JP2999785B2 - Hydrogen storage alloy electrode for alkaline storage batteries - Google Patents
Hydrogen storage alloy electrode for alkaline storage batteriesInfo
- Publication number
- JP2999785B2 JP2999785B2 JP2012932A JP1293290A JP2999785B2 JP 2999785 B2 JP2999785 B2 JP 2999785B2 JP 2012932 A JP2012932 A JP 2012932A JP 1293290 A JP1293290 A JP 1293290A JP 2999785 B2 JP2999785 B2 JP 2999785B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- electrode
- hydrogen
- alloy
- storage alloy
- Prior art date
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Classifications
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- 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
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
吸蔵合金電極に関する。The present invention relates to a hydrogen storage alloy electrode used as a negative electrode of an alkaline storage battery.
（ロ） 従来の技術 従来から使用されている蓄電池としては、ニッケル−
カドミウム電池の如きアルカリ蓄電池、あるいは鉛蓄電
池などが挙げられるが、近年これらの電池よりも軽量、
高容量で高エネルギー密度となる可能性のある水素吸蔵
合金電極を備えた金属酸化物−水素アルカリ蓄電池が注
目を浴びている。この蓄電池に用いられる水素吸蔵合金
としては、例えば特公昭59−49671号公報に示されてい
るように、LaNi5や、その改良であるLaNi4Co、LaNi4.8F
e0.2などの水素吸蔵合金が用いられ、またLa、Ce、Pr、
Nd、Smなどのランタン系の混合物であるミッシュメタル
（Mm）を用いた水素吸蔵合金が開発されている（例えば
特開昭62−20245号公報参照）。(B) Conventional technology Conventional storage batteries include nickel-based batteries.
Alkaline storage batteries such as cadmium batteries, or lead storage batteries and the like, but in recent years lighter than these batteries,
Attention has been focused on metal oxide-hydrogen alkaline storage batteries provided with a hydrogen storage alloy electrode that can have a high capacity and a high energy density. As the hydrogen storage alloy used for this storage battery, for example, as shown in JP-B-59-49671, LaNi 5 and its improved LaNi 4 Co, LaNi 4.8 F
A hydrogen storage alloy such as e 0.2 is used, and La, Ce, Pr,
A hydrogen storage alloy using misch metal (Mm), which is a lanthanum-based mixture such as Nd and Sm, has been developed (see, for example, JP-A-62-20245).
この水素吸蔵合金を用いた水素極は、水素吸蔵合金上
で水素極の反応を進行させ充電時に生成する水素を水素
吸蔵合金中に吸蔵させてしまうものである。そして特に
水素吸蔵量が大きく、水素極の電極触媒能力に優れた水
素吸蔵合金を負極材料として用いると、高エネルギー密
度の電極を構成することができる。しかも充放電電位が
カドミウム電極と類似していることから、カドミウムを
負極とするニッケル−カドミウム電池と完全な互換性を
有している。The hydrogen electrode using this hydrogen storage alloy causes the reaction of the hydrogen electrode to proceed on the hydrogen storage alloy and causes the hydrogen generated during charging to be stored in the hydrogen storage alloy. In particular, when a hydrogen storage alloy having a large hydrogen storage amount and excellent hydrogen electrode catalytic performance is used as a negative electrode material, a high energy density electrode can be formed. In addition, since the charge / discharge potential is similar to that of a cadmium electrode, it is completely compatible with a nickel-cadmium battery using cadmium as a negative electrode.
この水素吸蔵合金を負極に用いた電池はニッケル−水
素電池と呼ばれているが、例えば同一体積の密閉型ニッ
ケル−水素電池と、ニッケル−カドミウム電池とを比較
すると、ニッケル−水素電池はニッケル−カドミウム電
池の約1.5倍のエネルギー密度を有している。A battery using this hydrogen storage alloy for the negative electrode is called a nickel-hydrogen battery. For example, comparing a sealed nickel-hydrogen battery with the same volume and a nickel-cadmium battery, the nickel-hydrogen battery has a nickel-hydrogen battery. It has about 1.5 times the energy density of cadmium batteries.
