JPH03219036A - Hydrogen storage alloy electrode for alkaline storage battery - Google Patents
Hydrogen storage alloy electrode for alkaline storage batteryInfo
- Publication number
- JPH03219036A JPH03219036A JP2012932A JP1293290A JPH03219036A JP H03219036 A JPH03219036 A JP H03219036A JP 2012932 A JP2012932 A JP 2012932A JP 1293290 A JP1293290 A JP 1293290A JP H03219036 A JPH03219036 A JP H03219036A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- hydrogen storage
- storage alloy
- electrode
- alkaline
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 56
- 239000000956 alloy Substances 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 238000010494 dissociation reaction Methods 0.000 claims abstract 2
- 230000005593 dissociations Effects 0.000 claims abstract 2
- 150000004678 hydrides Chemical class 0.000 claims abstract 2
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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
【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ｉ電池の負極として用いられる水素１
１．＆蔵合金電極に関する。[Detailed description of the invention] (a) Industrial application field The present invention relates to hydrogen 1 used as a negative electrode of an alkaline i-battery.
1. & Concerning Kura alloy electrodes.
（ロ） 従来の技術
？に米から使用されている蓄電池としては、二！ケルー
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、
高容槍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１例、−ば特公昭５９ ４９６７１号公報に示
されているように、１．ａＮｉ＋や、その改良であるＬ
ａ人＋ ＋ Ｃｏ、■、ａｓ ＋（、＠ Ｆｅｏ、 １
などの水素ＩＩ＆蔵合金合金いられ、またＬａ、Ｃｅ、
Ｐｒ、Ｎｄ、Ｓｍなどのランタン系の；昆合物である
ミ・ノシュメタル（Ｍｍｊを用いた水素吸蔵合金が開発
さｔ？、ている（例えば特開昭６２−２０２．４５号公
報参照）。(b) Conventional technology? As a storage battery that has been used since the United States, there are two! Examples include alkaline storage batteries such as Kelu cadmium batteries, and lead-acid batteries, but in recent years they have become lighter and lighter than these batteries.
Metal oxide-hydrogen alkaline storage batteries equipped with hydrogen-absorbing alloy electrodes are attracting attention because of their high capacity and potential for high energy density. One example of the hydrogen storage alloy used in this storage battery is 1. aNi+ and its improved L
a person + + Co, ■, as + (, @ Feo, 1
Hydrogen II & storage alloys such as La, Ce,
A hydrogen storage alloy using Mmj, which is a combination of lanthanum-based materials such as Pr, Nd, and Sm, has been developed (for example, see Japanese Patent Laid-Open No. 62-202.45).
この水素吸蔵合金を用いた水素極は、水素吸蔵合金−Ｌ
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
ａ＆蔵合金中に吸蔵させてしまうものである。そして特
に７ド素吸Ｉｉｉ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ｔｉを隔成することができる。しかも充放
ｉｔ位がカドミウム電極と類似していることがら、カド
ミウムを負極とするニッケルーカドミウム電池と完全な
互換性を有している。A hydrogen electrode using this hydrogen storage alloy is hydrogen storage alloy-L
The reaction at the hydrogen electrode proceeds, and the hydrogen generated during charging is occluded in the hydrogen a/storage alloy. In particular, when a hydrogen storage alloy having a large amount of 7-d element adsorption and excellent electrode catalytic ability of the hydrogen electrode is used as the negative electrode material, a high energy density ti can be formed. Moreover, since the charging and discharging potential is similar to that of a cadmium electrode, it is completely compatible with a nickel-cadmium battery using cadmium as the negative electrode.
この水素吸蔵合金を負極に用いた電池はニアケル−水素
電池と呼ばれているが、例えば同一体積の密閉ヤニツケ
ルー水素電池と、ニッケルーカドミウム電池とを比較す
ると、ニッケルーｙ％素を池は二ｌケルーカドミウム電
池の約１５倍のエネルギー密度を有している。Batteries using this hydrogen storage alloy as the negative electrode are called Ni-Kel-Hydrogen batteries. For example, if you compare a sealed Yan-Kel-Hydrogen battery with the same volume and a Nickel-Cadmium battery, the battery will have a nickel-y% element of 2 liters. It has an energy density approximately 15 times that of a Kelu cadmium battery.
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１吸蔵ｒ？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？りられないと
いう問題があった。即ち、水素ｇ＆蔵会合金電極初期か
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７０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Ｆ＋！象が見られ
、放電効率の点で問題があった。In this way, from the viewpoint of high energy density, water 1 absorbs and releases a large amount of hydrogen in the normal temperature range where batteries are normally used. Emphasis has been placed on gold in development, but when using the alloys developed to date, the initial charge/discharge efficiency is low, making it difficult to maintain sufficient electrochemical capacity from the beginning of the charge/discharge cycle. There was a problem that I couldn't get into it. In other words, charging is easy from the initial stage of hydrogen g & storage alloy electrode, but in the case of discharging, the rate-determining step is the 70 cess, in which hydrogen diffuses from within the alloy to the surface of the alloy, and the polarity is reversed while hydrogen remains within the alloy. Shut up F+! There were problems with discharge efficiency.
（ハ） 発明が解決しようとする課題
＋発明はこのような問題点に鑑みて工）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Ｉ！Ｉ
電池、特にニッケルー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 invention was devised in view of these problems, and the I! I
The present invention provides a hydrogen storage alloy electrode for alkaline storage batteries used in batteries, particularly nickel-metal hydride storage batteries.
（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合金電極は、式Ｒｅ
Ｂ＼Ｎ１ｙ、
但し、Ｒｅ゛希土類元素、アルカリ土類元素の一種以上
、
Ｂニホウ素、
Ｍ ： Ｎｉ、 Ｃｏ、 Ｍｎ、Ａｌ．Ｃｒ、 Ｆｅ、
Ｃｕ、Ｓｎ、 Ｓｂ、 Ｍｃ〕、ｖ、Ｎｂ。(d) Means for Solving the Problems The hydrogen storage alloy electrode for alkaline storage batteries of the present invention has the formula Re
B\N1y, however, Re: one or more of rare earth elements and alkaline earth elements, B: diboron, M: Ni, Co, Mn, Al. Cr, Fe,
Cu, Sn, Sb, Mc], v, Nb.
Ｔａ、Ｚｎ、Ｚｒ、Ｔｉのうちから選 ばれた一種以上、 ０ 、００３＜ ｘ ＜ １ 、０． ０．５＜！／＜６．０、 で表される水素吸蔵合金からなるらのである。Select from Ta, Zn, Zr, Ti One or more types that have been discovered, 0, 003<x<1, 0. 0.5<! /<6.0, It is made of a hydrogen storage alloy represented by
（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ｊ
１上、並びにＮ１、ＣＯ１ＭｎＡｌ、 Ｃｒ、Ｆｅ、Ｃ
ｕ、Ｓｎ、Ｓｂ、Ｍｏ、Ｖ、Ｎｂ、Ｔａ、Ｚｎ。(E) Effect As in the present invention, a type of rare earth element or alkaline earth element j
1, and N1, CO1MnAl, Cr, Fe, C
u, Sn, Sb, Mo, V, Nb, Ta, Zn.
ｚｒ、Ｔｉのうちから選ばれた−・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彩成される。こ
のホウ素すッチ用は水素の吸蔵放出の際の膨張、収縮が
非常に大きいので、このホウぶリッチ相を有する水素Ｉ
ｌ＆蔵合金合金極材料として用いた場合、ｌサイクル目
の充放電でホウ素ｊ・ｌ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。A boron-rich phase is formed in the hydrogen storage alloy by incorporating boron into the hydrogen storage alloy whose main component is a metal selected from among Zr and Ti. This boron-rich hydrogen I
When used as an electrode material for the l&zo alloy, cracks are generated from the boron j and lch phases during the l-th charge/discharge cycle, and the electrolyte permeates into the cracks, thereby increasing the reaction area of the electrode. In this way, the charging and discharging efficiency of the storage battery at the beginning of the cycle is improved.
（・＼） 実施例
一般に市販されている原料を秤駿し、高周波誘導炉を用
いて「第１図」に示す３５種類の合金を１ヤ製した。第
１図は各種合金組成における電極特性を・Ｒす図である
。なお、融点の高い元素につ０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３
０μｍ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４００ｂを混りし、ペースト状とした。(・＼) Example Generally commercially available raw materials were weighed and a high frequency induction furnace was used to produce 35 types of alloys shown in "Figure 1" in one batch. FIG. 1 is a diagram showing electrode characteristics in various alloy compositions. Note that elements with high melting points were dissolved in Ni in advance to prepare alloys. The alloy was mechanically crushed to an average particle size of 3
After making the powder into 0 μm powder, polytetrafluoroethylene powder 400b was mixed as a binder to make a paste.
次にこのペーストを二ｌケルメツシュで包み込んでｌｔ
。Next, wrap this paste in 2 liters of kelmetshu.
.
ｎ／’ｃｍ”の圧力で加圧成型し、水素Ｏ＆蔵合金を極
を得た。そしてこれらの各を極について、３０％のＫ
ＯＨ中で５気圧の加圧容器中で充放電テストを行った。The hydrogen O & storage alloy was press-molded at a pressure of n/'cm'' to obtain electrodes.
A charge/discharge test was conducted in a pressurized container at 5 atmospheres in OH.
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４００ ｍ 、Ａ 、’ ｇの電ｉＡ
Ｅ値で電極電位が−０、７Ｖ ｖ ｓ Ｈｇ ｙ’ Ｈ
ｇ Ｏに達するまで行った。この充放電の１サイクル目
と４０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。The charging and discharging conditions at that time were: charging at a current value of 50 mA/'g for 8 hours, and discharging at a current value of 400 m, A,' g.
Electrode potential is -0 at E value, 7V v s Hg y' H
The process continued until g O was reached. The initial charging and discharging efficiency was compared based on the ratio of the electrochemical capacities obtained at the 1st cycle and the 40th cycle of charging and discharging.
この第１図から明らかなように、水素吸蔵合金電極の１
サイクル口とＩＯ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ＬａＮ１ｇの場合、ｌサイクル目
容量と４０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．
３モル添加すると９６．７％（Ｎｏ、３）、また１モル
添加すると９５ 、 ：ｉ ’／（ｌいｏ、４）となり
、いずれもホウ素を添加しない乙の（＼ｏ、 ｌ ｌに
比較して１サイクル［１から充放電効率が高まっている
ことがわがる。As is clear from Fig. 1, 1 of the hydrogen storage alloy electrode
Comparing the charging and discharging efficiency at the beginning of the cycle based on the electrochemical capacity ratio between the cycle opening and the IO cycle, it can be seen that the alloy containing boron (B) is superior. That is, in the case of 1 g of LaN, which is a typical hydrogen storage alloy, the ratio of the 1st cycle capacity to the 40th cycle capacity is 91.2% (electrode number No. 1), but when 0.05 mol of boron is added to this, When added, it becomes 94.7% (No, 2) and 0.
When 3 moles are added, it becomes 96.7% (No, 3), and when 1 mole is added, it becomes 95, :i'/(lo, 4), both of which are compared to (\o, l l) of B where no boron is added. It can be seen that the charging and discharging efficiency increases from 1 cycle [1].
通常、希を類−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ｒ字物である
ミツシュメタル（Ｍｍ）に置換して用いられることが多
い。Ｍｍ−Ｘｉ金合金ＬａＮ＋＋に比べて水素吸蔵平衡
圧は高圧であり、４０℃で５気圧以りである。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′２Ｘ、圧であることが望ましい。このた
め蓄電池用の〜ｌｍ−Ｘ１系合金の＼ｌ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。持にＣｏは耐食性向」−の面からも重要な元素
である（、Ｔｉ極番号Ｎｏ、７以降）。Usually, from the viewpoint that rare-Ni alloys are inexpensive and have excellent corrosion resistance, the La portion is often replaced with Mitshu metal (Mm), which is a rare earth mixture. Compared to the Mm-Xi gold alloy LaN++, the hydrogen storage equilibrium pressure is higher than 5 atm at 40°C. However, in order to use it as a material for a sealed storage battery, it is desirable that the hydrogen storage equilibrium pressure is 0.05 to 5'2X. Therefore, the \l component of ~lm-X1 alloy for storage batteries is Co
Alloys partially substituted with Al, Mn, etc. are often used. In particular, Co is an important element from the viewpoint of corrosion resistance (Ti pole number No. 7 and later).
ＡＩ、Ｍ ｎ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
るらのの、Ａｌ、Ｍｎを添加しないらのに比較して、初
期光１ｉＩＣ１ｅＬ効率を低ｆ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会金
箔子の体積が増加し、＋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。As mentioned above, the replacement elements of AI and Mn have the effect of lowering the hydrogen storage equilibrium pressure and increasing the electrochemical capacity, but compared to not adding Al and Mn, the initial light 1iIC1eL efficiency is lower. This includes the problem of low f. The reason for this is that by adding Al and Mn, the volume of the metal foil increases, making it difficult for cracks to occur even when occluding and releasing positive elements. This is thought to be due to the fact that the oxide film layer formed on the surface of the Mn-added alloy tends to act as a barrier to hydrogen diffusion.
ところがこのようなＭｎを含む合金に対してもホウ素を
１奈１ｕ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簿状態は、電極番号Ｎｏ、
１２のものと電極番号Ｎｏ、１３のらのとを比較すれば
明らかであろう。However, even for such an alloy containing Mn, the initial activation characteristics are improved by adding 1 μ of boron. The bookkeeping status due to this boron addition is electrode number No.
This will be clear if you compare the electrode No. 12 and the electrode No. 13.
また理由は詳ではないが、それらの合金にＭ。Although the reason is not clear, these alloys contain M.
Ｚｒ、Ｃｒを共存させると更に活性化特性が向上する。When Zr and Cr coexist, the activation characteristics are further improved.
ホウ素の添加量は第１図に示した実験結果から、０．０
０ Ｓ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−Ｎ１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Ｎ１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 Figure 1, the amount of boron added is 0.0
The effective range is from 0 S mol to 1.0 mol. Although it is possible to replace the Ni component with other elements in the rare earth-N1 alloy, N1 is an essential element for the electrode reaction to proceed, and 1.0 mol or more is required.
またＲｃ置換成分（希土類元素、アルカリ土類ル素の総
和）と、１３＼Ｎｌ＞・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３，６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
以下にして低串ｆｌ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］二であることが好ましい。その理由は合金中に
ホウ素すンチ層が増加し、実際に水素を吸蔵放出する部
分の化学ｉｔ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。Furthermore, the stoichiometric ratio of the Rc substitution component (the sum of rare earth elements and alkaline earth elements) and 13\Nl>. is normally 5, but it needs to be optimized depending on the mixed components. For example, when adding about 0.05 mole of boron, the stoichiometric ratio is preferably 5 or less. The reason for this is that by adding boron, the hydrogen absorption pressure shifts to the high pressure side, albeit slightly, so the stoichiometric ratio is reduced to 5.0.
This is because it is necessary to maintain a low skewer fl pressure as follows. Further, when approximately 1.0 mol of boron is added, the stoichiometric ratio is preferably 5 or more. The reason for this is that the number of boron dipping layers in the alloy increases, and the stoichiometric ratio of the portion that actually absorbs and releases hydrogen is expected to become even smaller.
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、〜１はＮｉ、 Ｃｏ、Ｍｎ、 ＡＩ、Ｃ「、Ｆ
ｅ、 Ｃｕ、 Ｓｎ、 Ｓｂ、 Ｍｏ、’ｖ”、
Ｎｂ、 Ｔａ、Ｚ ｎ、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ｘ１）は３．５から６．０が望まし
い範囲と云うことができる。Taking these things together, in the chemical formula represented by ReBxMy, Re is one or more of rare earth elements and alkaline earth elements, and ~1 is Ni, Co, Mn, AI, C'', F.
e, Cu, Sn, Sb, Mo, 'v'',
One or more metals selected from Nb, Ta, Zn, Zr, and Ti, and X is 0.005 to 1.0
It can be said that the desirable range is 3.5 to 6.0 for x1).
次に本発明に係る水素吸蔵合金を掻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４０ ｗ
ｔ ’Ｆｆｙ含有するＮ１との母合金（Ｎ＋ｔ８３）を
用いた。Ｂを含有するＸｉ母合金を用いるのは、Ｂの単
体は融点が高＜（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４０ ｗ ｔ
％含有するＮ１との母合金の融点は＋ ４００℃である
。これらの原料を、Ｎ１Ｔ；＼ｉ＋ｃｏ：〜ｂ
＝ １ ° ３．４ ３ ３ ： ０．７ ：
０．８ ： ０．０ １ ７の割合に秤暖し高周
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 method of manufacturing the hydrogen storage alloy according to the present invention will be explained using electrode number No. 13. Approximately 40 w of Mm, Ni, Co, Mn, and B are used as raw materials.
A master alloy (N+t83) with N1 containing t'Ffy was used. The reason why the Xi master alloy containing B is used is that B alone has a high melting point (2180° C.) and cannot be melted in a normal high frequency induction furnace. In addition, approximately 40 wt of B
The melting point of the master alloy with N1 containing % is + 400 ° C. These raw materials are N1T; \i + co: ~ b = 1 ° 3.4 3 3: 0.7:
The desired hydrogen storage alloy is obtained by heating the mixture in a ratio of 0.8:0.017 and melting it in a high frequency induction furnace.
このようにして得た水Ｊ／：吸蔵合金を用いた電極番号
Ｎｏ、１３の電極に対してｌ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−′Ｆ）ｌ
Ｉ造を示す走査型電子顕微鏡写真（１へ率４０００倍）
を、第２図及び第３図に示す。第２図は水素Ｑｌｋ蔵合
金合金表面３図は表面層１１後のものである。対比例と
してｔ極番号Ｎｏ、＋２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（ｆへ率４０００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
の粒イー（Ｊ￥Ｊ＆をボ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、１２１に比べて大きなりう
７りが多く生じており、ｌサイクル目からｔ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
生するのはホウ素かり・／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、この部分の水素原りの拡散はホウ素のない表面層よ
り速いものと推祭される。これらの理由によりＬａＮｉ
、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」−に効果があることがわかる
。Water J/ thus obtained: Hydrogen storage alloy particles in the electrode after charging and discharging the electrode No. 13 using the storage alloy for 1 cycles -'F)l
Scanning electron micrograph showing I structure (4000x magnification)
are shown in FIGS. 2 and 3. FIG. 2 shows the surface of the hydrogen Qlk storage alloy. As a comparison, scanning electron micrographs (4000x magnification) showing the particle structure of the hydrogen storage alloy under the same conditions in a boron-free electrode with t-pole number No. +2 are shown in Figures 4 and 5. As shown in the figure. As is clear from the comparison of the photos of the grains E (J\J&) in Figures 2, 3, 4, and 5, the boron-doped electrode (No. 13) is Compared to the electrode (No. 121) that is not exposed to heat, many large cracks occur, and it can be confirmed that the t-pole reaction surface increases from the 1st cycle.These cracks occur due to boron. It is thought that the area near the surface of the newly formed surface becomes a boron-rich layer, but the diffusion of hydrogen atoms in this area is assumed to be faster than in the surface layer without boron. For these reasons, LaNi
It can be seen that the addition of boron to the rare earth-Ni alloy represented by , is effective in the initial activation of the electrode.
（ト） 発明の効果
本発明は以りの説明から明らかなように、希を類元素、
アルカリを類元素の一種以Ｌ、及びＮＩＣｏ、 Ｍｎ、
Ａ Ｉ、Ｃｒ、 Ｆｅ、Ｃｕ、 Ｓｎ、 Ｓｂ、 Ｍｏ
、Ｖ、Ｎｂ、Ｔａ、Ｚｎ、Ｚｒ、Ｔｉのうちから選ばれ
た一種以りの金属を主成分とする水１ｇ吸蔵合金にホウ
素を含ませているので、充放電の１サイクルロからｉｔ
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ｔ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 Invention As is clear from the following explanation, the present invention is based on rare elements,
One or more of the alkali elements, and NICo, Mn,
AI, Cr, Fe, Cu, Sn, Sb, Mo
, V, Nb, Ta, Zn, Zr, Ti, etc. Since boron is included in the water-absorbing alloy containing one or more metals selected from the group consisting mainly of metals selected from the group consisting of one or more metals selected from among,
The electrodes can be activated, high charging and discharging efficiency can be obtained from the initial stage of charging and discharging, and an alkaline storage battery having a sufficient t-vapor chemical capacity can be formed.
第１図は各ｆＩ重合組成における電極特性を示す図、第
２図乃至第５図はいずれら＠横巾における水素吸蔵給金
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ｔｉの１サイクル目充放電終了後の
粒子構造を示す写真、第１ｔｓ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 the electrode characteristics for each fI polymerization composition, and Figs. FIG. 3 is a photograph showing the particle structure of the inventive electrode after the first charging/discharging cycle, and FIG. 1TS and FIG. 5 are photographs showing the particle structure of the conventional electrode after the first charging/discharging cycle.
Claims (5)
、 Ｂ：ホウ素、 Ｍ：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、 ０．００５＜ｘ＜１．０、 ０．５＜ｙ＜６．０、 で表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。(1) Formula ReBxMy, where Re: one or more of rare earth elements and alkaline earth elements, B: boron, M: Ni, Co, Mn, Al, Cr, Fe, Cu, Sn
, Sb, Mo, V, Nb, Ta, Zn, Zr, and Ti, represented by 0.005<x<1.0, 0.5<y<6.0 Hydrogen storage alloy electrode for alkaline storage batteries made of hydrogen storage alloy.
℃の温度において、０．０５〜５気圧の範囲にある請求
項（１）記載のアルカリ蓄電池用水素吸蔵合金電極。(2) The equilibrium dissociation pressure of the hydride in the above hydrogen storage alloy is 40
The hydrogen storage alloy electrode for an alkaline storage battery according to claim 1, which has a pressure in the range of 0.05 to 5 atm at a temperature of .degree.
いることを特徴とする請求項（１）または（２）記載の
アルカリ蓄電池用水素吸蔵合金電極。(3) The hydrogen storage alloy electrode for an alkaline storage battery according to claim 1 or 2, wherein the component represented by M contains Co and Al.
いることを特徴とする請求項（１）または（２）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 or 2, wherein the component represented by M contains Co and Mn.
のうちのいずれかと、Ｍｏ、Ｚｒ、Ｃｒのうちから選ば
れた少なくとの一種と、が含まれていることを特徴とす
る請求項（１）または（２）記載のアルカリ蓄電池用水
素吸蔵合金電極。(5) The component represented by M above includes Co, Al or Mn.
The hydrogen storage alloy for alkaline storage batteries according to claim (1) or (2), characterized in that it contains at least one selected from Mo, Zr, and Cr. electrode.
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 true JPH03219036A (en) | 1991-09-26 |
| JP2999785B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0609609A3 (en) * | 1993-02-05 | 1994-08-31 | Sanyo Electric Co | |
| JP2012509399A (en) * | 2008-11-21 | 2012-04-19 | バオトウ リサーチ インスティチュート オブ レア アース | RE-Fe-B hydrogen storage alloy and use thereof |
-
1990
- 1990-01-22 JP JP2012932A patent/JP2999785B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0609609A3 (en) * | 1993-02-05 | 1994-08-31 | Sanyo Electric Co | |
| US5376474A (en) * | 1993-02-05 | 1994-12-27 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy for a negative electrode and manufacturing method therefor |
| JP2012509399A (en) * | 2008-11-21 | 2012-04-19 | バオトウ リサーチ インスティチュート オブ レア アース | RE-Fe-B hydrogen storage alloy and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2999785B2 (en) | 2000-01-17 |
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