JPH0652655B2 - Hydrogen storage electrode - Google Patents
Hydrogen storage electrodeInfo
- Publication number
- JPH0652655B2 JPH0652655B2 JP60131283A JP13128385A JPH0652655B2 JP H0652655 B2 JPH0652655 B2 JP H0652655B2 JP 60131283 A JP60131283 A JP 60131283A JP 13128385 A JP13128385 A JP 13128385A JP H0652655 B2 JPH0652655 B2 JP H0652655B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- alloy
- electrode
- titanium
- cobalt
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 (イ)産業上の利用分野 本発明はアルカリ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。TECHNICAL FIELD The present invention relates to a hydrogen storage electrode used as a negative electrode of an alkaline storage battery, and particularly to a hydrogen storage electrode improved so as to maintain a high capacity for a long period of time.
(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ッ
ケル−カドミウム電池があるが、近年これら電池より軽
量で且つ高容量となる可能性があるということで、特に
低圧に於いて負極活物質である水素を可逆的に吸蔵及び
放出することのできる水素吸蔵合金を備えた電極を負極
に用い、水酸化ニッケルなどの金属酸化物からなる正極
活物質を備えた電極を正極に用いた金属−水素アルカリ
蓄電池が注目されている。(B) Conventional technology Conventionally frequently used storage batteries include lead batteries and nickel-cadmium batteries, but in recent years they are lighter in weight and have a higher capacity, and thus negative electrodes, especially at low voltage. An electrode having a hydrogen storage alloy capable of reversibly occluding and releasing hydrogen as an active material was used as a negative electrode, and an electrode having a positive electrode active material made of a metal oxide such as nickel hydroxide was used as a positive electrode. Metal-hydrogen alkaline storage batteries are receiving attention.
この金属−水素アルカリ蓄電池の負極となる水素吸蔵電
極に用いる水素吸蔵合金は従来から種々提案されてお
り、特公昭５９−３１８２９号公報ではこの水素吸蔵合
金としてチタンとコバルトからなる合金が使用できるこ
とが開示されている。しかしながら、チタン−コバルト
の二元合金を備えた水素吸蔵電極は、電極容量を規定す
る水素吸蔵量が充分ではなく、充放電によるサイクル寿
命も短いため充分に満足できるとは言えなかつた。Various hydrogen storage alloys for use in the hydrogen storage electrode serving as the negative electrode of this metal-hydrogen alkaline storage battery have been proposed in the past, and in JP-B-59-31829, an alloy composed of titanium and cobalt can be used as the hydrogen storage alloy. It is disclosed. However, the hydrogen storage electrode provided with a binary alloy of titanium-cobalt cannot be said to be sufficiently satisfactory because the hydrogen storage capacity that defines the electrode capacity is not sufficient and the cycle life due to charge and discharge is short.
(ハ)発明が解決しようとする問題点 本発明は水素吸蔵合金としてチタン−コバルト系合金を
備えた水素吸蔵電極に於いて不充分であつた水素吸蔵量
を増加させると共に、サイクル寿命の向上をはかろうと
するものである。(C) Problems to be solved by the present invention The present invention increases the hydrogen storage amount, which was insufficient in the hydrogen storage electrode provided with the titanium-cobalt alloy as the hydrogen storage alloy, and improves the cycle life. It is an attempt.
(ニ)問題点を解決するための手段 上記目的を達成するための本発明に係る水素吸蔵電極
は、チタン−コバルト合金のチタン及び／又はコバルト
の一部を元素Ｍ1及び／又はＭ2で置換してなるＴｉ
(1-x)Ｍ1 xＣｏ(1-y)Ｍ2 y〔式中、０≦ｘ≦０．２、０≦
ｙ≦０．２（但し、ｘ＝ｙ＝０の場合を除く。）であ
り、Ｍ1はＹ、Ｎｂ、Ｍｏ、Ｈｆ及びＴａから選ばれた
少なくとも一種の元素であり、またＭ2はＡｌ、Ｓｉ、
Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ及びアルカリ土類金
属から選ばれた少なくとも一種の元素である。〕が電極
材料として用いられてなる。(D) Means for Solving the Problems In the hydrogen storage electrode according to the present invention for achieving the above object, a part of titanium and / or cobalt of a titanium-cobalt alloy is replaced by the elements M 1 and / or M 2 . Substituted Ti
(1-x) M 1 x Co (1-y) M 2 y [wherein 0 ≦ x ≦ 0.2, 0 ≦
y ≦ 0.2 (excluding the case where x = y = 0), M 1 is at least one element selected from Y, Nb, Mo, Hf, and Ta, and M 2 is Al , Si,
It is at least one element selected from V, Cr, Mn, Fe, Cu, Zn and alkaline earth metals. ] Is used as an electrode material.