このように高エネルギー密度の観点から、電池が通常
用いられる常温域で水素吸蔵放出量の多い水素吸蔵合金
に開発の重きが置かれていたが、現在までに開発された
合金を用いた場合、初期の充放電効率が低く、充放電の
サイクル初期から充分な電気化学容量が得られないとい
う問題があった。即ち、水素吸蔵合金電極は初期から充
電は容易であるが、放電の場合は合金内から合金表面に
水素が拡散するプロセスが律速段階となり、合金内に水
素が残留したまま転極してしまう現象が見られ、放電効
率の点で問題があった。Thus, from the viewpoint of high energy density, the emphasis was placed on the development of hydrogen storage alloys with a large amount of hydrogen storage and release in the normal temperature range where batteries are normally used.However, when using alloys developed to date, There is a problem that the initial charge / discharge efficiency is low and a sufficient electrochemical capacity cannot be obtained from the initial charge / discharge cycle. In other words, the hydrogen storage alloy electrode is easy to charge from the beginning, but in the case of discharge, the process of diffusing hydrogen from inside the alloy to the alloy surface becomes the rate-determining step, and the phenomenon occurs in which the polarity is reversed while hydrogen remains in the alloy. And there was a problem in terms of discharge efficiency.
（ハ） 発明が解決しようとする課題 本発明はこのような問題点に鑑みて為されたものであ
って、初期の充放電効率とサイクル性能に優れた蓄電
池、特にニッケル−水素蓄電池に用いられるアルカリ蓄
電池用水素吸蔵合金電極を提供するものである。(C) Problems to be Solved by the Invention The present invention has been made in view of such problems, and is used for a storage battery having excellent initial charge / discharge efficiency and cycle performance, particularly for a nickel-hydrogen storage battery. It is intended to provide a hydrogen storage alloy electrode for an alkaline storage battery.
（ニ）課題を解決するための手段 本発明のアルカリ蓄電池用水素吸蔵電極は、組成式Re
BxMy（但し、組成式中、Reは希土類元素、アルカリ土類
元素の一種以上、Ｂはホウ素、Ｍはアルミニウム若しく
はマンガンの少なくとも一方とニッケルとコバルトとを
含んでおり、前記Ｍの含有量が0.5＜ｙ＜6.0である）で
表わされる水素吸蔵合金から構成され、上記組成式にお
けるホウ素の含有量ｘが、0.005＜ｘ＜1.0であり、前記
水素吸蔵合金中にホウ素リッチ相が形成されたものであ
ることを特徴とする。(D) Means for Solving the Problems The hydrogen storage electrode for an alkaline storage battery of the present invention has a composition formula of Re.
BxMy (where, in the composition formula, Re is one or more of a rare earth element and an alkaline earth element, B is boron, M contains at least one of aluminum or manganese, nickel and cobalt, and the content of M is 0.5 <Y <6.0), wherein the boron content x in the above composition formula is 0.005 <x <1.0, and a boron-rich phase is formed in the hydrogen storage alloy. It is characterized by being.
この水素吸蔵合金が、水素を吸蔵して水素化物となっ
た場合、この水素化物の平衡解離圧が40℃の温度におい
て、0.05〜５気圧の範囲にあるものが好ましい。When this hydrogen storage alloy becomes a hydride by storing hydrogen, it is preferable that the equilibrium dissociation pressure of the hydride be in the range of 0.05 to 5 atm at a temperature of 40 ° C.
そして、前記組成式におけるＭは、Cr、Fe、Cu、Sn、
Sb、Mo、Ｖ、Nb、Ta、Zn、Zr、Tiのうちから選ばれた少
なくとも一種を含んでいてもよい。M in the above composition formula is Cr, Fe, Cu, Sn,
At least one selected from Sb, Mo, V, Nb, Ta, Zn, Zr, and Ti may be included.
更には、前記組成式におけるＭは、Mo、Zr、Crのうち
から選ばれた少なくとも一種を含んでいるのが好まし
い。Further, it is preferable that M in the above composition formula contains at least one selected from Mo, Zr, and Cr.
