JP3454615B2 - Hydrogen storage alloy electrode and method for producing the same - Google Patents
Hydrogen storage alloy electrode and method for producing the sameInfo
- Publication number
- JP3454615B2 JP3454615B2 JP21455995A JP21455995A JP3454615B2 JP 3454615 B2 JP3454615 B2 JP 3454615B2 JP 21455995 A JP21455995 A JP 21455995A JP 21455995 A JP21455995 A JP 21455995A JP 3454615 B2 JP3454615 B2 JP 3454615B2
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- JP
- Japan
- Prior art keywords
- alloy
- hydrogen storage
- powder
- storage alloy
- electrode
- 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.)
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Links
- 239000000956 alloy Substances 0.000 title claims description 199
- 229910045601 alloy Inorganic materials 0.000 title claims description 198
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 84
- 239000001257 hydrogen Substances 0.000 title claims description 84
- 238000003860 storage Methods 0.000 title claims description 81
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000843 powder Substances 0.000 claims description 104
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 32
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 32
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 32
- 238000007747 plating Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 238000010303 mechanochemical reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 4
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 4
- 229910018605 Ni—Zn Inorganic materials 0.000 claims description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 2
- 229910018106 Ni—C Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 86
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000000227 grinding Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005204 segregation Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910018062 Ni-M Inorganic materials 0.000 description 4
- 229910010969 Ti—V—Ni Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000005266 casting Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009689 gas atomisation Methods 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
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気化学的な水素
の吸蔵・放出を可逆的に行える水素吸蔵合金電極および
その製造方法に関する。TECHNICAL FIELD The present invention relates to a hydrogen storage alloy electrode capable of reversibly electrochemically storing and releasing hydrogen, and a method for producing the same.
【０００２】[0002]
【従来の技術】水素を可逆的に吸蔵・放出する水素吸蔵
合金を用いた水素吸蔵合金電極は、理論容量密度がカド
ミウム電極より大きく、亜鉛電極のような変形やデンド
ライトの形成などもないので、長寿命・無公害であり、
しかも高エネルギー密度を有するアルカリ蓄電池用負極
として注目されている。このような水素吸蔵合金電極に
用いられる合金は、通常アーク溶解法や高周波誘導加熱
溶解法などで作製され、例えば、ＡＢ5タイプ（Ａ：Ｌ
ａ、Ｚｒ、Ｔｉなどの水素との親和性の大きい元素、
Ｂ：Ｎｉ、Ｍｎ、Ｃｒなどの遷移元素）のＬａ（または
Ｍｍ）−Ｎｉ系の多元系合金やＡＢ2タイプのラーベス
相を有する合金は、近年電極材料として盛んに開発が進
められている。特に、Ｍｍ−Ｎｉ系の多元系合金は、す
でに実用化されている。しかし、これらの水素吸蔵合金
は、アルカリ電解液により合金表面が腐食され、金属酸
化物や金属水酸化物が析出し、水素の吸蔵・放出能が低
下する。その結果、サイクル寿命特性が悪くなるという
問題があった。2. Description of the Related Art A hydrogen storage alloy electrode using a hydrogen storage alloy capable of reversibly storing and releasing hydrogen has a theoretical capacity density larger than that of a cadmium electrode and does not cause deformation such as a zinc electrode or formation of dendrites. Long life and no pollution,
Moreover, it has been drawing attention as a negative electrode for alkaline storage batteries having a high energy density. An alloy used for such a hydrogen storage alloy electrode is usually produced by an arc melting method, a high frequency induction heating melting method, or the like. For example, an AB 5 type (A: L
a, Zr, Ti, and other elements with a high affinity for hydrogen,
B (transition elements such as Ni, Mn, and Cr) La (or Mm) -Ni-based multi-component alloys and AB 2 -type Laves phase alloys have been actively developed in recent years as electrode materials. In particular, Mm-Ni based multi-component alloys have already been put to practical use. However, in these hydrogen storage alloys, the surface of the alloy is corroded by the alkaline electrolyte, metal oxides and metal hydroxides are deposited, and the hydrogen storage / release capacity is reduced. As a result, there is a problem that the cycle life characteristic is deteriorated.
【０００３】これを解決するために、合金表面にＮｉあ
るいはＮｉ合金をメッキする方法が提案されている（例
えば、特開昭６１−１６３５６９号公報や特開平２−７
９３６９号公報）。また、正極から発生した酸素ガスに
よる合金の酸化を防ぐために、メカノケミカル反応によ
り遷移金属を合金表面に付着する方法が提案されている
（例えば、特開平６−１２４７０５号公報）。さらに、
初期活性を向上させ、充放電効率を向上させるために、
合金粉末とＮｉ粉末を焼結させる方法が提案されている
（例えば、特開平５−２５８７５０号公報）。In order to solve this, a method of plating the surface of the alloy with Ni or a Ni alloy has been proposed (for example, Japanese Patent Laid-Open No. 61-163569 and Japanese Patent Laid-Open No. 2-7).
9369). Further, in order to prevent the alloy from being oxidized by the oxygen gas generated from the positive electrode, a method of adhering a transition metal to the alloy surface by a mechanochemical reaction has been proposed (for example, JP-A-6-124705). further,
In order to improve the initial activity and charge / discharge efficiency,
A method of sintering an alloy powder and a Ni powder has been proposed (for example, JP-A-5-258750).
【０００４】これらに対して、体心立方構造を有するＴ
ｉ−Ｖ−Ｎｉ系の水素吸蔵合金は、上記合金に比べてさ
らに大きな水素吸蔵量を持つ合金として注目されてお
り、いくつかの合金組成が提案されている。On the other hand, T having a body-centered cubic structure
The i-V-Ni-based hydrogen storage alloy is drawing attention as an alloy having a larger hydrogen storage capacity than the above alloys, and several alloy compositions have been proposed.
【０００５】[0005]
【発明が解決しようとする課題】体心立方構造を有する
Ｔｉ−Ｖ−Ｎｉ系の水素吸蔵合金は、母相以外に偏析相
であるＴｉ−Ｎｉ合金相が存在し、母相にはＮｉを含ま
ない。したがって、体心立方構造を有するＴｉ−Ｖ−Ｎ
ｉ系の水素吸蔵合金を電極に用いた場合、上記のＡＢ5
タイプやＡＢ2タイプの合金とは異なり、Ｔｉ−Ｎｉ偏
析相が活性点となって電気化学的な水素の吸蔵・放出を
行うと考えられ、充放電サイクルの初期から大きな放電
容量が得られる。A Ti-V-Ni-based hydrogen storage alloy having a body-centered cubic structure has a Ti-Ni alloy phase which is a segregation phase in addition to the mother phase, and Ni is contained in the mother phase. Not included. Therefore, Ti-VN having a body-centered cubic structure
When an i-based hydrogen storage alloy is used for the electrode, the above AB 5
It is considered that the Ti—Ni segregated phase serves as an active point to electrochemically store and release hydrogen, unlike the alloys of the type and AB 2 type, and a large discharge capacity is obtained from the beginning of the charge and discharge cycle.