(ホ)作用 水素吸蔵合金として上記合金を備えた水素吸蔵電極を用
いると、チタン−コバルト二元合金を備えた水素吸蔵電
極に比べて、充放電時の水素の吸蔵及び放出量が増し容
量が増大すると共に、充放電の繰り返しによるサイクル
寿命が向上する。(E) Action When a hydrogen storage electrode provided with the above alloy as a hydrogen storage alloy is used, compared with a hydrogen storage electrode provided with a titanium-cobalt binary alloy, the amount of storage and release of hydrogen at the time of charging / discharging is increased and the capacity is increased. As the number of cycles increases, the cycle life due to repeated charging and discharging improves.
(ヘ)実施例 市販のチタン及びコバルトを組成比でTi：Co＝１：１に
なるように混合し、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TiCo粉末を得た。(F) Example Commercially available titanium and cobalt were mixed in a composition ratio of Ti: Co = 1: 1, placed in an arc melting furnace, heated, melted, alloyed and pulverized to obtain TiCo powder. It was
また、チタン、コバルト及びアルミニウムを組成比でT
i：Co：Al＝１：0.9：0.1になるよう混合し、同様にし
て加熱、溶解によつて合金化した後粉砕を行ないTiCo0.
9Al0.1粉末を得ると共に、前記混合、合金化及び粉砕と
いう操作を行なつて組成が種々異なる各種水素吸蔵合金
粉末を得た。こうして得られた各種水素吸蔵合金粉末８
０重量％、導電材としてのアセチレンブラック１０重量
％及び結着剤としてのフッ素樹脂粉末１０重量％を混合
機で均一に混合すると共にフッ素樹脂を繊維化する。そ
して得られた混練物をニッケル金網で包み込み3ton/cm2
で加圧成型することにより、外面がニッケル金網で覆わ
れた水素吸蔵電極を作製した。尚、これら水素吸蔵電極
に用いた合金粉末は夫々約1.5ｇである。In addition, titanium, cobalt and aluminum are used in a composition ratio of T
i: Co: Al = 1: 0.9: 0.1 are mixed, and similarly heated and melted to form an alloy, which is then crushed to obtain TiCo0.
9Al0.1 powder was obtained, and the operations of mixing, alloying and pulverization were performed to obtain various hydrogen storage alloy powders having different compositions. Various hydrogen storage alloy powders 8 thus obtained
0% by weight, 10% by weight of acetylene black as a conductive material, and 10% by weight of fluororesin powder as a binder are uniformly mixed in a mixer and the fluororesin is made into fibers. Then, the kneaded material obtained was wrapped in nickel wire mesh to 3 ton / cm 2
By pressure molding with, a hydrogen storage electrode having an outer surface covered with a nickel wire mesh was produced. The alloy powder used for these hydrogen storage electrodes is about 1.5 g each.
次いで上記水素吸蔵電極を夫々理論容量が６００mAHの
焼結式ニッケル正極と組み合わせ電解液に水酸化カリウ
ム水溶液を用いて密閉型ニッケル−水素アルカリ蓄電池
を種々作製し、負極に用いた水素吸蔵合金の種類により
第１表に示す如く電池Ａ乃至Ｒとする。これら電池を0.