（ホ）作用 本発明の如く、希土類元素、アルカリ土類元素の一種
以上、並びにNi、Co、Mn、Al、Cr、Fe、Cu、Sn、Sb、M
o、Ｖ、Nb、Ta、Zn、Zr、Tiのうちから選ばれた一種以
上の金属を主成分とする水素吸蔵合金に、ホウ素を含ま
せることによって水素吸蔵合金中にホウ素リッチな相が
形成される。このホウ素リッチ相は水素の吸蔵放出の際
の膨張、収縮が非常に大きいので、このホウ素リッチ相
を有する水素吸蔵合金を電極材料として用いた場合、１
サイクル目の充放電でホウ素リッチ相からクラックが生
じ、そのクラックに電解液が浸透することによって電極
の反応面積が増大する。このようにして蓄電池のサイク
ル初期の充放電効率が改善される。(E) Action As in the present invention, one or more of rare earth elements and alkaline earth elements, and Ni, Co, Mn, Al, Cr, Fe, Cu, Sn, Sb, M
O-, V-, Nb-, Ta-, Zn-, Zr-, Ti-based hydrogen storage alloys containing at least one metal selected from the group consisting of boron as a main component to form a boron-rich phase in the hydrogen storage alloy Is done. Since this boron-rich phase has a very large expansion and contraction during the storage and release of hydrogen, when a hydrogen storage alloy having this boron-rich phase is used as an electrode material,
Cracks are generated from the boron-rich phase in the charge and discharge in the cycle, and the electrolyte permeates the cracks, thereby increasing the reaction area of the electrode. In this way, the charge / discharge efficiency of the storage battery at the beginning of the cycle is improved.
（ヘ） 実施例 一般に市販されている原料を秤量し、高周波誘導炉を
用いて「第１図」に示す35種類の合金を作製した。第１
図は各種合金組成における電極特性を示す図である。な
お、融点の高い元素については予めNiに固溶させて合金
を作製した。合金は機械的に粉砕し、平均粒径50μｍの
粉末とした後、結着剤としてポリテトラフルオロエチレ
ン粉末10％を混合し、ペースト状とした。次にこのペー
ストをニッケルメッシュで包み込んで1ton/cm2の圧力で
加圧成型し、水素吸蔵合金電極を得た。そしてこれらの
各電極について、30％のKOH中で５気圧の加圧容器中で
充放電テストを行った。その時の充放電条件は、充電が
50mA/gの電流値で８時間、放電は100mA/gの電流値で電
極電位が−0.7VvsHg/HgOに達するまで行った。この充放
電の１サイクル目と10サイクル目に得られる電気化学容
量の比で初期の充放電効率の優劣比較を行った。(F) Example Generally, commercially available raw materials were weighed, and 35 kinds of alloys shown in FIG. 1 were produced using a high-frequency induction furnace. First
The figure shows electrode characteristics for various alloy compositions. It should be noted that an element having a high melting point was previously dissolved in Ni to form an alloy. The alloy was mechanically pulverized to obtain a powder having an average particle diameter of 50 μm, and then 10% of polytetrafluoroethylene powder was mixed as a binder to form a paste. Next, the paste was wrapped in a nickel mesh and pressed under a pressure of 1 ton / cm 2 to obtain a hydrogen storage alloy electrode. Each of these electrodes was subjected to a charge / discharge test in a pressurized container at 5 atm in 30% KOH. The charge and discharge conditions at that time are as follows:
Discharging was performed at a current value of 50 mA / g for 8 hours until the electrode potential reached −0.7 VvsHg / HgO at a current value of 100 mA / g. Initial charge / discharge efficiency was compared based on the ratio of the electrochemical capacities obtained at the first and tenth cycles of the charge / discharge.