【０００６】しかし、充放電を繰り返すと、Ｔｉ−Ｎｉ
偏析相からアルカリ電解液中にＴｉが溶出することによ
り導電性が低下し、放電容量が小さくなるという問題が
あった。本発明は、充放電サイクルを繰り返しても放電
容量の低下の少ない水素吸蔵合金電極を提供することを
目的とする。However, when charging and discharging are repeated, Ti--Ni
The elution of Ti from the segregation phase into the alkaline electrolyte lowers the conductivity and reduces the discharge capacity. It is an object of the present invention to provide a hydrogen storage alloy electrode that has a small decrease in discharge capacity even when a charge / discharge cycle is repeated.
【０００７】[0007]
【課題を解決するための手段】本発明の水素吸蔵合金電
極は、体心立方構造を有し、一般式Ｔｉ x Ｖ y Ｍ
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される水素吸蔵合金
粉末（以下、Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末という）の表面
に、粒径１μｍ以下のＮｉ粉末またはＴｉ−Ｎｉ合金粉
末をＮｉ量が前記水素吸蔵合金の１〜１０重量％の範囲
で配置した粉末から構成したものである。また、本発明
の水素吸蔵合金電極は、Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末を主
体とする電極の表面に、Ｎｉまたは、Ｎｉ−Ｃｏ合金、
Ｎｉ−Ｓｎ合金、Ｎｉ−Ｚｎ合金、およびＮｉ−Ｍｏ合
金からなる群より選ばれる合金のメッキ層を厚さ０．５
〜１μｍの範囲で、かつＮｉ量が前記水素吸蔵合金の１
〜１０重量％の範囲で被覆したものである。Means for Solving the Problems The hydrogen storage alloy electrode of the present invention
The pole has a body-centered cubic structure,General formula Ti x V y M
1-xy (However, M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6)Hydrogen storage alloy
Powder (Below, Ti x V y M 1-xy Alloy powder) Surface
Ni powder or Ti-Ni alloy powder with a particle size of 1 μm or less
The powder contains Ni in the range of 1 to 10% by weight of the hydrogen storage alloy.
It is composed of the powder arranged in (1). Also, the present invention
The hydrogen storage alloy electrode ofTi x V y M 1-xy Mainly alloy powder
On the surface of the body electrode, Ni or Ni-Co alloy,
Ni-Sn alloy, Ni-Zn alloy, and Ni-Mo alloy
The thickness of the plated layer of the alloy selected from the group consisting of gold is 0.5
In the range of 1 μm to 1 μm, and the Ni content is 1 of the above hydrogen storage alloy.
The coating is performed in the range of 10% by weight.
【０００８】本発明の水素吸蔵合金電極の製造方法は、
Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末の表面に、メカノケミカル反
応により、粒径１μｍ以下のＮｉ粉末またはＴｉ−Ｎｉ
合金粉末をＮｉ量が前記水素吸蔵合金の１〜１０重量％
の範囲で付着させる工程を有する。また、本発明の水素
吸蔵合金電極の製造方法は、Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末
の表面に、粒径１μｍ以下のＮｉ粉末またはＴｉ−Ｎｉ
合金粉末をＮｉ量が前記水素吸蔵合金の１〜１０重量％
の範囲で付着させる工程、および、前記Ｎｉ粉末または
Ｔｉ−Ｎｉ合金粉末を付着した水素吸蔵合金粉末を温度
４００〜１０００℃で１〜６時間焼結する工程を有す
る。さらに、本発明の水素吸蔵合金電極の製造方法は、
Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末の表面に、粒径１μｍ以下の
Ｎｉ粉末またはＴｉ−Ｎｉ合金粉末をＮｉ量が前記水素
吸蔵合金の１〜１０重量％の範囲で付着させる工程、前
記Ｎｉ粉末またはＴｉ−Ｎｉ合金粉末を付着した水素吸
蔵合金粉末を主体とする電極を成形する工程、および、
得られた成形体を温度４００〜１０００℃で１〜６時間
焼結する工程を有する。The method for producing a hydrogen storage alloy electrode of the present invention comprises:
On the surface of the Ti x V y M 1-xy alloy powder, Ni powder or Ti-Ni having a particle size of 1 μm or less is formed by mechanochemical reaction.
The alloy powder contains Ni in an amount of 1 to 10% by weight of the hydrogen storage alloy.
The step of adhering in the range of. In addition, the method for producing a hydrogen storage alloy electrode of the present invention is characterized in that Ni powder or Ti-Ni powder having a particle size of 1 μm or less is formed on the surface of Ti x V y M 1-xy alloy powder.
The alloy powder contains Ni in an amount of 1 to 10% by weight of the hydrogen storage alloy.
And a step of sintering the hydrogen storage alloy powder having the Ni powder or the Ti—Ni alloy powder adhered thereto at a temperature of 400 to 1000 ° C. for 1 to 6 hours. Furthermore, the method for producing the hydrogen storage alloy electrode of the present invention,
A step of depositing Ni powder or Ti—Ni alloy powder having a particle diameter of 1 μm or less on the surface of the Ti x V y M 1-xy alloy powder in an amount of 1 to 10% by weight of the hydrogen storage alloy; Powder or a step of forming an electrode mainly composed of a hydrogen storage alloy powder to which a Ti-Ni alloy powder is attached, and
The method has a step of sintering the obtained molded body at a temperature of 400 to 1000 ° C. for 1 to 6 hours.
【０００９】Ｔｉ x Ｖ y Ｍ 1-x-y 合金粉末の表面にＮｉ粉
末またはＴｉ−Ｎｉ合金粉末を配置ないしは付着させる
方法としては、ボールミルなどによる機械的造粒法ある
いは圧縮摩砕式超微粉砕機により、圧縮力および摩砕力
よりなる機械エネルギーを作用させるというメカノケミ
カル反応（メカノフュージョン）が好ましい。As a method for disposing or adhering the Ni powder or the Ti—Ni alloy powder on the surface of the Ti x V y M 1-xy alloy powder, a mechanical granulation method such as a ball mill or a compression grinding ultrafine pulverizer is used. Therefore, a mechanochemical reaction (mechanofusion) in which mechanical energy composed of compressive force and attrition force is applied is preferable.
【００１０】ここに用いる水素吸蔵合金粉末は、粒径７
５μｍ以下のものが好ましい。 また、水素吸蔵合金粉末
は、合金材料を溶解後、１０3〜１０7℃／秒の冷却速度
で急冷した合金であることが好ましい。The hydrogen storage alloy powder used here has a particle size of 7
It is preferably 5 μm or less . Also, the hydrogen storage alloy powder, were dissolved alloy material is preferably 10 3 ~10 7 ℃ / sec quenched alloy at a cooling rate of.
【００１１】体心立方構造を有するＴｉ−Ｖ−Ｎｉ系の
水素吸蔵合金には、母相以外に偏析相であるＴｉ−Ｎｉ
合金相が存在し、母相にはＮｉを含まない。従来のＡＢ
5タイプやＡＢ2タイプの合金は、通常Ｎｉは母相に含ま
れ、Ｎｉを含む偏析相が存在すると、その偏析相は放電
特性に悪影響を及ぼす。一方、体心立方構造を有するＴ
ｉ−Ｖ−Ｎｉ系の水素吸蔵合金では、Ｔｉ−Ｎｉ偏析相
が活性点となり、母相が水素の吸蔵・放出を行うと考え
られる。また、従来のＡＢ5タイプやＡＢ2タイプの合金
は、良好な放電特性を得るためには、合金中に３５〜５
０重量％のＮｉ量を含む必要がある。これに対して、体
心立方構造を有するＴｉ−Ｖ−Ｎｉ系の水素吸蔵合金で
は、２０重量％程度のＮｉ量があれば十分であり、充放
電サイクルの初期から大きな放電容量が得られる。In the Ti-V-Ni-based hydrogen storage alloy having a body-centered cubic structure, the segregation phase of Ti-Ni is present in addition to the matrix phase.
An alloy phase exists, and the parent phase does not contain Ni. Conventional AB
In the 5 type and AB 2 type alloys, Ni is usually contained in the matrix phase, and if there is a segregated phase containing Ni, the segregated phase adversely affects the discharge characteristics. On the other hand, T having a body-centered cubic structure
In the i-V-Ni-based hydrogen storage alloy, it is considered that the Ti-Ni segregated phase serves as an active point and the parent phase stores and releases hydrogen. Further, in order to obtain good discharge characteristics, the conventional AB 5 type and AB 2 type alloys have an alloy content of 35-5.
It is necessary to include 0% by weight of Ni. On the other hand, in a Ti-V-Ni-based hydrogen storage alloy having a body-centered cubic structure, a Ni content of about 20% by weight is sufficient, and a large discharge capacity can be obtained from the beginning of the charge / discharge cycle.
【００１２】以上のように、Ｎｉはすべて偏析相に含ま
れ、その偏析相が電気化学的な水素の吸蔵・放出の活性
点となり、少量のＮｉ量で大きな放電容量が得られるこ
とが体心立方構造を有するＴｉ−Ｖ−Ｎｉ系の水素吸蔵
合金の大きな特徴である。しかし、充放電を繰り返す
と、Ｔｉ−Ｎｉ偏析相からアルカリ電解液中にＴｉが溶
出することにより導電性が低下し、放電容量が小さくな
る。この場合、単純に考えれば、Ｔｉが溶出すればＮｉ
が残ることになり、このＮｉは活性であると考えられる
ので、導電性は維持されると思われる。しかし、実際に
はそう簡単ではない。Ｔｉ−Ｎｉ偏析相は、母相に比べ
て水素吸蔵量が少ないため、母相とＴｉ−Ｎｉ偏析相と
は水素吸蔵による体積膨張率が異なる。従って、充放電
を繰り返すと、母相と偏析相との間に隙間ができると考
えられる。そのため、偏析相からＴｉが溶出すると、母
相と偏析相との分離が促進され、全体として導電性が低
下することになると考えられる。また、ほとんど充放電
できなくなった合金でも水素吸蔵能は有していることか
ら、母相は耐アルカリ性が大きいと考えられる。As described above, Ni is entirely contained in the segregation phase, and the segregation phase serves as an active point for electrochemical hydrogen storage / release, and a large discharge capacity can be obtained with a small amount of Ni. This is a major feature of the Ti-V-Ni-based hydrogen storage alloy having a cubic structure. However, when charging and discharging are repeated, Ti is eluted from the Ti—Ni segregation phase into the alkaline electrolyte to lower the conductivity and reduce the discharge capacity. In this case, simply thinking, if Ti elutes, Ni
Remains, and this Ni is considered to be active, so that the conductivity is considered to be maintained. But it's not really that easy. Since the Ti-Ni segregated phase has a smaller hydrogen storage amount than the mother phase, the mother phase and the Ti-Ni segregated phase have different volume expansion rates due to hydrogen storage. Therefore, it is considered that when charging and discharging are repeated, a gap is formed between the matrix phase and the segregation phase. Therefore, it is considered that when Ti is eluted from the segregated phase, the separation of the mother phase and the segregated phase is promoted and the conductivity as a whole is lowered. Further, it is considered that the parent phase has a high alkali resistance because the alloy having almost no charge / discharge has hydrogen storage capacity.
【００１３】そこで、本発明は、体心立方構造を有し、
組成にＮｉを含まない水素吸蔵合金粉末の表面に、Ｎｉ
を配置するものである。体心立方構造を有し、組成にＮ
ｉを含まない水素吸蔵合金は、水素吸蔵量が大きく、合
金表面に配置されたＮｉが電気化学的な水素の吸蔵・放
出の活性点となるため、大きな放電容量が得られる。そ
して、この構成によると、上記のような母相と活性点と
の分離は起こらないので、長期にわたって高容量を維持
することができる。水素吸蔵合金粉末の表面にＮｉを配
置する方法としては、メッキ、またはボールミルなどに
よる機械的造粒法あるいは圧縮摩砕式超微粉砕機により
圧縮力および摩砕力よりなる機械エネルギーを作用させ
るメカノケミカル反応（メカノフュージョン法）のいず
れかが簡便でよい。Therefore, the present invention has a body-centered cubic structure,
Ni on the surface of the hydrogen storage alloy powder that does not contain Ni
Is to be placed. It has a body-centered cubic structure and its composition is N
A hydrogen storage alloy not containing i has a large hydrogen storage capacity, and Ni disposed on the alloy surface serves as an electrochemical active point for hydrogen storage / release, so that a large discharge capacity can be obtained. Further, according to this configuration, since the separation of the mother phase and the active sites as described above does not occur, a high capacity can be maintained for a long period of time. As a method of arranging Ni on the surface of the hydrogen-absorbing alloy powder, a mechanical granulation method such as plating or a ball mill, or a mechanical energy applying compressive force and a grinding force by a compression grinding type ultrafine pulverizer is used. Any of the chemical reactions (mechanofusion method) may be convenient.
【００１４】合金表面に配置されたＮｉは、水素吸蔵合
金に対して１重量％より小さいと活性点としての効果が
得られないが、上記のように少量のＮｉ量で十分な電気
化学的活性が得られるので、上限としては１０重量％も
あれば十分であり、それより多くしてもＮｉ量が増加し
た分だけ電極としての容量が小さくなる。その上、Ｎｉ
の粒径が１μｍ以下であれば活性点としての効果が得ら
れるが、それより大きいと、活性点としてのＮｉの表面
積が小さくなり、効果が低下する。したがって、合金表
面に配置されたＮｉは、水素吸蔵合金に対して１〜１０
重量％であり、かつＮｉの粒径が１μｍ以下であること
により十分な効果が得られる。また、メッキの場合はＮ
ｉ層の厚みが０．５μｍより小さいと活性点としての効
果が得られないが、上記と同様に上限としては１μｍも
あれば十分であり、それより多くしてもＮｉ量が増加し
た分だけ電極としての容量が小さくなる。If the Ni disposed on the alloy surface is less than 1% by weight with respect to the hydrogen storage alloy, the effect as an active point cannot be obtained, but as described above, a small amount of Ni is sufficient for electrochemical activity. Therefore, 10 wt% is sufficient as the upper limit, and even if the upper limit is increased, the capacity of the electrode becomes smaller as the Ni content increases. Besides, Ni
If the particle size is less than 1 μm, the effect as an active site can be obtained, but if it is larger than that, the surface area of Ni as an active site becomes small and the effect is reduced. Therefore, Ni arranged on the alloy surface is 1 to 10 with respect to the hydrogen storage alloy.
Sufficient effects can be obtained when the content of Ni is 1% by weight and the particle size of Ni is 1 μm or less. In the case of plating, N
If the thickness of the i layer is less than 0.5 μm, the effect as an active point cannot be obtained, but as in the above case, the upper limit of 1 μm is sufficient. The capacity as an electrode becomes small.
【００１５】また、体心立方構造を有し、組成にＮｉを
含まない水素吸蔵合金粉末の表面にＴｉ−Ｎｉ合金粉末
を配置させても上記の問題は解決できる。この場合はＴ
ｉ−Ｎｉ粉末からＴｉが溶出し、ラネー状のＮｉが生成
するため、これが活性点となる。しかし、合金表面のＴ
ｉ−Ｎｉ粉末とＴｉ−Ｎｉ偏析相とは異なるものである
から、上記のような母相と活性点との分離は起こらない
ので、長期にわたって高容量を維持することができる。
この場合も、ボールミルなどによる機械的造粒法あるい
は圧縮摩砕式超微粉砕機により圧縮力および摩砕力より
なる機械エネルギーを作用させるメカノケミカル反応が
簡便でよい。合金表面に配置されたＴｉ−Ｎｉ合金粉末
のＮｉ量は、水素吸蔵合金に対して１重量％より小さい
と活性点としての効果が得られないが、上記と同様に上
限としては１０重量％もあれば十分であり、それより多
くしてもＮｉ量が増加した分だけ電極としての容量が小
さくなる。その上、Ｔｉ−Ｎｉ合金粉末が１０μｍ以下
であれば細かいラネー状のＮｉが生成するので、活性点
としての効果が得られるが、それより大きいと十分な効
果が得られない。したがって、合金表面に配置したＴｉ
−Ｎｉ合金粉末は、Ｎｉ量が水素吸蔵合金に対して１〜
１０重量％であり、かつＴｉ−Ｎｉ合金粉末の粒径が１
０μｍ以下であることが必要である。The above problem can also be solved by disposing the Ti—Ni alloy powder on the surface of the hydrogen storage alloy powder having a body-centered cubic structure and not containing Ni in the composition. In this case T
Ti is eluted from the i-Ni powder and Raney-like Ni is produced, and this becomes the active site. However, T on the alloy surface
Since the i-Ni powder and the Ti-Ni segregated phase are different from each other, the separation of the mother phase and the active sites as described above does not occur, so that the high capacity can be maintained for a long time.
Also in this case, a mechanochemical reaction in which mechanical energy consisting of compression force and grinding force is applied by a mechanical granulation method using a ball mill or a compression grinding type ultrafine crusher may be simple. If the amount of Ni of the Ti-Ni alloy powder arranged on the alloy surface is less than 1% by weight with respect to the hydrogen storage alloy, the effect as an active point cannot be obtained, but as with the above, the upper limit is 10% by weight. It is sufficient if the amount of Ni is increased, and the capacity of the electrode is reduced by the amount of increase in the amount of Ni. Moreover, if the Ti-Ni alloy powder is 10 μm or less, fine Raney-like Ni is produced, so that the effect as an active point can be obtained, but if it is larger than that, a sufficient effect cannot be obtained. Therefore, Ti deposited on the alloy surface
In the Ni alloy powder, the Ni content is 1 to the hydrogen storage alloy.
10% by weight, and the particle size of the Ti-Ni alloy powder is 1
It should be 0 μm or less.
【００１６】また、Ｎｉ粉末またはＴｉーＮｉ合金粉末
を付着した水素吸蔵合金粉末を焼結する場合、温度が４
００℃より低いか焼結時間が１時間より短いと、実質的
に焼結されない。また、１０００℃を超える温度で焼結
するか焼結時間が６時間を超えると、焼結が進み過ぎ、
合金粉末とＮｉとが部分的に合金化するため、水素吸蔵
量が減少する。したがって、焼結は温度範囲４００〜１
０００℃で１〜６時間にする必要がある。When sintering the hydrogen storage alloy powder to which the Ni powder or the Ti-Ni alloy powder is attached, the temperature is 4
When the temperature is lower than 00 ° C or the sintering time is shorter than 1 hour, substantially no sintering is performed. Also, if the sintering is performed at a temperature over 1000 ° C. or the sintering time exceeds 6 hours, the sintering proceeds too much,
Since the alloy powder and Ni are partially alloyed, the hydrogen storage amount is reduced. Therefore, sintering takes place in the temperature range of 400-1.
It is necessary to set the temperature at 000 ° C for 1 to 6 hours.
【００１７】さらに、体心立方構造を有し、組成にＮｉ
を含まない水素吸蔵合金粉末から構成した電極表面をＮ
ｉ−Ｃｏ合金、Ｎｉ−Ｓｎ合金、Ｎｉ−Ｚｎ合金、Ｎｉ
−Ｍｏ合金のいずれかのメッキ層で被覆することによっ
ても上記の問題は解決できる。この場合はＮｉ−Ｍ（Ｍ
はＣｏ、Ｓｎ、Ｚｎ、Ｍｏのいずれか一種）合金メッキ
層からＭが溶出し、ラネー状のＮｉが生成するため、こ
れが活性点となる。しかし、この場合も、上記のような
母相と活性点との分離は起こらないので、長期にわたっ
て高容量を維持することができる。Ｎｉ−Ｍ合金メッキ
層のＮｉ量は、水素吸蔵合金に対して１重量％より小さ
いと活性点としての効果が得られないが、上記と同様に
上限としては１０重量％もあれば十分であり、それより
多くしてもＮｉ量が増加した分だけ電極としての容量が
小さくなる。その上、Ｎｉ−Ｍ合金メッキ層の厚みが
０．５μｍより小さいと活性点としての効果が得られな
い。また、メッキ層の厚みが１μｍ以下であれば、細か
いラネー状のＮｉが生成するので活性点としての効果が
得られるが、それより大きいと十分な効果が得られな
い。したがって、Ｎｉ−Ｍ合金メッキ層のＮｉ量は水素
吸蔵合金に対して１〜１０重量％であり、かつメッキ層
の厚みが０．５〜１μｍである必要がある。Further, it has a body-centered cubic structure and has a composition of Ni.
