニツケル−カドミウム電池があるが、近年
これら電池より軽量で高容量となる可能性がある
ということで、特に低圧で水素を可逆的に吸蔵・
放出することのできる水素吸蔵合金を水素極とし
て用いたニツケル−水素電池などが注目されてい
る。
この水素を吸蔵及び放出することのできる水素
吸蔵合金を備えた負極は、特公昭49−25135号
公報に見られるように水素吸蔵合金粉末に固着剤
を加えてなるペーストを支持体に塗着、乾燥した
後焼結して得たもの、特開昭53−103541号公報
に見られるように水素吸蔵合金粉末及びアセチレ
ンブラツクを結着剤により支持体に固着して得た
ものなど従来より種々の提案がなされているが、
これら電極に水素吸蔵合金としてよく用いられる
Ca（１−ｘ）LaxNi5等の合金は、水素の吸蔵及
び放出によつて合金格子が変形し合金粒子の微粉
化が起こるため、これらの合金を水素吸蔵材とし
て用いた場合には合金粒子の微粉化による脱落が
生じ電池容量が劣化し、また特に前記の方法に
よつて作製された焼結多孔体を水素吸臓電極とし
た時には、この合金粒子の微粉化とそれに伴う脱
落による電極の機械的強度及び導電性の低下が著
しく、長期にわたつて電池性能を維持することが
困難であるという問題点があつた。
(ハ) 発明が解決しようとする問題点
本発明は解決しようとする問題点は水素吸蔵材
の微粉末による脱落で生じる電池容量の劣化と電
極の機械的強度及び電導性低下に伴う電池性能の
劣化である。
(ニ) 問題点を解決するための手段
本発明の水素吸蔵電極はかかる問題点を解決す
るために水素吸蔵材にCa（１−ｘ）La−Ni（５−
ｙ）Ayからなる分子式で表わされ前記ＡがAl、
Mn、CuまたはCrである合金を用いたものであ
る。
(ホ) 作用
Ca（１−ｘ）LaxNi（５−ｙ）Ayからなる分式
式で表わされ前記ＡがAl、Mn、CuまたはCrで
ある水素吸蔵材は充放電による水素の吸蔵及び放
出の際に結晶格子の変形が小さく微細化が起こり
難い。
(ヘ) 実施例
市販のカルシウム、ランタン、ニツケル、アル
ミニウムを原子比でCa：La：Ni：Al＝（１−
ｘ）：ｘ：（５−ｙ）：ｙ：（ｘは0.1〜0.5、ｙは0.1
〜0.3）になるよう混合し、アーク溶解炉に入れ
て加熱、溶解して合金化した後粉砕してCa（１−
ｘ）LaxNi（５−ｙ）Aly粉末を得た。また同様
の操作でアルミニウムにかえてマンガン、導及び
クロムを夫々用いCa（１−ｘ）LaxNi（５−ｙ）
Mny粉末Ca（１−ｘ）LaxNi（５−ｙ）Cuy粉末
及びCa（１−ｘ）LaxNi（５−ｙ）Cry粉末（何れ
もｘは0.1〜0.5、ｙは0.1〜0.3）を得た。
こうして得られたCa（１−ｘ）LaxNi（５−ｙ）
Aly粉末、Ca（１−ｘ）LaxNi（５−ｙ）Mny粉
末、Ca（１−ｘ）LaxNi（５−ｙ）Cuy粉末ある
いはCa（１−ｘ）LaxNi（５−ｙ）Cry粉末80重量
％と、導電材としてのアセチレンブラツク10重量
％及び結着剤としてのフツ素樹脂粉末10重量％を
混合し温度280〜300℃、加圧力3t／cm2で成型し
て、直径２cm、厚さ1.2mmの円型の水素吸蔵電極
を種々作製した。この水素吸蔵電極に用いられた
合金粉末は約1.5ｇであり、約300〜350ｍAHに相
当する容量を有している。
次いでこうして作製された水素吸蔵電極を理論
容量が500ｍAHである公知のニツケル正極と組
み合わせて本発明に於けるアルカリ蓄電池を作製
した。
この電池を負極に水素吸蔵材として用いた合金
粉末により下表に示す様に電池Ａ乃至Ｌとする。
(a) Industrial Application Field The present invention relates to a hydrogen storage electrode used as a negative electrode of a storage battery, and particularly to a hydrogen storage electrode that has been improved to maintain high capacity over a long period of time. (b) Conventional technology Lead-acid batteries and nickel-cadmium batteries have traditionally been commonly used storage batteries, but in recent years, it has been discovered that they can be made lighter and have higher capacity than these batteries. occlusion/
Nickel-hydrogen batteries that use hydrogen-absorbing alloys as hydrogen electrodes are attracting attention. A negative electrode equipped with a hydrogen storage alloy that can store and release hydrogen is produced by applying a paste made by adding a binder to hydrogen storage alloy powder to a support, as shown in Japanese Patent Publication No. 49-25135. There have been a variety of conventional methods, including those obtained by drying and sintering, and those obtained by fixing hydrogen storage alloy powder and acetylene black to a support with a binder, as seen in JP-A-53-103541. Although proposals have been made,
Often used as a hydrogen storage alloy in these electrodes
In alloys such as Ca(1-x)LaxNi 5 , the alloy lattice is deformed due to absorption and release of hydrogen, and the alloy particles become pulverized. Therefore, when these alloys are used as hydrogen storage materials, the alloy particles In particular, when the sintered porous material produced by the above method is used as a hydrogen absorbing electrode, the electrode may drop due to the pulverization of the alloy particles and the accompanying shedding. There was a problem in that the mechanical strength and conductivity decreased significantly, making it difficult to maintain battery performance over a long period of time. (C) Problems to be Solved by the Invention The problems to be solved by the present invention are the deterioration of battery capacity caused by shedding of the hydrogen storage material due to fine powder, and the deterioration of battery performance due to the decrease in mechanical strength and conductivity of the electrodes. It is deterioration. (d) Means for solving the problems In order to solve the problems, the hydrogen storage electrode of the present invention uses Ca(1-x)La-Ni(5-x) as the hydrogen storage material.
y) Represented by a molecular formula consisting of Ay, where A is Al,
It uses an alloy of Mn, Cu or Cr. (E) Action A hydrogen storage material represented by the partial formula Ca(1-x)LaxNi(5-y)Ay, where A is Al, Mn, Cu, or Cr, absorbs and releases hydrogen by charging and discharging. During this process, the deformation of the crystal lattice is small and refinement is difficult to occur. (F) Example Commercially available calcium, lanthanum, nickel, and aluminum in atomic ratio Ca:La:Ni:Al=(1-
x):x:(5-y):y:(x is 0.1 to 0.5, y is 0.1
Ca(1-
x) LaxNi(5-y)Aly powder was obtained. Similarly, Ca(1-x)LaxNi(5-y) was prepared using manganese, conductive material, and chromium instead of aluminum.
Mny powder Ca(1-x)LaxNi(5-y)Cuy powder and Ca(1-x)LaxNi(5-y)Cry powder (x is 0.1 to 0.5 and y is 0.1 to 0.3 in both cases) were obtained. Ca(1-x)LaxNi(5-y) thus obtained
Aly powder, Ca(1-x)LaxNi(5-y)Mny powder, Ca(1-x)LaxNi(5-y)Cuy powder or Ca(1-x)LaxNi(5-y)Cry powder 80% by weight 10% by weight of acetylene black as a conductive material and 10% by weight of fluororesin powder as a binder were mixed and molded at a temperature of 280 to 300°C and a pressure of 3t/cm 2 to a diameter of 2cm and a thickness of 1.2cm. Various circular hydrogen storage electrodes of mm diameter were fabricated. The alloy powder used in this hydrogen storage electrode weighs about 1.5 g and has a capacity equivalent to about 300 to 350 mAH. Next, the hydrogen storage electrode thus produced was combined with a known nickel positive electrode having a theoretical capacity of 500 mAH to produce an alkaline storage battery according to the present invention. These batteries were made into batteries A to L as shown in the table below by using alloy powder as a hydrogen storage material for the negative electrode.
【表】【table】
【表】
また比較として負極の水素吸蔵材としてCa0.3
La0.7Ni5を用いその他は前記実施例と同一の比較
電池Ｑを作製した。
図面は本発明による水素吸蔵電極を負極に用い
た電池Ａ乃至Ｐと比較電池Ｑのサイクル特性図で
あり、0.1C電流で16時間充電し、0.2C電流で放電
して終止電圧を1.0Vとするサイクル条件で充放
電を行ない、電池の初期容量を100として示して
いる。
図面より明らかなように電池Ａ乃至Ｐは共に比
較電池Ｑに比しサイクル寿命が向上していること
がわかる。これはCa0.3La0.7N5を水素吸蔵材とし
て用いた負極を備えた比較電池Ｅが充放電に伴う
負極の水素の吸蔵及び放出によつて水素吸蔵合金
粒子の微粉化が起こり200サイクルから急激な容
量低下が生じているのに対し、電池Ａ乃至Ｄは負
極の水素吸蔵材の水素の吸蔵及び放出による微粉
化が起り難く、結着剤によつて形成されるマトリ
ツクスによる水素吸蔵材粉末の強固な保持が継続
されるため、機械的強度や導電性の低下が抑制さ
れ、より長期にわたり電池容量の劣化が抑えられ
たからと考えられる。
(ト) 発明の効果
本発明の水素吸蔵電極はCa（１−ｘ）LaxNi
（５−ｙ）Ayからなる分子式で表わされ前記Ａが
Al、Mn、CuまたはCrである水素吸蔵材を備え
たものであるから、水素の吸蔵及び放出による前
記水素吸蔵材の脱落及びこれに伴う機械的強度や
導電性の低下が抑制され、より長期にわたつて高
容量を維持する電池を提供せしめることができ
る。[Table] Also, for comparison, Ca 0.3 was used as a hydrogen storage material for the negative electrode.
A comparative battery Q was prepared using La 0.7 Ni 5 and otherwise the same as in the above example. The figure is a cycle characteristic diagram of batteries A to P using the hydrogen storage electrode according to the present invention as the negative electrode, and comparative battery Q, in which they were charged at a current of 0.1C for 16 hours and discharged at a current of 0.2C to reach a final voltage of 1.0V. Charging and discharging were performed under the following cycle conditions, and the initial capacity of the battery is shown as 100. As is clear from the drawings, it can be seen that both batteries A to P have improved cycle lives compared to comparative battery Q. This is because Comparative Battery E, which has a negative electrode using Ca 0.3 La 0.7 N 5 as a hydrogen storage material, undergoes rapid pulverization of the hydrogen storage alloy particles from the 200th cycle due to hydrogen storage and release from the negative electrode during charging and discharging. In contrast, in batteries A to D, pulverization due to absorption and release of hydrogen in the hydrogen storage material of the negative electrode is difficult to occur, and the hydrogen storage material powder is reduced by the matrix formed by the binder. This is thought to be because the continued strong retention suppressed the decline in mechanical strength and conductivity, and suppressed deterioration of battery capacity over a longer period of time. (g) Effect of the invention The hydrogen storage electrode of the invention is made of Ca(1-x)LaxNi
(5-y) It is represented by a molecular formula consisting of Ay, and the above A is
Since it is equipped with a hydrogen storage material such as Al, Mn, Cu, or Cr, it is possible to suppress the falling off of the hydrogen storage material due to absorption and release of hydrogen and the accompanying decrease in mechanical strength and conductivity, and it can be used for a longer period of time. It is possible to provide a battery that maintains high capacity over a long period of time.
図面は本発明の水素吸蔵電極を用いた電池及び
従来の電池のサイクル特性図である。
Ａ乃至Ｐ……本発明の水素吸蔵電極を用いた電
池、Ｑ……従来の電池。
The drawings are cycle characteristic diagrams of a battery using the hydrogen storage electrode of the present invention and a conventional battery. A to P: Batteries using the hydrogen storage electrode of the present invention, Q: Conventional batteries.
Claims (1)
子式で表わされ前記ＡがAl、Mn、CuまたはCr
である水素吸蔵材を備えたことを特徴とする水素
吸蔵電極。1 Ca(1-x)LaxNi(5-y)Ay, and the above A is Al, Mn, Cu or Cr.
A hydrogen storage electrode characterized by comprising a hydrogen storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59138753A JPS6119061A (en) | 1984-07-04 | 1984-07-04 | Hydrogen occlusion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59138753A JPS6119061A (en) | 1984-07-04 | 1984-07-04 | Hydrogen occlusion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6119061A JPS6119061A (en) | 1986-01-27 |
| JPH0582025B2 true JPH0582025B2 (en) | 1993-11-17 |
Family
ID=15229374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59138753A Granted JPS6119061A (en) | 1984-07-04 | 1984-07-04 | Hydrogen occlusion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119061A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7411045A (en) * | 1974-08-19 | 1976-02-23 | Philips Nv | RECHARGEABLE ELECTROCHEMICAL CELL. |
| JPS55154301A (en) * | 1979-05-18 | 1980-12-01 | Sanyo Electric Co Ltd | Hydrogen storing material |
| JPS5623244A (en) * | 1979-08-03 | 1981-03-05 | Sanyo Electric Co Ltd | Hydrogen storing material |
-
1984
- 1984-07-04 JP JP59138753A patent/JPS6119061A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6119061A (en) | 1986-01-27 |
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