この第１図から明らかなように、水素吸蔵合金電極の
１サイクル目と10サイクル目の電気化学容量比からサイ
クル初期の充放電効率を比較すると、ホウ素（Ｂ）を添
加した合金の方が優れていることがわかる。即ち代表的
な水素吸蔵合金であるLaNi5の場合、１サイクル目容量
と10サイクル目容量との比は91.2％（電極番号No.1）で
あるが、これに0.05モルのホウ素を添加すると、94.7％
（No.2）となり、0.5モル添加すると96.7％（No.3）、
また１モル添加すると95.3％（No.4）となり、いずれも
ホウ素を添加しないもの（No.1）に比較して１サイクル
目から充放電効率が高まっていることがわかる。As is apparent from FIG. 1, when the charge and discharge efficiency at the beginning of the cycle is compared from the electrochemical capacity ratio of the first cycle and the tenth cycle of the hydrogen storage alloy electrode, the alloy to which boron (B) is added is superior. You can see that it is. That is, in the case of LaNi 5 which is a typical hydrogen storage alloy, the ratio between the first cycle capacity and the 10th cycle capacity is 91.2% (electrode number No. 1). 94.7%
(No. 2), and 96.7% (No. 3) when 0.5 mole is added,
Also, when 1 mol is added, it becomes 95.3% (No. 4), and it can be seen that the charge and discharge efficiency is increased from the first cycle as compared with the case where no boron is added (No. 1).
通常、希土類−Ni系合金は安価で耐食性に優れている
という観点から、Laの部分は希土類の混合物であるミッ
シュメタル（Mm）に置換して用いられることが多い。Mm
−Ni合金はLaNi5に比べて水素吸蔵平衡圧は高圧であ
り、40℃で５気圧以上である。ところが密閉型蓄電池の
材料として用いるには水素吸蔵平衡圧は0.05〜５気圧で
あることが望ましい。このため蓄電池用のMm−Ni系合金
のNiの成分は、Co、Al、Mnなどで一部置換された合金が
用いられることが多い。特にCoは耐食性向上の面からも
重要な元素である（電極番号No.7以降）。Usually, from the viewpoint that rare earth-Ni alloys are inexpensive and have excellent corrosion resistance, La is often replaced with misch metal (Mm), which is a mixture of rare earth elements. Mm
-Ni alloy is high-pressure hydrogen storage equilibrium pressure than the LaNi 5, is at least 5 atm at 40 ° C.. However, the hydrogen storage equilibrium pressure is desirably 0.05 to 5 atm for use as a material for a sealed storage battery. For this reason, as the Ni component of the Mm-Ni alloy for storage batteries, an alloy partially substituted with Co, Al, Mn or the like is often used. In particular, Co is an important element from the viewpoint of improving corrosion resistance (electrode number No. 7 or later).
Al、Mnの置換元素については上記したように水素吸蔵
平衡圧を下げて電気化学容量を増加させる効果があるも
のの、Al、Mnを添加しないものに比較して、初期充放電
効率を低下させる問題点を含んでいる。その理由はAl、
Mnを添加することによって合金格子の体積が増加し、水
素の吸蔵、放出に対してもクラックが生じにくくなるこ
とと、Al、Mnを添加した合金の表面に形成される酸化膜
層は水素の拡散に対する障壁となりやすいことに起因す
るものと考えられている。ところがこのようなMnを含む
合金に対してもホウ素を添加することによって初期の活
性化特性が改善される。このホウ素添加による改善状態
は、電極番号No.12のものと電極番号No.13のものとを比
較すれば明らかであろう。Al and Mn substitution elements have the effect of lowering the hydrogen storage equilibrium pressure and increasing the electrochemical capacity as described above, but have the problem of lowering the initial charge / discharge efficiency compared to those without the addition of Al and Mn. Contains dots. The reason is Al,
The addition of Mn increases the volume of the alloy lattice, making it difficult for cracks to be absorbed and released, and the oxide film layer formed on the surface of the alloy containing Al and Mn contains hydrogen. It is believed that it is likely to be a barrier to diffusion. However, even in such an alloy containing Mn, the initial activation characteristics are improved by adding boron. The state of improvement by the addition of boron will be apparent when the electrode No. 12 and the electrode No. 13 are compared.
また理由は詳ではないが、それらの合金にMo、Zr、Cr
を共存させると更に活性化特性が向上する。Although the reason is not clear, Mo, Zr, Cr
The coexistence further improves the activation characteristics.
ホウ素の添加量は第１図に示した実験結果から、0.00
5モルから1.0モルの範囲が効果がある領域である。また
希土類−Ni系合金においてNi成分を他元素に置き換える
ことは可能であるが、電極反応を進行させるに当りNiは
必須元素であり、1.0モル以上は必要である。From the experimental results shown in FIG.
The range of 5 mol to 1.0 mol is an effective region. Although it is possible to replace the Ni component with another element in the rare earth-Ni alloy, Ni is an essential element for the electrode reaction to proceed, and at least 1.0 mol is required.
またRe置換成分（希土類元素、アルカリ土類元素の総
和）と、BxMyの化学量論比については通常は５である
が、混合成分によってはその最適化が必要である。例え
ばホウ素を0.05モル程度添加する場合は化学量論比は５
以下であることが望ましい。その理由はホウ素を添加す
ることによって僅かではあるが水素吸蔵圧が高圧側にシ
フトするために、化学量論比を5.0以下にして低平衡圧
を保つ必要があるからである。またホウ素を1.0モル程
度添加した場合には化学量論比は５以上であることが好
ましい。その理由は合金中にホウ素リッチ層が増加し、
実際に水素を吸蔵放出する部分の化学量論比は更に小さ
くなっていることが予想されるからである。The stoichiometric ratio of the Re-substituted component (sum of the rare earth element and the alkaline earth element) to BxMy is usually 5, but depending on the mixed component, its optimization is required. For example, when adding about 0.05 mol of boron, the stoichiometric ratio is 5
It is desirable that: The reason is that the addition of boron slightly shifts the hydrogen storage pressure to the high pressure side, so that the stoichiometric ratio needs to be 5.0 or less to maintain a low equilibrium pressure. When about 1.0 mol of boron is added, the stoichiometric ratio is preferably 5 or more. The reason is that the boron rich layer increases in the alloy,
This is because it is expected that the stoichiometric ratio of the portion that actually stores and releases hydrogen is further reduced.
これらのことを総合すると、ReBxMyで表される化学式
中で、Reは希土類元素、アルカリ土類元素の一種以上
で、Ｍは、Ni、Co、Mn、Al、Cr、Fe、Cu、Sn、Sb、Mo、
Ｖ、Nb、Ta、Zn、Zr、Tiのうちから選ばれた一種以上の
金属であり、またｘは0.005から1.0の範囲であり、且つ
ｘ＋ｙは3.5から6.0が望ましい範囲と云うことができ
る。In sum, in the chemical formula represented by ReBxMy, Re is a rare earth element or one or more of alkaline earth elements, and M is Ni, Co, Mn, Al, Cr, Fe, Cu, Sn, Sb. , Mo,
It is one or more metals selected from V, Nb, Ta, Zn, Zr, and Ti. X is in the range of 0.005 to 1.0, and x + y is in the range of 3.5 to 6.0.
次に本発明に係る水素吸蔵合金電極の具体的な製造方
法を、電極番号No.13のものについて説明する。原材料
としてMm、Ni、Co、Mnと、Ｂを約10wt％含有するNiとの
母合金（Ni4B3）を用いた。Ｂを含有するNi母合金を用
いるのは、Ｂの単体は融点が高く（2180℃）、通常の高
周波誘導炉では溶解しないためである。なお、Ｂを約10
wt％含有するNiとの母合金の融点は1100℃である。これ
らの原料を、 Mm:Ni:Co:Mn:Ni4B3 ＝1:3.433:0.7:0.8:0.017 の割合に秤量し高周波誘導炉で溶解させて所望の水素吸
蔵合金を得ている。Next, a specific manufacturing method of the hydrogen storage alloy electrode according to the present invention will be described with reference to electrode No. 13. As a raw material, a mother alloy (Ni 4 B 3 ) of Mm, Ni, Co, Mn and Ni containing about 10 wt% of B was used. The Ni mother alloy containing B is used because the simple substance of B has a high melting point (2180 ° C.) and does not melt in a normal high-frequency induction furnace. B is about 10
The melting point of the master alloy with Ni containing wt% is 1100 ° C. These raw materials are weighed in a ratio of Mm: Ni: Co: Mn: Ni 4 B 3 = 1: 3.433: 0.7: 0.8: 0.017 and melted in a high frequency induction furnace to obtain a desired hydrogen storage alloy.
このようにして得た水素吸蔵合金を用いた電極番号N
o.13の電極に対して１サイクルの充放電を行わしめた後
の電極中における、水素吸蔵合金の粒子構造を示す走査
型電子顕微鏡写真（倍率1000倍）を、第２図及び第３図
に示す。第２図は水素吸蔵合金表面、第３図は表面研摩
後のものである。対比例として電極番号No.12のホウ素
を含有しない電極中における同条件下の、水素吸蔵合金
の粒子構造を示す走査型電子顕微鏡写真（倍率1000倍）
を、第４図及び第５図に示す。この第２図、第３図及び
第４図、第５図の粒子構造を示す写真の対比から明白な
ように、ホウ素が添加された電極（No.13）はホウ素が
添加されていない電極（No.12）に比べて大きなクラッ
クが多く生じており、１サイクル目から電極反応面が増
加していることが確認できる。これらのクラックが発生
するのはホウ素がリッチな面であり、新たにできた面の
表面付近はホウ素リッチ層になるものと考えられるが、
この部分の水素原子の拡散はホウ素のない表面層より速
いものと推察される。これらの理由によりLaNi5に代表
される希土類−Ni系合金中へのホウ素の添加は電極の初
期活性化の向上に効果があることがわかる。Electrode number N using the hydrogen storage alloy thus obtained
FIGS. 2 and 3 show scanning electron micrographs (1000-fold magnification) showing the particle structure of the hydrogen storage alloy in the electrode after one cycle of charging and discharging of the o.13 electrode. Shown in FIG. 2 shows the surface of the hydrogen storage alloy, and FIG. 3 shows the surface after surface polishing. Scanning electron micrograph (1000x magnification) showing the particle structure of the hydrogen-absorbing alloy under the same conditions in the electrode containing No. 12 containing no boron as a comparative example.
Are shown in FIG. 4 and FIG. As is clear from the comparison of the photographs showing the particle structures in FIGS. 2, 3, 4 and 5, the electrode with boron added (No. 13) was the electrode without boron added (No. 13). No. 12), many large cracks occurred, and it can be confirmed that the electrode reaction surface increased from the first cycle. It is thought that these cracks occur on the boron-rich surface, and the vicinity of the newly formed surface becomes a boron-rich layer.
It is presumed that diffusion of hydrogen atoms in this part is faster than the surface layer without boron. For these reasons, it can be seen that the addition of boron to a rare earth-Ni alloy represented by LaNi 5 is effective in improving the initial activation of the electrode.
（ト） 発明の効果 本発明は以上の説明から明らかなように、希土類元
素、アルカリ土類元素の一種以上、及びNi、Co、Mn、A
l、Cr、Fe、Cu、Sn、Sb、Mo、Ｖ、Nb、Ta、Zn、Zr、Ti
のうちから選ばれた一種以上の金属を主成分とする水素
吸蔵合金にホウ素を含ませているので、充放電の１サイ
クル目から電極の活性化が図れ、充放電の初期から高い
充放電効率が得られ、充分な電気化学容量を有するアル
カリ蓄電池を形成することができる。(G) Effects of the present invention As is apparent from the above description, the present invention provides one or more rare earth elements and alkaline earth elements, and Ni, Co, Mn, and A.
l, Cr, Fe, Cu, Sn, Sb, Mo, V, Nb, Ta, Zn, Zr, Ti
Since boron is contained in the hydrogen storage alloy containing at least one metal selected from among the above, the electrodes can be activated from the first cycle of charge and discharge, and high charge and discharge efficiency can be achieved from the beginning of charge and discharge. And an alkaline storage battery having a sufficient electrochemical capacity can be formed.
第１図は各種合金組成における電極特性を示す図、第２
図乃至第５図はいずれも電極中における水素吸蔵合金の
粒子構造を示す走査型電子顕微鏡写真であり、第２図及
び第３図は本発明電極の１サイクル目充放電終了後の粒
子構造を示す写真、第４図及び第５図は従来電極の１サ
イクル目充放電終了後の粒子構造を示す写真である。FIG. 1 is a diagram showing electrode characteristics in various alloy compositions, and FIG.