The electrode surface composed of hydrogen storage alloy powder containing no
i-Co alloy, Ni-Sn alloy, Ni-Zn alloy, Ni
The above problem can also be solved by coating with one of the plating layers of Mo alloy. In this case, Ni-M (M
Is any one of Co, Sn, Zn, and Mo) M elutes from the alloy plating layer to produce Raney-like Ni, which becomes an active point. However, also in this case, since the separation of the mother phase and the active sites as described above does not occur, a high capacity can be maintained for a long period of time. If the Ni content of the Ni-M alloy plated layer is less than 1% by weight with respect to the hydrogen storage alloy, the effect as an active point cannot be obtained, but as with the above, an upper limit of 10% by weight is sufficient. However, even if it is more than that, the capacity as the electrode becomes smaller by the amount of the increase in the Ni content. Moreover, if the thickness of the Ni-M alloy plating layer is smaller than 0.5 μm, the effect as an active point cannot be obtained. Further, if the thickness of the plating layer is 1 μm or less, fine Raney-like Ni is generated, so that the effect as an active point can be obtained, but if it is larger than that, a sufficient effect cannot be obtained. Therefore, the Ni content of the Ni-M alloy plating layer needs to be 1 to 10% by weight with respect to the hydrogen storage alloy, and the thickness of the plating layer needs to be 0.5 to 1 μm.
【００１８】電極を構成する水素吸蔵合金粉末の粒径は
７５μｍを越えると、電極の成形が困難になり、電極か
らの合金粉末の脱落も多くなる。したがって、水素吸蔵
合金粉末の粒径は７５μｍ以下であることが好ましい。
以上のような水素吸蔵合金は、通常、アーク溶解法や鋳
造法により作製するが、合金の冷却速度を１０3℃／秒
以上にすると、合金の各構成元素が均一に分布するよう
になり、特に水素吸蔵量が大きくなる。しかし、合金の
冷却速度が１０7℃／秒を越えると、逆に水素吸蔵量は
低下する。これは、部分的にアモルファス相を生じるた
めと思われる。したがって、合金の冷却速度を１０3〜
１０7℃／秒とすることにより、優れた水素化特性が得
られる。このような冷却速度を持つ合金製造法として
は、ガスアトマイズ法や水アトマイズ法、ロール急冷法
などがある。また、体心立方構造を有し、組成にＮｉを
含まない水素吸蔵合金としては、一般式ＴｉxＶyＭ
1-x-y（ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される合金であれ
ば、特に水素吸蔵量が大きくなる。If the particle size of the hydrogen-absorbing alloy powder constituting the electrode exceeds 75 μm, it becomes difficult to mold the electrode, and the alloy powder often drops from the electrode. Therefore, the particle size of the hydrogen storage alloy powder is preferably 75 μm or less.
The above hydrogen storage alloy is usually produced by an arc melting method or a casting method. However, when the cooling rate of the alloy is set to 10 3 ° C / sec or more, each constituent element of the alloy becomes uniformly distributed, Particularly, the hydrogen storage amount becomes large. However, when the cooling rate of the alloy exceeds 10 7 ° C / sec, the hydrogen storage amount decreases. This is probably because the amorphous phase is partially generated. Therefore, the cooling rate of the alloy is 10 3 to
Excellent hydrogenation characteristics can be obtained by setting the temperature to 10 7 ° C / sec. As an alloy manufacturing method having such a cooling rate, there are a gas atomizing method, a water atomizing method, a roll quenching method and the like. Further, as a hydrogen storage alloy having a body-centered cubic structure and not containing Ni in the composition, a general formula Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
At least one element selected from the group consisting of Al, Si, P, B, and rare earth elements, and 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6), the hydrogen storage amount becomes particularly large.
【００１９】[0019]
【発明の実施の形態】以下に本発明の実施例について説
明する。
［実施例１］体心立方構造を有し、組成にＮｉを含まな
い水素吸蔵合金の一例として、Ｔｉ0.3Ｖ0.5Ｃｒ0.2合
金をアーク溶解により作製した。次いで、この合金を水
素化による粉砕を行い、７５μｍ以下に分級した。この
合金粉末に無電解メッキにより０．５μｍのＮｉメッキ
層で被覆したもの（合金Ａ）、ボールミルを用いて合金
粉末と０．８μｍのＮｉ粉末とを混合することにより、
合金粉末の表面に５重量％のＮｉ粉末を付着したもの
（合金Ｂ）、および、圧縮摩砕式超微粉砕機を用いて合
金粉末と０．８μｍのＮｉ粉末とを混合することによ
り、合金粉末の表面に５重量％のＮｉ粉末を付着したも
の（合金Ｃ）を作製した。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. Has a [Example 1] body-centered cubic structure, as an example of a hydrogen storage alloy containing no Ni on the composition, was prepared by arc melting the Ti 0.3 V 0.5 Cr 0.2 alloy. Next, this alloy was pulverized by hydrogenation and classified to 75 μm or less. This alloy powder coated with a 0.5 μm Ni plating layer by electroless plating (alloy A), and the alloy powder and 0.8 μm Ni powder are mixed using a ball mill,
An alloy powder having 5% by weight of Ni powder adhered to the surface (alloy B) and an alloy powder prepared by mixing the alloy powder with 0.8 μm Ni powder using a compression grinding ultrafine pulverizer. A powder (alloy C) having 5% by weight of Ni powder deposited on the surface of the powder was prepared.
【００２０】ここで、合金粉末の表面にＮｉを付着する
前にフッ化水素酸の１重量％水溶液に１０分間浸漬する
前処理をしたものと前処理をしなかったものとを比べる
と、前処理をしたものの方がＮｉが均一に付着している
ことがわかった。したがって、前処理後に上記のように
Ｎｉを合金表面に付着したものをそれぞれ試料とした。
また、体心立方構造を有し、合金組成にＮｉを含むＴｉ
0.2Ｖ0.4Ｃｒ0.2Ｎｉ0 .2合金をアーク溶解により作製
し、水素化により粉砕し、７５μｍ以下に分級したもの
を比較例とした。以上のような合金試料について、電気
化学的な充放電反応によるアルカリ蓄電池用負極として
の電極特性を評価するために単電池試験を行った。各合
金粉末にポリビニルアルコール３重量％水溶液を加えて
ペースト状にした。次いで、このペ−ストを多孔度９５
％、厚さ０．８ｍｍの発泡状ニッケル板に充填し、加圧
して電極を得た。Here, comparing the pretreatment of immersing in a 1% by weight aqueous solution of hydrofluoric acid for 10 minutes before deposition of Ni on the surface of the alloy powder and the non-pretreatment, It was found that Ni was more uniformly attached to the treated one. Therefore, samples having Ni adhered to the alloy surface as described above after the pretreatment were used as samples.
In addition, Ti having a body-centered cubic structure and containing Ni in the alloy composition
The 0.2 V 0.4 Cr 0.2 Ni 0 .2 alloy prepared by arc melting, milled by hydrogenation, and the comparative example those classified to 75μm or less. The above alloy samples were subjected to a single cell test in order to evaluate the electrode characteristics as a negative electrode for an alkaline storage battery by an electrochemical charge / discharge reaction. A 3 wt% aqueous solution of polyvinyl alcohol was added to each alloy powder to form a paste. The paste is then porosity 95
%, 0.8 mm thick foamed nickel plate was filled and pressed to obtain an electrode.