1Ｃ電流で１６時間充電した後、0.2Ｃ電流で放電して電
池電圧が1.0Ｖになつた時点で放電停止するサイクル条
件で充放電を繰り返し行ない電池性能を測定し、各電池
の放電容量を第１表に示すと共にそのサイクル特性を各
電池の初期容量を夫々１００として第１図に示す。Next, the above hydrogen storage electrodes were respectively combined with a sintered nickel positive electrode having a theoretical capacity of 600 mAH to prepare various sealed nickel-hydrogen alkaline storage batteries using an aqueous solution of potassium hydroxide as an electrolyte, and the kind of hydrogen storage alloy used for the negative electrode. As a result, batteries A to R are obtained as shown in Table 1. Replace these batteries with 0.
After charging at 1C current for 16 hours, discharging at 0.2C current and stopping charging when the battery voltage reaches 1.0V, charge and discharge are repeated under the cycle condition, and the battery performance is measured. Table 1 and its cycle characteristics are shown in FIG. 1 with the initial capacity of each battery being 100.
第１表及び第１図から明らかなようにチタン−コバルト
合金に上記各種元素を含有させた水素吸蔵合金を負極に
用いた電池Ｂ乃至Ｒは、TiCoを負極に用いた電池Ａと比
較して何れも放電容量及びサイクル寿命が向上してい
る。放電容量に関しては特に電池Ｂ、Ｅ、Ｆ及びＨが著
しく増加しており、サイクル寿命に関しては特に電池
Ｊ、Ｋ及びＭに於いて大きな向上がみられる。これによ
つて、放電容量を増大するためにはAl、Cr、Mn及びCuを合
金に含有させることが効果的であり、またサイクル特性
を向上させるためにはＹ、Nb及びHfを合金に含有させる
ことが効果的であると推測できる。 As is clear from Table 1 and FIG. 1, the batteries B to R using the hydrogen storage alloy containing the above various elements in the titanium-cobalt alloy as the negative electrode are compared with the battery A using TiCo as the negative electrode. Both have improved discharge capacity and cycle life. The discharge capacities of the batteries B, E, F, and H are remarkably increased, and the cycle life of the batteries J, K, and M is greatly improved. Therefore, it is effective to contain Al, Cr, Mn and Cu in the alloy in order to increase the discharge capacity, and Y, Nb and Hf are contained in the alloy in order to improve the cycle characteristics. It can be inferred that it is effective.
また、ＴｉＭｎ合金のＭｎをＣｏで一部置換した合金を
用いた負極を備える電池Ｗは、放電容量が、本発明に係
る電池Ｂ〜Ｒに比し、放電容量が小さいことが分かる。Further, it is found that the battery W including the negative electrode using the alloy in which Mn of the TiMn alloy is partially replaced with Co has a smaller discharge capacity than the batteries B to R according to the present invention.
上記結果によりチタン−コバルト合金のチタン又はコバ
ルトの一部を第１表に示す一種類の元素で置換してなる
水素吸蔵合金を負極に備えた電池の放電容量及びサイク
ル寿命が向上することは明らかであるが、同時にして二
種以上の元素で置換した場合にも同様の効果が得られ
る。以下にTiCoをベースとし二種以上の元素で置換した
水素吸蔵合金を負極に用いた電池について示す。From the above results, it is apparent that the discharge capacity and cycle life of the battery having the negative electrode of the hydrogen storage alloy obtained by substituting a part of titanium or cobalt of the titanium-cobalt alloy with one element shown in Table 1 are improved. However, the same effect can be obtained when two or more elements are simultaneously substituted. The following is a battery using a hydrogen storage alloy based on TiCo and substituted with two or more elements for the negative electrode.
前述と同様の操作でTi0.9Nb0.1Co0.9Mn0.1、TiCo0.8Mg
0.1Al0.1及びTi0.8Nb0.1Ca0.1Co粉末を作製すると共
に、これら合金を負極に使用して電池を組立て電池性能
を測定した。こうして作製した電池を第２表に示すよう
に電池Ｓ、Ｔ及びＵとし第２表にその放電容量を、また
第２図にそのサイクル特性を夫々示す。Ti0.9Nb0.1Co0.9Mn0.1, TiCo0.8Mg by the same operation as above
0.1Al0.1 and Ti0.8Nb0.1Ca0.1Co powders were produced, and batteries were assembled by using these alloys for the negative electrode and the battery performance was measured. The batteries thus produced are referred to as batteries S, T and U as shown in Table 2, and the discharge capacity is shown in Table 2 and the cycle characteristics are shown in FIG.