5 to 5 are scanning electron micrographs showing the particle structure of the hydrogen storage alloy in the electrode. FIGS. 2 and 3 show the particle structure of the electrode of the present invention after the first cycle charge / discharge. FIG. 4 and FIG. 5 are photographs showing the particle structure of the conventional electrode after the first cycle of charging and discharging.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 亀岡 誠司 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 田所 幹朗 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (56)参考文献 特開 昭60−155641（ＪＰ，Ａ) 特開 平３−108273（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 19/00 H01M 4/38 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Kameoka 2-18-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Mikiro Tadoko 2--18 Keihanhondori, Moriguchi-shi, Osaka (56) References JP-A-60-155561 (JP, A) JP-A-3-108273 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C22C 19 / 00 H01M 4/38
Claims (4)
類元素、アルカリ土類元素の一種以上、Ｂはホウ素、Ｍ
はアルミニウム若しくはマンガンの少なくとも一方とニ
ッケルとコバルトとを含んでおり、前記Ｍの含有量が0.
5＜ｙ＜6.0である）で表わされる水素吸蔵合金からなる
アルカリ蓄電池用水素吸蔵合金電極において、 上記組成式におけるホウ素の含有量ｘが、0.005＜ｘ＜
1.0であり、 前記水素吸蔵合金中にホウ素リッチ相が形成されたもの
であることを特徴とするアルカリ蓄電池用水素吸蔵合金
電極。A composition formula ReBxMy (wherein, Re is at least one of a rare earth element and an alkaline earth element, B is boron, M
Contains at least one of aluminum or manganese, nickel and cobalt, and the content of M is 0.
5 <y <6.0), wherein the boron content x in the above composition formula is 0.005 <x <
1.0, wherein a boron-rich phase is formed in the hydrogen storage alloy. A hydrogen storage alloy electrode for an alkaline storage battery.
が40℃の温度において、0.05〜５気圧の範囲にある請求
項記載のアルカリ蓄電池用水素吸蔵合金電極。2. The hydrogen storage alloy electrode for an alkaline storage battery according to claim 1, wherein the equilibrium dissociation pressure of the hydride of the hydrogen storage alloy is in the range of 0.05 to 5 atm at a temperature of 40 ° C.
n、Sb、Mo、Ｖ、Nb、Ta、Zn、Zr、Tiのうちから選ばれ
た少なくとも一種を含んでいることを特徴とする請求項
記載のアルカリ蓄電池用水素吸蔵合金電極。3. In the above composition formula, M is Cr, Fe, Cu, S
The hydrogen storage alloy electrode for an alkaline storage battery according to claim 1, comprising at least one selected from n, Sb, Mo, V, Nb, Ta, Zn, Zr, and Ti.
ちから選ばれた少なくとも一種を含んでいることを特徴
とする請求項記載のアルカリ蓄電池用水素吸蔵合金電
極。4. The hydrogen storage alloy electrode for an alkaline storage battery according to claim 1, wherein M in said composition formula includes at least one selected from Mo, Zr, and Cr.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012932A JP2999785B2 (en) | 1990-01-22 | 1990-01-22 | Hydrogen storage alloy electrode for alkaline storage batteries |
| DE4101753A DE4101753A1 (en) | 1990-01-22 | 1991-01-22 | Hydrogen absorbing metal-alloy for use in alkaline batteries - gives improved charging-discharging as well as cycling performance due to presence of boron-rich phase |
| US08/019,340 US5290509A (en) | 1990-01-22 | 1993-02-18 | Multiphase hydrogen-absorbing alloy electrode for an alkaline storage cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012932A JP2999785B2 (en) | 1990-01-22 | 1990-01-22 | Hydrogen storage alloy electrode for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03219036A JPH03219036A (en) | 1991-09-26 |
| JP2999785B2 true JP2999785B2 (en) | 2000-01-17 |
Family
ID=11819069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012932A Expired - Lifetime JP2999785B2 (en) | 1990-01-22 | 1990-01-22 | Hydrogen storage alloy electrode for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2999785B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376474A (en) * | 1993-02-05 | 1994-12-27 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy for a negative electrode and manufacturing method therefor |
| WO2010057367A1 (en) * | 2008-11-21 | 2010-05-27 | 包头稀土研究院 | RE-Fe-B SERIES HYDROGEN STORAGE ALLOY AND USE THEREOF |
-
1990
- 1990-01-22 JP JP2012932A patent/JP2999785B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03219036A (en) | 1991-09-26 |
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