【００２１】これらの電極を負極とし、対極に過剰の電
気容量を有する酸化ニッケル正極を配し、電解液に比重
１．３０の水酸化カリウム水溶液を用い、電解液が豊富
な開放系電池を構成した。この電池は、水素吸蔵合金負
極で容量が規制される。この電池を水素吸蔵合金１ｇ当
たり１００ｍＡの電流で５．５時間充電し、合金１ｇ当
たり５０ｍＡで端子電圧が０．８Ｖになるまで放電する
充放電を繰り返した。各合金を用いた負極のサイクル特
性を図１に示す。合金Ａ、Ｂ、Ｃを用いた電極は、比較
例に比べて優れたサイクル特性を示すことがわかる。な
お、合金粉末の表面に付着するＮｉが合金に対して１０
重量％を越える場合およびＮｉの粒径が１μｍを越える
場合についても検討した。その結果、初期の放電容量が
低下することがわかった。These electrodes are used as negative electrodes, a nickel oxide positive electrode having an excess electric capacity is arranged as a counter electrode, and an aqueous potassium hydroxide solution having a specific gravity of 1.30 is used as an electrolytic solution to form an open system battery rich in the electrolytic solution. did. The capacity of this battery is regulated by the hydrogen storage alloy negative electrode. This battery was charged at a current of 100 mA per gram of hydrogen storage alloy for 5.5 hours and discharged at 50 mA per gram of alloy until the terminal voltage became 0.8 V, which was repeated. The cycle characteristics of the negative electrode using each alloy are shown in FIG. It can be seen that the electrodes using the alloys A, B and C exhibit excellent cycle characteristics as compared with the comparative example. It should be noted that Ni adhering to the surface of the alloy powder is 10% with respect to the alloy.
An examination was also made for a case where the content of Ni exceeds 1% by weight and a case where the particle size of Ni exceeds 1 μm. As a result, it was found that the initial discharge capacity was reduced.
【００２２】［実施例２］実施例１の合金Ａ、Ｂおよび
Ｃをそれぞれ加圧してペレット状にし、真空中８００℃
で３時間焼結した。この燒結体を機械的に粉砕し、７５
μｍ以下に分級した。これらの粉末を用いて実施例１と
同様に発泡状ニッケル板に充填して作製した電極をそれ
ぞれ電極Ｅ、ＦおよびＧとする。また、実施例１の合金
Ａ、ＢおよびＣを用いて、実施例１と同様の方法で電極
を作製した後、真空中８００℃で３時間焼結した。そし
てポリビニルアルコールの３重量％水溶液に浸漬し、乾
燥した。これらの電極をそれぞれ電極Ｈ、ＩおよびＪと
する。[Example 2] Alloys A, B and C of Example 1 were pressed to form pellets, and the pellets were vacuumed at 800 ° C.
Sintered for 3 hours. This sintered body is mechanically crushed,
It was classified to be less than μm. Electrodes prepared by filling the foamed nickel plate with these powders in the same manner as in Example 1 were designated as electrodes E, F and G, respectively. Further, using the alloys A, B and C of Example 1, an electrode was produced in the same manner as in Example 1, and then sintered in vacuum at 800 ° C. for 3 hours. Then, it was immersed in a 3% by weight aqueous solution of polyvinyl alcohol and dried. These electrodes are referred to as electrodes H, I, and J, respectively.
【００２３】これらの各電極を用いて実施例１と同様に
して単電池試験を行い、サイクル特性を調べた。その結
果を、実施例１で用いた比較例とともに図２および図３
に示す。電極Ｅ、Ｆ、Ｇ、Ｈ、ＩおよびＪは、比較例に
比べて優れたサイクル特性を示すことがわかった。な
お、合金粉末の表面に付着するＮｉが合金に対して１０
重量％を越える場合およびＮｉの粒径が１μｍを越える
場合についても検討を行った結果、初期の放電容量が低
下することがわかった。Using each of these electrodes, a single cell test was conducted in the same manner as in Example 1 to examine the cycle characteristics. The results are shown in FIG. 2 and FIG. 3 together with the comparative example used in Example 1.
Shown in. It was found that the electrodes E, F, G, H, I and J exhibited excellent cycle characteristics as compared with the comparative example. It should be noted that Ni adhering to the surface of the alloy powder is 10% with respect to the alloy.
As a result of conducting investigations in the case of exceeding the weight% and in the case of the particle diameter of Ni exceeding 1 μm, it was found that the initial discharge capacity decreased.
【００２４】［実施例３］実施例１で作製したＴｉ0.3
Ｖ0.5Ｃｒ0.2合金の７５μｍ以下の粉末を用いた。ま
ず、この合金粉末と１０μｍ以下のＴｉ−Ｎｉ合金粉末
（Ｔｉ−Ｎｉ合金中のＮｉ量が５５重量％）とをボール
ミルにより混合して、合金粉末の表面にＮｉ量として５
重量％になるようにＴｉ−Ｎｉ合金粉末を付着した（合
金Ｋ）。また、合金粉末と上記と同じＴｉ−Ｎｉ合金粉
末とを圧縮摩砕式超微粉砕機を用いて混合し、合金粉末
の表面にＮｉ量として５重量％になるようにＴｉ−Ｎｉ
合金粉末を付着した（合金Ｌ）。ここで、合金粉末の表
面にＴｉ−Ｎｉ合金粉末を付着する前に、フッ化水素酸
の１重量％水溶液に１０分間浸漬する前処理をしたもの
と前処理をしなかったものとを比べると、前処理をした
ものの方がＴｉ−Ｎｉ合金粉末が均一に付着しているこ
とがわかった。したがって、前処理後に上記のようにＴ
ｉ−Ｎｉ合金粉末を合金表面に付着したものをそれぞれ
試料とした。Example 3 Ti 0.3 produced in Example 1
A powder of V 0.5 Cr 0.2 alloy having a particle size of 75 μm or less was used. First, this alloy powder and a Ti—Ni alloy powder of 10 μm or less (the amount of Ni in the Ti—Ni alloy is 55% by weight) are mixed by a ball mill, and the amount of Ni on the surface of the alloy powder becomes
Ti-Ni alloy powder was deposited so that the weight percent was (Alloy K). Further, the alloy powder and the same Ti-Ni alloy powder as described above are mixed using a compression grinding type ultrafine pulverizer, and Ti-Ni is mixed on the surface of the alloy powder so that the amount of Ni becomes 5% by weight.
Alloy powder was deposited (alloy L). Here, before the Ti-Ni alloy powder is attached to the surface of the alloy powder, a comparison is made between a pretreatment in which the Ti-Ni alloy powder is immersed in a 1% by weight aqueous solution of hydrofluoric acid for 10 minutes and a non-pretreatment. It was found that the Ti-Ni alloy powder was more uniformly attached to the pretreated product. Therefore, after pretreatment, as described above, T
Samples were prepared by depositing i-Ni alloy powder on the alloy surface.
【００２５】このようにして作製した合金を用いて、実
施例１と同様にして電極を作製し、単電池試験を行っ
た。各電極のサイクル特性を実施例１で用いた比較例と
ともに図４に示す。合金Ｋ、Ｌを用いて作製した電極
は、比較例に比べて優れたサイクル特性を示すことがわ
かった。なお、合金粉末の表面に付着するＴｉ−Ｎｉ合
金粉末が合金に対してＮｉ量として１０重量％を越える
場合およびＴｉ−Ｎｉ合金粉末の粒径が１０μｍを越え
る場合についても検討を行った結果、初期の放電容量が
低下することがわかった。Using the alloy thus produced, an electrode was produced in the same manner as in Example 1 and a single cell test was conducted. The cycle characteristics of each electrode are shown in FIG. 4 together with the comparative example used in Example 1. It was found that the electrodes produced using the alloys K and L exhibited excellent cycle characteristics as compared with the comparative example. In addition, as a result of studying also when the Ti-Ni alloy powder adhering to the surface of the alloy powder exceeds 10% by weight as the amount of Ni with respect to the alloy and the particle size of the Ti-Ni alloy powder exceeds 10 μm, It was found that the initial discharge capacity was reduced.
【００２６】［実施例４］実施例１で作製したＴｉ0.3
Ｖ0.5Ｃｒ0.2合金の７５μｍ以下の粉末を用いて、実施
例１と同様の方法で４枚の電極を作製した。そして、硫
酸ニッケルおよび硫酸コバルトを含むメッキ浴を用いて
電極表面をＮｉ−Ｃｏ合金メッキ層で被覆したもの（電
極Ｍ）、硫酸ニッケルおよび硫酸スズを含むメッキ浴を
用いて電極表面をＮｉ−Ｓｎ合金メッキ層で被覆したも
の（電極Ｎ）、硫酸ニッケルおよび塩化亜鉛を含むメッ
キ浴を用いて電極表面をＮｉ−Ｚｎ合金メッキ層で被覆
したもの（電極Ｐ）、および、硫酸ニッケルおよびモリ
ブデン酸アンモニウムを含むメッキ浴を用いて電極表面
をＮｉ−Ｍｏ合金メッキ層で被覆したもの（電極Ｑ）を
作製した。いずれの電極においても、メッキ層のＮｉ量
が合金に対して約５重量％となるようにし、メッキ層の
厚みは０．５〜０．９μｍとした。ここで、それぞれの
メッキを行う前に合金粉末をフッ化水素酸の１重量％水
溶液に１０分間浸漬する前処理をしたものと前処理をし
なかったものとを比べると、前処理をしたものの方がメ
ッキ層が均一に付着していることがわかった。したがっ
て、前処理後に上記のようにメッキしたものをそれぞれ
試料とした。Example 4 Ti 0.3 produced in Example 1
Four electrodes were prepared in the same manner as in Example 1 using powder of V 0.5 Cr 0.2 alloy having a particle size of 75 μm or less. Then, the electrode surface is coated with a Ni-Co alloy plating layer using a plating bath containing nickel sulfate and cobalt sulfate (electrode M), and the electrode surface is coated with Ni-Sn using a plating bath containing nickel sulfate and tin sulfate. One coated with an alloy plating layer (electrode N), one coated with a Ni—Zn alloy plating layer using a plating bath containing nickel sulfate and zinc chloride (electrode P), and nickel sulfate and ammonium molybdate. An electrode surface was coated with a Ni-Mo alloy plating layer (electrode Q) using a plating bath containing. In each of the electrodes, the Ni content of the plating layer was set to about 5% by weight with respect to the alloy, and the thickness of the plating layer was 0.5 to 0.9 μm. Here, when the pretreatment in which the alloy powder is immersed in a 1% by weight aqueous solution of hydrofluoric acid for 10 minutes before the respective plating is compared with that without the pretreatment, It was found that the plated layer was evenly attached. Therefore, the samples plated as described above after the pretreatment were used as samples.
【００２７】このようにして作製した各電極を用いて実
施例１と同様にして単電池試験を行い、サイクル特性を
調べた。実施例１で用いた比較例とともに図５に示す。
電極Ｍ、Ｎ、ＰおよびＱは、比較例に比べて優れたサイ
クル特性を示すことがわかった。なお、電極表面を被覆
する合金メッキ層のＮｉ量が合金に対して１０重量％を
越える場合および合金メッキ層の厚みが１μｍを越える
場合についても検討を行った結果、初期の放電容量が低
下することがわかった。Using each of the electrodes thus produced, a single cell test was conducted in the same manner as in Example 1 to examine the cycle characteristics. It is shown in FIG. 5 together with the comparative example used in Example 1.
It was found that the electrodes M, N, P and Q exhibited excellent cycle characteristics as compared with the comparative example. Note that, when the amount of Ni of the alloy plating layer covering the electrode surface exceeds 10% by weight with respect to the alloy and the case where the thickness of the alloy plating layer exceeds 1 μm, the initial discharge capacity decreases as a result of the examination. I understood it.
【００２８】[0028]
【発明の効果】以上のように本発明によれば、高容量
で、サイクル寿命特性に優れた水素吸蔵合金電極が得ら
れる。As described above, according to the present invention, a hydrogen storage alloy electrode having a high capacity and excellent cycle life characteristics can be obtained.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の実施例１および比較例の合金を用いた
電極のサイクル特性を示した図である。FIG. 1 is a diagram showing cycle characteristics of electrodes using alloys of Example 1 and Comparative Example of the present invention.
【図２】本発明の実施例２および比較例の合金を用いた
電極のサイクル特性を示した図である。FIG. 2 is a diagram showing cycle characteristics of electrodes using the alloys of Example 2 and Comparative Example of the present invention.
【図３】本発明の実施例２および比較例の合金を用いた
電極のサイクル特性を示した図である。FIG. 3 is a diagram showing cycle characteristics of electrodes using the alloys of Example 2 and Comparative Example of the present invention.
【図４】本発明の実施例３および比較例の合金を用いた
電極のサイクル特性を示した図である。FIG. 4 is a diagram showing cycle characteristics of electrodes using the alloys of Example 3 and Comparative Example of the present invention.
【図５】本発明の実施例４および比較例の合金を用いた
電極のサイクル特性を示した図である。FIG. 5 is a diagram showing cycle characteristics of electrodes using the alloys of Example 4 and Comparative Example of the present invention.