(ト)発明の効果 本発明の水素吸蔵合金電極はチタン−コバルト合金のチ
タン及び／又はコバルトの一部を元素Ｍ1及び／又はＭ2
で置換してなるＴｉ(1-x)Ｍ1 xＣｏ(1-y)Ｍ2 y〔式中、０
≦ｘ≦０．２、０≦ｙ≦０．２（但し、ｘ＝ｙ＝０の場
合を除く。）であり、Ｍ1はＹ、Ｎｂ、Ｍｏ、Ｈｆ及び
Ｔａから選ばれた少なくとも一種の元素であり、またＭ
2はＡｌ、Ｓｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ及
びアルカリ土類金属から選ばれた少なくとも一種の元素
である。〕が電極材料として用いられてなるものであ
り、放電容量の増大及びサイクル寿命の向上がはかれ、
この水素吸蔵電極を負極に用いることにより優れた性能
の蓄電池を提供することができるため、その工業的価値
は極めて大きい。 (G) Effect of the Invention In the hydrogen storage alloy electrode of the present invention, a part of titanium and / or cobalt of the titanium-cobalt alloy is used as the element M 1 and / or M 2.
Ti (1-x) M 1 x Co (1-y) M 2 y substituted by
≦ x ≦ 0.2, 0 ≦ y ≦ 0.2 (excluding the case where x = y = 0), and M 1 is at least one selected from Y, Nb, Mo, Hf, and Ta. Is an element and also M
2 is at least one element selected from Al, Si, V, Cr, Mn, Fe, Cu, Zn and alkaline earth metals. ] Is used as an electrode material, the discharge capacity and cycle life are improved.
By using this hydrogen storage electrode for the negative electrode, a storage battery with excellent performance can be provided, and therefore its industrial value is extremely large.
第１図及び第２図は各種水素吸蔵電極を負極に備えた電
池のサイクル特性図である。FIG. 1 and FIG. 2 are cycle characteristic diagrams of a battery provided with various hydrogen storage electrodes on the negative electrode.
Claims (1)
コバルトの一部を元素Ｍ1及び／又はＭ2で置換してなる
Ｔｉ(1-x)Ｍ1 xＣｏ(1-y)Ｍ2 y（式中、０≦ｘ≦０．２、
０≦ｙ≦０．２〔但し、ｘ＝ｙ＝０の場合を除く。）で
あり、Ｍ1はＹ、Ｎｂ、Ｍｏ、Ｈｆ及びＴａから選ばれ
た少なくとも一種の元素であり、またＭ2はＡ、Ｓ
ｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ及びアルカリ土
類金属から選ばれた少なくとも一種の元素である。〕が
電極材料として用いられてなる水素吸蔵電極。 1. Ti (1-x) M 1 x Co (1-y) M 2 y obtained by substituting a part of titanium and / or cobalt of a titanium-cobalt alloy with elements M 1 and / or M 2. (Where 0 ≦ x ≦ 0.2,
0 ≦ y ≦ 0.2 [However, the case where x = y = 0 is excluded. ), M 1 is at least one element selected from Y, Nb, Mo, Hf and Ta, and M 2 is A, S
It is at least one element selected from i, V, Cr, Mn, Fe, Cu, Zn and alkaline earth metals. ] Is used as an electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131283A JPH0652655B2 (en) | 1985-06-17 | 1985-06-17 | Hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131283A JPH0652655B2 (en) | 1985-06-17 | 1985-06-17 | Hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61288373A JPS61288373A (en) | 1986-12-18 |
| JPH0652655B2 true JPH0652655B2 (en) | 1994-07-06 |
Family
ID=15054325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60131283A Expired - Lifetime JPH0652655B2 (en) | 1985-06-17 | 1985-06-17 | Hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0652655B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6016064B2 (en) * | 1976-08-30 | 1985-04-23 | 松下電器産業株式会社 | Manufacturing method for storage battery cathode plates |
-
1985
- 1985-06-17 JP JP60131283A patent/JPH0652655B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61288373A (en) | 1986-12-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |