JPH0227656A - Manufacture of alkaline storage battery and hydrogen storage alloy for alkaline storage battery - Google Patents
Manufacture of alkaline storage battery and hydrogen storage alloy for alkaline storage batteryInfo
- Publication number
- JPH0227656A JPH0227656A JP63178802A JP17880288A JPH0227656A JP H0227656 A JPH0227656 A JP H0227656A JP 63178802 A JP63178802 A JP 63178802A JP 17880288 A JP17880288 A JP 17880288A JP H0227656 A JPH0227656 A JP H0227656A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- metal
- alkaline
- storage battery
- storage alloy
- 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
- 238000003860 storage Methods 0.000 title claims abstract description 99
- 239000001257 hydrogen Substances 0.000 title claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 63
- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 239000006104 solid solution Substances 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 238000005266 casting Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910020794 La-Ni Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000006023 eutectic alloy Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- 229910008340 ZrNi Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、水素吸蔵合金を負極に用いる金属−水素アル
カリ蓄電池及びその水素吸蔵合金の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a metal-hydrogen alkaline storage battery using a hydrogen storage alloy as a negative electrode, and a method for manufacturing the hydrogen storage alloy.
（ロ）従来の技術
水素吸蔵合金を負極に備えたアルカリ蓄電池、例えばニ
ッケル酸化物正極と組み合わせたニッケルー水素蓄電池
等が、負極としてカドミウム極を用いるニッケルーカド
ミウム蓄電池に代わる新しいアルカリ蓄電池系として、
近年、研究開発が盛んに行われている。これら新型アル
カリ蓄電池では、負極の水素吸蔵合金を適当に選択する
ことにより、長寿命で、且つ高エネルギー密度を得るこ
とが可能である。(b) Conventional technology Alkaline storage batteries equipped with hydrogen storage alloys as negative electrodes, such as nickel-hydrogen storage batteries in combination with nickel oxide positive electrodes, are being used as new alkaline storage battery systems to replace nickel-cadmium storage batteries that use cadmium electrodes as negative electrodes.
In recent years, research and development has been actively conducted. These new types of alkaline storage batteries can have a long life and high energy density by appropriately selecting a hydrogen storage alloy for the negative electrode.
しかし、これら新型アルカリ蓄電池の自己放電に関して
は、前記ニッケルーカドミウム蓄電池と比べ自己放電量
が多くなることが知られており、その特性の改善が望ま
れる。However, regarding the self-discharge of these new type alkaline storage batteries, it is known that the amount of self-discharge is greater than that of the nickel-cadmium storage batteries, and it is desired to improve their characteristics.
ところで、上記自己放電の機構に間しては未だ十分に解
明されていないが、例えば前記ニッケルー水素蓄電池の
場合には、主に以下に示す理由によって自己放電が発生
するものと考えられる。Incidentally, although the mechanism of self-discharge has not yet been fully elucidated, it is thought that, for example, in the case of the nickel-metal hydride storage battery, self-discharge occurs mainly for the following reasons.
（１）水素極からの水素解離とニッケル正極の水素消費
。(1) Hydrogen dissociation from the hydrogen electrode and hydrogen consumption at the nickel positive electrode.
（２） ニッケル正極からの酸素発生と水素極の酸素消
費。(2) Oxygen generation from the nickel positive electrode and oxygen consumption at the hydrogen electrode.
そこで例えば、特開昭６２−１５７６０号公報や、特開
昭６１−２８５６５８号公報に示すように、水素吸蔵合
金粉末をアルカリ処理することによりその表面に酸化物
を形成させ、水素解離速度を抑制させるようなものが提
案されている。For example, as shown in JP-A-62-15760 and JP-A-61-285658, hydrogen storage alloy powder is treated with alkali to form oxides on its surface, thereby suppressing the rate of hydrogen dissociation. Something has been proposed to do so.
しかし、上記の如く水素吸蔵合金粉末をアルカリ処理し
た場合には、酸化物の被膜を合金の表面に均一に形成す
ることが困難であり、自己放電の抑制には十分ではない
。However, when the hydrogen storage alloy powder is treated with alkali as described above, it is difficult to uniformly form an oxide film on the surface of the alloy, and this is not sufficient to suppress self-discharge.
上記問題を解決するため、本発明者等は、水素吸蔵合金
粉末及びアルカリ溶液中で標準水素発生電位より卑な電
位を示す金属粉末の混合物からなる負極を電池缶内に挿
入した後、アルカリ電解液を電池缶内に注入し、前記添
加せる金属粉末をアルカリ電解液と反応させる密閉型ア
ルカリ蓄電池の製造方法を提案しなく特願昭６２−２６
４７５７号）。In order to solve the above problem, the present inventors inserted a negative electrode made of a mixture of hydrogen-absorbing alloy powder and metal powder that exhibits a potential less base than the standard hydrogen generation potential in an alkaline solution into a battery can, and then carried out alkaline electrolysis. Patent Application No. 1982-26 proposes a manufacturing method for a sealed alkaline storage battery in which a liquid is injected into a battery can and the added metal powder is reacted with an alkaline electrolyte.
No. 4757).
上記方法によれば、水素吸蔵合金と標準水素発生電位よ
り卑な電位を示す金属粉末とをアルカリ電解液と反応さ
せると、前記金属粉末は溶出し、酸化される。この際、
前記金属粉末の酸化物は。According to the above method, when a hydrogen storage alloy and a metal powder exhibiting a potential less noble than a standard hydrogen generation potential are reacted with an alkaline electrolyte, the metal powder is eluted and oxidized. On this occasion,
The metal powder oxide.
水素吸蔵合金表面に均一な酸化被膜を形成することがで
きる。その結果、正極から発生せる酸素ガスの水素極で
の吸収反応及び水素極からの水素解離反応、それぞれの
速度を小さくできるので、自己放電の抑制された電池を
得ることができる。A uniform oxide film can be formed on the surface of the hydrogen storage alloy. As a result, the rates of the absorption reaction of oxygen gas generated from the positive electrode at the hydrogen electrode and the hydrogen dissociation reaction from the hydrogen electrode can be reduced, making it possible to obtain a battery in which self-discharge is suppressed.
（桐発明が解決しようとする課題
前記方法では、工程中に水素吸蔵合金粉末と、標準水素
発生電位よりも卑な電位を示す添加金属粉末の粒度調整
、混合、撹拌の工程が必要である。(Problems to be Solved by the Paulownia Invention) The method described above requires steps of particle size adjustment, mixing, and stirring of the hydrogen-absorbing alloy powder and the additive metal powder exhibiting a potential less base than the standard hydrogen generation potential.
そこでこれらの工程を簡略化すると共に、均一に両者を
混合することができれば、かかる方法により得られた水
素吸蔵合金の保存特性を更に向上させることが可能とな
る。Therefore, if these steps can be simplified and both can be mixed uniformly, it will be possible to further improve the storage characteristics of the hydrogen storage alloy obtained by this method.
本発明はかかる問題点に鑑みてなされたものであって、
製造工程の簡易なアルカリ蓄電池用水素吸蔵合金の製造
方法を提案すると共に、かかる均質な組成の合金を負極
に用いた金属−水素アルカリ蓄電池を提供しようとする
ものである。The present invention has been made in view of such problems, and includes:
The present invention proposes a method for manufacturing a hydrogen storage alloy for alkaline storage batteries with a simple manufacturing process, and also attempts to provide a metal-hydrogen alkaline storage battery using such a homogeneous composition alloy for the negative electrode.
（ニ）課題を解決するための手段
本発明の金属−水素アルカリ蓄電池は、可逆的に水素を
吸蔵、放出し得る金属間化合物相と、アルカリ溶液中で
標準水素発生電位より卑なる電位を示す添加金属の純金
属相もしくはその固溶体相とからなる水素吸蔵合金を、
負極に用いたことを特徴とするものである。(d) Means for Solving the Problems The metal-hydrogen alkaline storage battery of the present invention has an intermetallic compound phase that can reversibly absorb and release hydrogen, and exhibits a potential less noble than the standard hydrogen evolution potential in an alkaline solution. A hydrogen storage alloy consisting of a pure metal phase of an additive metal or its solid solution phase,
It is characterized by being used as a negative electrode.
また本発明のアルカリ蓄電池用水素吸蔵合金の製造方法
は、可逆的に水素を吸蔵、放出し得る金属間化合物と、
アルカリ溶液中で標準水素発生電位より卑なる電位を示
す添加金属とを添加して溶湯となし、前記溶湯を冷却し
て水素吸蔵合金を鋳造することにより、前記添加金属の
純金属相もしくは固溶体相及び前記金属間化合物相とを
前記水素吸蔵合金中に形成したことを特徴とするもので
ある。前記金属間化合物は、Ａ Ｂ ｑ型穴方晶構造を
有し、Ａは希土類元素もしくはＣａのうちから遼ばれた
少なくとも１種、Ｂは第１遷移金属のうちから選ばれた
少なくとも１種であることを特徴とするものである。Further, the method for producing a hydrogen storage alloy for alkaline storage batteries of the present invention includes an intermetallic compound that can reversibly store and release hydrogen;
A pure metal phase or a solid solution phase of the additive metal and a hydrogen storage alloy are formed by adding an additive metal exhibiting a potential less base than the standard hydrogen generation potential in an alkaline solution to form a molten metal, and cooling the molten metal to cast a hydrogen storage alloy. The intermetallic compound phase is formed in the hydrogen storage alloy. The intermetallic compound has an AB q-type holegonal crystal structure, A is at least one selected from rare earth elements or Ca, and B is at least one selected from first transition metals. It is characterized by certain things.
又、前記希土類元素としては、Ｌａ、Ｃｅ、Ｎｄ、、Ｐ
ｒ、Ｓｍのうちから選ばれた少なくとも１種、もしくは
それらの混合物、第１遷移金属としては、Ｃｒ、Ｍｎ、
Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕのうちから選ばれた少なくとも
１種が用いられる。In addition, the rare earth elements include La, Ce, Nd, P
At least one selected from r, Sm, or a mixture thereof, and the first transition metal is Cr, Mn,
At least one selected from Fe, Co, Ni, and Cu is used.
更に、前記金属間化合物相は、ＡＢ型立方晶樽造もしく
はＡＢ２型六方晶構造を有し、ＡはＴｉ、Ｚｒ、Ｖ、ア
ルカリ土類金属のうちから選ばれた少なくとも１種、Ｂ
は第１遷移金属のうちから選ばれた少なくとも１種であ
ることを特徴とするものである。そしてここにおいて、
前記アルカリ土類金属としては、Ｃａ、Ｍｇのうちから
選ばれた少なくとも１種、第１遷移金属としては、Ｃｒ
、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕのうちから選ばれた少
なくとも１種が用いられる。Furthermore, the intermetallic compound phase has an AB type cubic barrel structure or an AB2 type hexagonal structure, where A is at least one selected from Ti, Zr, V, and an alkaline earth metal;
is at least one selected from first transition metals. And here,
The alkaline earth metal is at least one selected from Ca and Mg, and the first transition metal is Cr.
, Mn, Fe, Co, Ni, and Cu.
また前記添加金属としては、ＡＱ、Ｚｎ、アルカリ土類
金属のうちから選ばれた少なくとも１種が使用され、更
に、アルカリ土類金属としては、Ｂｅ、Ｍｇ、Ｃａのう
ちから選ばれた少なくとも１種が用いられる。Further, as the additive metal, at least one selected from AQ, Zn, and an alkaline earth metal is used, and further, as the alkaline earth metal, at least one selected from Be, Mg, and Ca is used. Seeds are used.
（ネ）作 用
金属間化合物相と、純金属相もしくはその固溶体相より
なる共存組成の溶湯に、アルカリ溶液中で標準水素発生
電位よりも卑なる電位を示す添加金属を添加して、冷却
すると、水素を吸蔵、放出し得る金属間化合物相と、自
己放電抑制効果を有する前記添加金属の純金属相もしく
は固溶体相が生成する。これは共晶組織と呼ばれ、良電
気伝導体であり、数ミクロンの間隔で層状となっている
。その結果、自己放電を抑制する効果を有する添加金属
が、水素を吸蔵、放出し得る金属間化合物の組成に直接
影響を与えず、金属間化合物のまわりに均一に分布する
ことになり、アルカリ溶液と反応させることにより金属
間化合物を前記添加金属の酸化物層で均一に被覆するこ
とができる。(4) Effect When a molten metal with a coexisting composition consisting of an intermetallic compound phase and a pure metal phase or its solid solution phase is added with an additive metal exhibiting a potential less base than the standard hydrogen generation potential in an alkaline solution and cooled, An intermetallic compound phase that can absorb and release hydrogen, and a pure metal phase or solid solution phase of the added metal that has a self-discharge suppressing effect are generated. This is called a eutectic structure, which is a good electrical conductor, and is layered at intervals of several microns. As a result, the added metal, which has the effect of suppressing self-discharge, does not directly affect the composition of the intermetallic compound that can absorb and release hydrogen, but is uniformly distributed around the intermetallic compound, and the alkaline solution By reacting with the intermetallic compound, the intermetallic compound can be uniformly coated with the oxide layer of the added metal.
従って、この合金を一定粒度に粉砕するだけで負極に用
いることができ、従来の如く、水素吸蔵合金と添加金属
を各々粉砕し、両者の粒度調整を行い、その後混合、撹
拌するという一連の煩雑な工程を簡略化しうる。Therefore, this alloy can be used for a negative electrode simply by pulverizing it to a certain particle size, and unlike conventional methods, it requires a series of complicated steps such as pulverizing the hydrogen storage alloy and the additive metal, adjusting the particle size of both, and then mixing and stirring. The process can be simplified.
更に・前記組成を有する合金は、添加金属が、水素吸蔵
合金中に均一に含まれているので、均質なものが得られ
る。その結果、添加金属を粉末状で単に添加するものに
比べ、分散性が高くなり、保存特性を向上させる作用を
発揮する酸化物層の金属間化合物表面への形成が、きわ
めて効率良く行える。Furthermore, since the alloy having the above composition contains the additive metal uniformly in the hydrogen storage alloy, a homogeneous alloy can be obtained. As a result, compared to the case where the additive metal is simply added in powder form, the dispersibility becomes higher and an oxide layer that exhibits the effect of improving storage characteristics can be formed on the surface of the intermetallic compound extremely efficiently.
（へ）実施例 以下、本発明の詳細な説明する。(f) Example The present invention will be explained in detail below.
（実施例１）
先ず始めに、ＬａＮｉ、相とＡＩ２を含むＮｉ相から成
る共晶合金を、以下の手順で作成した。(Example 1) First, a eutectic alloy consisting of a LaNi phase and a Ni phase containing AI2 was created by the following procedure.
原料金属であるＬａ、Ｎｉ及びＡ？アルカリ溶液中で標
準水素発生電位より卑なる電位を示す添加金属）を、Ｌ
ａとＮｉの共晶組成である、Ｌａ１８重量％、Ｎｉ８１
重量％、Ａρ１重呈％となるように秤量、混合した後、
所望寸法にプレス成型する。次に水冷銅鋳型内にて、ア
ルゴンアークにより溶解後溶湯とし、鋳造して、Ｌ、Ｎ
ｉ、相反光学顕微鏡観察の結果、層間隔が数μｍ乃至数
十μｍの層状の共晶組織を呈することを確認した。Raw material metals La, Ni and A? The additive metal (which exhibits a potential more base than the standard hydrogen evolution potential in an alkaline solution) is
The eutectic composition of a and Ni is 18% by weight of La and 81% of Ni.
After weighing and mixing so that weight% and Aρ1 weight%,
Press mold to desired dimensions. Next, in a water-cooled copper mold, the molten metal is melted with an argon arc and cast.
i. As a result of reciprocal optical microscopy observation, it was confirmed that the material exhibited a layered eutectic structure with a layer spacing of several μm to several tens of μm.
更に、この共晶合金のＬ４Ｎｉ、相とＮｉ相との比率は
状態図より３：２（重量比）と推定され、Ｎｉ相は約４
０重量％含まれる。こうして得られた共晶組織をもつ水
素吸蔵合金を、機械的に５０μｍ以下になるように粉砕
し、これに対して結着剤としてのポリテトラフルオロエ
チレン（ＰＴＦＥ）を１０重量％の割合で添加した後、
これらを混合してペーストを作製する。しかる後、この
ペーストを集電体の両面に貼り付け、水素吸蔵合金負極
（以下、水素極と略す）を作製した。この後、この水素
極を公知の１．２ＡＨｒ焼結式ニッケル極、及び不織布
（セパレータ）と共に巻き取り、電極体を作製する。次
いで、この電極体を電池缶内に挿入した後、上記電池缶
内にアルカリ電解液（３０％ＫＯＨ溶液）を注入する０
次に電池缶を封入し、密閉型ニッケルー水素蓄電池を作
製した。Furthermore, the ratio of the L4Ni phase to the Ni phase in this eutectic alloy is estimated to be 3:2 (weight ratio) from the phase diagram, and the Ni phase is approximately 4:2 (weight ratio).
Contains 0% by weight. The thus obtained hydrogen storage alloy with a eutectic structure is mechanically crushed to a size of 50 μm or less, and polytetrafluoroethylene (PTFE) is added as a binder at a ratio of 10% by weight. After that,
These are mixed to make a paste. Thereafter, this paste was applied to both sides of the current collector to produce a hydrogen storage alloy negative electrode (hereinafter abbreviated as hydrogen electrode). Thereafter, this hydrogen electrode is wound together with a known 1.2AHr sintered nickel electrode and a nonwoven fabric (separator) to produce an electrode body. Next, after inserting this electrode body into the battery can, an alkaline electrolyte (30% KOH solution) is injected into the battery can.
Next, the battery can was sealed to create a sealed nickel-metal hydride storage battery.
以下、この電池を本発明電池Ａと称する。Hereinafter, this battery will be referred to as the battery A of the present invention.
電池の自己放電特性を比較するため、従来の水（比較例
１）
ＬａとＮｉとの重量比が、３２重量％と６８重量％とな
るように秤ｉ後、アーク炉で合金化し、この合金を５０
μｍ以下に粉砕後、４００メツシユ以下の粒度のＮｉ粉
末を上記合金粉末重量に対して４０重量％添加し、均一
に混合、撹拌する。In order to compare the self-discharge characteristics of batteries, conventional water (Comparative Example 1) was weighed so that the weight ratio of La and Ni was 32% by weight and 68% by weight, and then alloyed in an arc furnace. 50
After pulverizing to micrometers or less, Ni powder having a particle size of 400 mesh or less is added in an amount of 40% by weight based on the weight of the alloy powder, and the mixture is uniformly mixed and stirred.
この混合粉末に対して結着剤を加えた以外は、以比較電
池Ｘと称する。この比較電池Ｘには、ＡＱが添加されて
いない。This battery will be referred to as Comparative Battery X, except that a binder was added to this mixed powder. AQ was not added to this comparative battery X.
（比較例２）
ＬａとＮｉとの重量比が、３２重量％と６８重量％とな
るようにアーク炉で合金化し、この合金を５０μｍ以下
に粉砕後、４００メツシユ以下の粒度のＮｉ粉末を上記
合金粉末重量に対して４０重量％、粒度調整を行い４０
０メツシユ以下としたＡρ粉末を１重量％添加し、均一
に混合、撹拌する。この混合粉末に対して結着剤を加え
た以外は、以下実施例１と同様の手順で、負極及び密閉
型ニッケルー水素蓄電池を作需した。以下、この電池を
比較電池Ｙと称する。(Comparative Example 2) Alloyed in an arc furnace so that the weight ratio of La and Ni was 32% by weight and 68% by weight, and after pulverizing this alloy to 50 μm or less, Ni powder with a particle size of 400 mesh or less was added to the above. 40% by weight based on the alloy powder weight, particle size adjusted to 40%
Add 1% by weight of Aρ powder having a mesh size of 0 or less, and mix and stir uniformly. A negative electrode and a sealed nickel-metal hydride storage battery were prepared in the same manner as in Example 1 except that a binder was added to this mixed powder. Hereinafter, this battery will be referred to as comparative battery Y.
ここで上記本発明電池Ａと、比較電池Ｘ及び比較電池Ｙ
とを所定期間保存し、これらの電池の残存容量率を測定
した。この結果を、第１図に示す。Here, the above invention battery A, comparative battery X, and comparative battery Y
and were stored for a predetermined period of time, and the remaining capacity ratio of these batteries was measured. The results are shown in FIG.
尚、保存条件は常温（３０℃）とした。Note that the storage conditions were room temperature (30°C).
第１図より明らかなように、本発明電池Ａの１０日間保
存後の残存容量率は約８０％であり、この値はＡρ粉末
を添加しない比較電池Ｙの約３０％に対してかなり大き
い値と言える。また、／１７２粉末の粒度調整、混合、
撹拌工程をもつ比較電池Ｙと比較しても、負極に用いた
水素吸蔵合金が均一な組成である本発明電池Ａは、保存
特性において優れていることがわかる。As is clear from FIG. 1, the remaining capacity rate of the battery A of the present invention after 10 days of storage is approximately 80%, which is considerably larger than the approximately 30% of the comparative battery Y, which does not contain Aρ powder. I can say that. In addition, /172 powder particle size adjustment, mixing,
Even when compared with Comparative Battery Y, which has a stirring process, it can be seen that Battery A of the present invention, in which the hydrogen storage alloy used in the negative electrode has a uniform composition, has excellent storage characteristics.
（実施例２）
前記実施例１において、アルカリ溶液中で標準水素発生
電位より卑なる電位を示す添加金属である八ρの代わり
にＺｎを用いた以外は前記実施（比較例３）
前記比較例２おいてＡｐの代わりにＺｎを用比較電池Ｚ
とする。(Example 2) In the above-mentioned Example 1, except that Zn was used instead of 8ρ, which is an additive metal that exhibits a potential more base than the standard hydrogen generation potential in an alkaline solution (Comparative Example 3) The above-mentioned Comparative Example Comparative battery Z using Zn instead of Ap in 2
shall be.
ここで本発明電池Ｂ、前記比較電池Ｙ及び比較電池Ｚを
用い、前記同様の保存特性の比較を行った。Here, using the present invention battery B, the comparative battery Y, and the comparative battery Z, the storage characteristics were compared in the same manner as described above.
この結果を、第２図に示す。これより本発明電池Ｂの１
０日間保存後の残存容量率は約７０％であり、Ｚｎ粉末
を添加しない比較電池Ｙの約３０％に比してかなり優れ
た保存特性を有している。The results are shown in FIG. From this, 1 of the invention battery B
The remaining capacity rate after storage for 0 days was about 70%, which was considerably better than about 30% for Comparative Battery Y to which no Zn powder was added.
又、Ｚｎ粉末の粒度調整、混合、撹拌工程を有する比較
電池Ｚに比して５本発明電池Ｂは負極の水素吸蔵合金が
均質な組成を有し、前記添加せる添加金属の酸化物層に
より金属間化合物全体がより一層均−に覆われているの
で、その分だけ保存特性において優れている。Furthermore, compared to Comparative Battery Z, which includes the steps of adjusting the particle size of Zn powder, mixing, and stirring, in Battery B of the present invention, the hydrogen storage alloy of the negative electrode has a homogeneous composition, and the oxide layer of the additive metal added Since the entire intermetallic compound is more evenly covered, the storage properties are improved accordingly.
この傾向は実施例１と同様であった。This tendency was the same as in Example 1.
但し、Ｚｎを添加した電池の保存特性は、Ａｐを添加し
た電池の特性より若干低いと言えるが、これはＺｎがＡ
ｐよりアルカリ中でやや酸化し難いためと考えられる。However, it can be said that the storage characteristics of batteries with Zn added are slightly lower than those of batteries with Ap added, but this is because Zn is
This is thought to be because it is slightly more difficult to oxidize in alkali than p.
尚、上記の実施例における添加する添加金属としてＡｐ
とＺｎとを示したが、これらの金属に限定されるもので
はなくアルカリ中で酸化される他の金属粉末Ｂｅ、Ｍｇ
、Ｃａ等のアルカリ土類金属であっても同様の効果を得
ることがあった。Incidentally, as the additive metal added in the above example, Ap
and Zn, but it is not limited to these metals, and other metal powders Be, Mg, which are oxidized in alkali.
Similar effects may be obtained even with alkaline earth metals such as , Ca, etc.
第３図に２本発明に用いたＬａ−Ｎｉ２元系合金の状態
図を示す。ここで本発明に用いる可逆的に水素を吸蔵、
放出し得る金属間化合物としては、次のものを用いる必
要がある。即ち、ＬａとＮｉの混合比率は、前記実施例
に示した共晶組成に限るものではなく、第３図に示すよ
うに、Ｎｉが６７．８重量％より大きく１００重量％未
満であれば、共晶組成を含む合金鋳塊を得ることができ
、本発明のアルカリ蓄電池用水素吸蔵合金として使用し
うる。FIG. 3 shows a phase diagram of the La-Ni binary alloy used in the present invention. Here, reversibly absorbing hydrogen used in the present invention,
As intermetallic compounds that can be released, it is necessary to use the following: That is, the mixing ratio of La and Ni is not limited to the eutectic composition shown in the above example, but as shown in FIG. 3, if Ni is greater than 67.8% by weight and less than 100% by weight, An alloy ingot containing a eutectic composition can be obtained and can be used as the hydrogen storage alloy for alkaline storage batteries of the present invention.
前記実施例においてはＬａ−Ｎｉ２元系合金を用いたが
、第３図と同様の状態図を示す、Ｃｅ、Ｎｄ、Ｐｒ、Ｓ
ｍなどの希土類あるいはこれらの混合物もしくはＣａと
、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕなどの第１遷移
金属とからなるＡＢ。Although the La-Ni binary alloy was used in the above example, Ce, Nd, Pr, S
AB consisting of a rare earth element such as m or a mixture thereof, or Ca, and a first transition metal such as Cr, Mn, Fe, Co, Ni, or Cu.
型六方晶構造の合金や、Ｔｉ、Ｚｒ、■又はＣａ、Ｍｇ
などのアルカリ土類金属とＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎ
ｉ、Ｃｕなどの第１遷移金属とからなるＡＢ型立方晶楕
遣もしくはＡＢＺ型六万晶構造の合金を用いることがで
きる。Hexagonal crystal structure alloys, Ti, Zr, ■ or Ca, Mg
Alkaline earth metals such as Cr, Mn, Fe, Co, N
An alloy having an AB type cubic elliptic structure or an ABZ type hexagonal crystal structure consisting of a first transition metal such as i, Cu, etc. can be used.
更にＡＢ、型合金の具体例としては、Ｌ ａ ＣＯ。Furthermore, as a specific example of AB type alloy, L a CO.
ＣａＮｉ、、ＬａＣｕ、等、ＡＢ型合金の具体例として
は、ＴｉＦｅ、Ｔ１Ｃｏ、Ｔ１Ｎｉ、ＺｒＮｉ等、ＡＢ
２型合金の具体例としては、ＴｉＭｎ１．５、ＺｎＭｎ
ｚ′Ｊ、更にはそれらの一部を置換したものが挙げられ
る。Specific examples of AB type alloys such as CaNi, LaCu, etc. include AB type alloys such as TiFe, T1Co, T1Ni, ZrNi, etc.
Specific examples of type 2 alloys include TiMn1.5, ZnMn
z'J, and further substituted parts thereof.
（ト）発明の効果
本発明によれば、自己放電を抑制しうる水素吸蔵合金の
製造工程を簡略化しうるちのであり、かかる均質な水素
吸蔵合金を負極に用いたアルカリ蓄電池の保存特性を向
上しうるので、その工業的価値は極めて大きい。(G) Effects of the Invention According to the present invention, the manufacturing process of a hydrogen storage alloy capable of suppressing self-discharge can be simplified, and the storage characteristics of an alkaline storage battery using such a homogeneous hydrogen storage alloy as a negative electrode can be improved. Therefore, its industrial value is extremely large.
第１図及び第２図は電池の保存・特性を示す図、第３図
はＬａ−Ｎｉ２元系合金の状態図の一部を示す図でｈろ
。
Ａ、Ｂ・・・本発明電池、ｘ、ｙ、ｚ・・・比較電池。Figures 1 and 2 are diagrams showing storage and characteristics of batteries, and Figure 3 is a diagram showing part of a phase diagram of a binary La-Ni alloy. A, B...Battery of the present invention, x, y, z...Comparative battery.
Claims (1)
とアルカリ溶液中で標準水素発生電位より卑なる電位を
示す添加金属の純金属相もしくはその固溶体相とからな
る水素吸蔵合金を、負極に用いたことを特徴とする金属
−水素アルカリ蓄電池。 （２）前記金属間化合物相は、ＡＢ＿５型六方晶構造を
有し、Ａは希土類元素もしくはＣａのうちから選ばれた
少なくとも１種、Ｂは第１遷移金属のうちから選ばれた
少なくとも１種であることを特徴とする請求項１記載の
金属−水素アルカリ蓄電池。 （３）前記希土類元素は、Ｌａ、Ｃｅ、Ｎｄ、Ｐｒ、Ｓ
ｍのうちから選ばれた少なくとも１種もしくはそれらの
混合物からなることを特徴とする請求項２記載の金属−
水素アルカリ蓄電池。 （４）前記第１遷移金属は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、
Ｎｉ、Ｃｕのうちから選ばれた少なくとも１種であるこ
とを特徴とする請求項２記載の金属−水素アルカリ蓄電
池。 （５）前記金属間化合物相は、ＡＢ型立方晶構造もしく
はＡＢ＿２型六方晶構造を有し、ＡはＴｉ、Ｚｒ、Ｖ、
アルカリ土類金属のうちから選ばれた少なくとも１種、
Ｂは第１遷移金属のうちから選ばれた少なくとも１種で
あることを特徴とする請求項１記載の金属−水素アルカ
リ蓄電池。 （６）前記アルカリ土類金属は、Ｃａ、Ｍｇのうちから
選ばれた少なくとも１種であることを特徴とする請求項
（５）記載の金属−水素アルカリ蓄電池。 （７）前記第１遷移金属は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、
Ｎｉ、Ｃｕのうちから選ばれた少なくとも１種であるこ
とを特徴とする請求項（５）記載の金属−水素アルカリ
蓄電池。 （８）前記添加金属は、Ａｌ、Ｚｎ、アルカリ土類金属
のうちから選ばれた少なくとも１種であることを特徴と
する請求項（１）記載の金属−水素アルカリ蓄電池。 （９）前記アルカリ土類金属は、Ｂｅ、Ｍｇ、Ｃａのう
ちから選ばれた少なくとも１種であることを特徴とする
請求項（８）記載の金属−水素アルカリ蓄電池。 （１０）可逆的に水素を吸蔵、放出し得る金属間化合物
と、アルカリ溶液中で標準水素発生電位より卑なる電位
を示す添加金属とを添加して溶湯となし、前記溶湯を冷
却して水素吸蔵合金を鋳造することにより、前記添加金
属の純金属相もしくは固溶体相及び前記金属間化合物相
とを前記水素吸蔵合金中に形成したことを特徴とするア
ルカリ蓄電池用水素吸蔵合金の製造方法。 （１１）前記金属間化合物相は、ＡＢ＿５型六方晶構造
を有し、Ａは希土類元素もしくはＣａのうちから選ばれ
た少なくとも１種、Ｂは第１遷移金属のうちから選ばれ
た少なくとも１種であることを特徴とする請求項（１０
）記載のアルカリ蓄電池用水素吸蔵合金の製造方法。 （１２）前記希土類元素は、Ｌａ、Ｃｅ、Ｎｄ、Ｐｒ、
Ｓｍのうちから選ばれた少なくとも１種、もしくはそれ
らの混合物からなることを特徴とする請求項（１１）記
載のアルカリ蓄電池用水素吸蔵合金の製造方法。 （１３）前記第１遷移金属は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ
、Ｎｉ、Ｃｕのうちから選ばれた少なくとも１種である
ことを特徴とする請求項（１１）記載のアルカリ蓄電池
用水素吸蔵合金の製造方法。 （１４）前記金属間化合物相は、ＡＢ型立方晶構造もし
くはＡＢ＿２型六方晶構造を有し、ＡはＴｉ、Ｚｒ、Ｖ
、アルカリ土類金属のうちから選ばれた少なくとも１種
、Ｂは、第１遷移金属のうちから選ばれた少なくとも１
種であることを特徴とする請求項（１０）記載のアルカ
リ蓄電池用水素吸蔵合金の製造方法。 （１５）前記アルカリ土類金属は、Ｃａ、Ｍｇのうちか
ら選ばれた少なくとも１種であることを特徴とする請求
項（１４）記載のアルカリ蓄電池用水素吸蔵合金の製造
方法。 （１５）前記第１遷移金属は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ
、Ｎｉ、Ｃｕのうちから選ばれた少なくとも１種である
ことを特徴とする請求項（１４）記載のアルカリ蓄電池
用水素吸蔵合金の製造方法。 （１７）前記添加金属は、Ａｌ、Ｚｎ、アルカリ土類金
属のうちから選ばれた少なくとも１種であることを特徴
とする請求項（１０）記載のアルカリ蓄電池用水素吸蔵
合金の製造方法。 （１８）前記アルカリ土類金属は、Ｂｅ、Ｍｇ、Ｃａの
うちから選ばれた少なくとも１種であることを特徴とす
る請求項（１７）記載のアルカリ蓄電池用水素吸蔵合金
の製造方法。[Scope of Claims] (1) Consisting of an intermetallic compound phase that can reversibly absorb and release hydrogen and a pure metal phase of the added metal or its solid solution phase that exhibits a potential less base than the standard hydrogen generation potential in an alkaline solution. A metal-hydrogen alkaline storage battery characterized by using a hydrogen storage alloy for the negative electrode. (2) The intermetallic compound phase has an AB_5 type hexagonal crystal structure, where A is at least one selected from rare earth elements or Ca, and B is at least one selected from first transition metals. The metal-hydrogen alkaline storage battery according to claim 1, characterized in that: (3) The rare earth elements include La, Ce, Nd, Pr, and S.
The metal according to claim 2, characterized in that the metal comprises at least one selected from m or a mixture thereof.
Hydrogen alkaline storage battery. (4) The first transition metal is Cr, Mn, Fe, Co,
The metal-hydrogen alkaline storage battery according to claim 2, characterized in that the metal-hydrogen alkaline storage battery is at least one selected from Ni and Cu. (5) The intermetallic compound phase has an AB type cubic structure or an AB_2 type hexagonal structure, and A is Ti, Zr, V,
At least one selected from alkaline earth metals,
2. The metal-hydrogen alkaline storage battery according to claim 1, wherein B is at least one selected from first transition metals. (6) The metal-hydrogen alkaline storage battery according to claim (5), wherein the alkaline earth metal is at least one selected from Ca and Mg. (7) The first transition metal is Cr, Mn, Fe, Co,
The metal-hydrogen alkaline storage battery according to claim 5, characterized in that the metal-hydrogen alkaline storage battery is at least one selected from Ni and Cu. (8) The metal-hydrogen alkaline storage battery according to claim (1), wherein the additive metal is at least one selected from Al, Zn, and alkaline earth metals. (9) The metal-hydrogen alkaline storage battery according to claim (8), wherein the alkaline earth metal is at least one selected from Be, Mg, and Ca. (10) A molten metal is prepared by adding an intermetallic compound that can reversibly absorb and release hydrogen and an additive metal that exhibits a potential less base than the standard hydrogen generation potential in an alkaline solution, and the molten metal is cooled to produce hydrogen. A method for producing a hydrogen storage alloy for an alkaline storage battery, characterized in that a pure metal phase or solid solution phase of the additive metal and the intermetallic compound phase are formed in the hydrogen storage alloy by casting the storage alloy. (11) The intermetallic compound phase has an AB_5 hexagonal structure, A is at least one selected from rare earth elements or Ca, and B is at least one selected from first transition metals. Claim (10)
) A method for producing a hydrogen storage alloy for alkaline storage batteries. (12) The rare earth elements include La, Ce, Nd, Pr,
The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim 11, characterized in that the hydrogen storage alloy is made of at least one selected from Sm or a mixture thereof. (13) The first transition metal is Cr, Mn, Fe, Co
12. The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim 11, wherein the hydrogen storage alloy is at least one selected from the group consisting of , Ni, and Cu. (14) The intermetallic compound phase has an AB type cubic structure or an AB_2 type hexagonal structure, and A is Ti, Zr, V
, at least one selected from alkaline earth metals, and B is at least one selected from first transition metals.
The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim 10, wherein the hydrogen storage alloy is a seed. (15) The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim (14), wherein the alkaline earth metal is at least one selected from Ca and Mg. (15) The first transition metal is Cr, Mn, Fe, Co
15. The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim 14, wherein the hydrogen storage alloy is at least one selected from among , Ni, and Cu. (17) The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim (10), wherein the additional metal is at least one selected from Al, Zn, and alkaline earth metals. (18) The method for producing a hydrogen storage alloy for an alkaline storage battery according to claim (17), wherein the alkaline earth metal is at least one selected from Be, Mg, and Ca.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63178802A JPH07118314B2 (en) | 1988-07-18 | 1988-07-18 | Method of manufacturing alkaline storage battery and hydrogen storage alloy for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63178802A JPH07118314B2 (en) | 1988-07-18 | 1988-07-18 | Method of manufacturing alkaline storage battery and hydrogen storage alloy for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0227656A true JPH0227656A (en) | 1990-01-30 |
| JPH07118314B2 JPH07118314B2 (en) | 1995-12-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63178802A Expired - Fee Related JPH07118314B2 (en) | 1988-07-18 | 1988-07-18 | Method of manufacturing alkaline storage battery and hydrogen storage alloy for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118314B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049230A (en) * | 2001-08-08 | 2003-02-21 | Japan Atom Energy Res Inst | Hydrogen storage alloy |
-
1988
- 1988-07-18 JP JP63178802A patent/JPH07118314B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049230A (en) * | 2001-08-08 | 2003-02-21 | Japan Atom Energy Res Inst | Hydrogen storage alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118314B2 (en) | 1995-12-18 |
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