フロントページの続き (72)発明者 山田 敏弘 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 豊口 ▲吉▼徳 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平２−65060（ＪＰ，Ａ) 特開 昭63−284758（ＪＰ，Ａ) 特開 昭54−45608（ＪＰ，Ａ) 特開 平５−28989（ＪＰ，Ａ) 特開 平５−174816（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/24 H01M 4/26 H01M 4/38 H01M 4/62 Front page continuation (72) Inventor Toshihiro Yamada 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) Reference JP-A-2-65060 (JP, A) JP-A-63-284758 (JP, A) JP-A-54-45608 (JP, A) JP-A-5-28989 (JP, A) JP-A-5-174816 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 4/24 H01M 4/26 H01M 4/38 H01M 4/62
Claims (7)
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される水素吸蔵合金
粉末の表面に、粒径１μｍ以下のＮｉ粉末またはＴｉ−
Ｎｉ合金粉末をＮｉ量が前記水素吸蔵合金の１〜１０重
量％の範囲で配置した粉末からなることを特徴とする水
素吸蔵合金電極。1. A body having a body-centered cubic structure and a general formula of Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6) on the surface of the hydrogen storage alloy powder, Ni powder or Ti-having a particle size of 1 μm or less.
A hydrogen storage alloy electrode comprising a Ni alloy powder in which the amount of Ni is arranged in the range of 1 to 10% by weight of the hydrogen storage alloy.
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される水素吸蔵合金
粉末を主体とする電極の表面に、Ｎｉまたは、Ｎｉ−Ｃ
ｏ合金、Ｎｉ−Ｓｎ合金、Ｎｉ−Ｚｎ合金、およびＮｉ
−Ｍｏ合金からなる群より選ばれる合金のメッキ層を厚
さ０．５〜１μｍの範囲で、かつＮｉ量が前記水素吸蔵
合金の１〜１０重量％の範囲で被覆したことを特徴とす
る水素吸蔵合金電極。2. It has a body-centered cubic structure and has the general formula Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6) on the surface of the electrode mainly composed of the hydrogen storage alloy powder, Ni or Ni—C
o alloy, Ni-Sn alloy, Ni-Zn alloy, and Ni
-Hydrogen coated with a plating layer of an alloy selected from the group consisting of Mo alloys in a thickness of 0.5 to 1 µm and a Ni content of 1 to 10% by weight of the hydrogen storage alloy. Storage alloy electrode.
以下である請求項１または２に記載の水素吸蔵合金電
極。3. The particle size of the hydrogen storage alloy powder is 75 μm.
The hydrogen storage alloy electrode according to claim 1 or 2, wherein:
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される水素吸蔵合金
粉末の表面に、メカノケミカル反応により、粒径１μｍ
以下のＮｉ粉末またはＴｉ−Ｎｉ合金粉末をＮｉ量が前
記水素吸蔵合金の１〜１０重量％の範囲で付着させる工
程を有する水素吸蔵合金電極の製造方法。4. A body-centered cubic structure having the general formula Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6) on the surface of the hydrogen storage alloy powder, the particle size is 1 μm due to the mechanochemical reaction.
A method for producing a hydrogen storage alloy electrode, comprising a step of depositing the following Ni powder or Ti-Ni alloy powder in an amount of Ni in the range of 1 to 10% by weight of the hydrogen storage alloy.
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示され る水素吸蔵合金
粉末の表面に、粒径１μｍ以下のＮｉ粉末またはＴｉ−
Ｎｉ合金粉末をＮｉ量が前記水素吸蔵合金の１〜１０重
量％の範囲で付着させる工程、および、前記Ｎｉ粉末ま
たはＴｉ−Ｎｉ合金粉末を付着した水素吸蔵合金粉末を
温度４００〜１０００℃で１〜６時間焼結する工程を有
する水素吸蔵合金電極の製造方法。5. Having a body-centered cubic structure, the general formula Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
On the surface of the hydrogen-absorbing alloy powder Ru indicated by 0.4,0.3 ≦ y ≦ 0.6), particle size 1μm or less of Ni powder or Ti-
A step of depositing the Ni alloy powder in an amount of Ni in the range of 1 to 10% by weight of the hydrogen storage alloy; and a hydrogen storage alloy powder having the Ni powder or the Ti—Ni alloy powder deposited at a temperature of 400 to 1000 ° C. A method for producing a hydrogen storage alloy electrode, comprising a step of sintering for ~ 6 hours.
1-x-y （ただし、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、
Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、
Ａｌ、Ｓｉ、Ｐ、Ｂ、および希土類元素からなる群より
選ばれる少なくとも一種の元素であり、０．２≦ｘ≦
０．４、０．３≦ｙ≦０．６）で示される水素吸蔵合金
粉末の表面に、粒径１μｍ以下のＮｉ粉末またはＴｉ−
Ｎｉ合金粉末をＮｉ量が前記水素吸蔵合金の１〜１０重
量％の範囲で付着させる工程、前記Ｎｉ粉末またはＴｉ
−Ｎｉ合金粉末を付着した水素吸蔵合金粉末を主体とす
る電極を成形する工程、および、得られた成形体を温度
４００〜１０００℃で１〜６時間焼結する工程を有する
水素吸蔵合金電極の製造方法。6. A body-centered cubic structure having the general formula Ti x V y M
1-xy (where M is Cr, Mn, Fe, Co, Cu,
Zn, Y, Zr, Nb, Mo, Ag, Hf, Ta, W,
From the group consisting of Al, Si, P, B, and rare earth elements
At least one element selected, 0.2 ≦ x ≦
0.4, 0.3 ≦ y ≦ 0.6) on the surface of the hydrogen storage alloy powder, Ni powder or Ti-having a particle size of 1 μm or less.
A step of depositing a Ni alloy powder in a range of 1 to 10% by weight of the hydrogen storage alloy, the Ni powder or Ti;
-A hydrogen storage alloy electrode having a step of forming an electrode mainly composed of hydrogen storage alloy powder to which Ni alloy powder is adhered, and a step of sintering the obtained formed body at a temperature of 400 to 1000 ° C for 1 to 6 hours. Production method.
以下である請求項４〜６のいずれかに記載の水素吸蔵合
金電極の製造方法。7. The particle size of the hydrogen storage alloy powder is 75 μm.
It is the following, The manufacturing method of the hydrogen storage alloy electrode in any one of Claims 4-6.
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|---|---|---|---|
| JP21455995A JP3454615B2 (en) | 1995-08-23 | 1995-08-23 | Hydrogen storage alloy electrode and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21455995A JP3454615B2 (en) | 1995-08-23 | 1995-08-23 | Hydrogen storage alloy electrode and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH0963569A JPH0963569A (en) | 1997-03-07 |
| JP3454615B2 true JP3454615B2 (en) | 2003-10-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21455995A Expired - Fee Related JP3454615B2 (en) | 1995-08-23 | 1995-08-23 | Hydrogen storage alloy electrode and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3454615B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6048644A (en) * | 1997-03-24 | 2000-04-11 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode |
| JP4601754B2 (en) * | 1999-02-17 | 2010-12-22 | パナソニック株式会社 | Hydrogen storage alloy electrode and manufacturing method thereof |
| US6309779B1 (en) * | 1999-02-17 | 2001-10-30 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode and method for manufacturing the same |
-
1995
- 1995-08-23 JP JP21455995A patent/JP3454615B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0963569A (en) | 1997-03-07 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |