JPS63266767A - Manufacture of hydrogen storage electrode - Google Patents
Manufacture of hydrogen storage electrodeInfo
- Publication number
- JPS63266767A JPS63266767A JP62100368A JP10036887A JPS63266767A JP S63266767 A JPS63266767 A JP S63266767A JP 62100368 A JP62100368 A JP 62100368A JP 10036887 A JP10036887 A JP 10036887A JP S63266767 A JPS63266767 A JP S63266767A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- electrode
- paste
- storage electrode
- metal
- 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 61
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 239000011230 binding agent Substances 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007772 electroless plating Methods 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 6
- 238000007747 plating Methods 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- -1 polyethylene Polymers 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000007769 metal material Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- GRFFKYTUNTWAGG-UHFFFAOYSA-N chloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N GRFFKYTUNTWAGG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003466 welding 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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】
産業上の利用分野
本発明は、水素を可逆的に吸蔵・放出する水素吸蔵合金
を用いる水素吸蔵電極の製造方法に関するもので、無公
害で高エネルギー密度のアルカリ蓄電池が提供できるも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a hydrogen storage electrode using a hydrogen storage alloy that reversibly stores and releases hydrogen. This is something that can be provided.
従来の技術
各種の電源のうち二次電池としては、鉛蓄電池とアルカ
リ蓄電池とが広く使われている。BACKGROUND OF THE INVENTION Among various power sources, lead-acid batteries and alkaline batteries are widely used as secondary batteries.
アルカリ蓄電池のうち、最も広く使われているのは、ニ
ッケルーカドミウム蓄電池である。この電池は性能的に
かなり優れているが、依然おして高エネルギー密度や無
公害への期待が高く新しい電池系が検討されている。The most widely used alkaline storage battery is the nickel-cadmium storage battery. Although this battery has considerably superior performance, new battery systems are still being considered with high expectations for high energy density and non-pollution.
例えばこの中で負極のカドミウムに代わって亜鉛が取り
上げられてきたが、よ（知られているように寿命に問題
があるので広い実用化には至っていない。For example, zinc has been used as a substitute for cadmium in the negative electrode, but it has not been widely put into practical use due to problems with its lifespan.
最近注目されてきたのは水素を可逆的に吸蔵・放出する
水素吸蔵合金を負極に用いるアルカリ蓄電池である。こ
の場合は、カドミウムや亜鉛などと同じ取扱いで電池を
構成でき、実際の放電可能な容量密度をカドミウムより
大きくできることや亜鉛のようなデンドライトの形成や
電極の形状変化などがないことから、高エネルギー密度
で長寿命、無公害のアルカリ蓄電池として有望である。Alkaline storage batteries that use a hydrogen storage alloy for the negative electrode, which reversibly stores and releases hydrogen, have recently attracted attention. In this case, batteries can be constructed using the same treatment as cadmium or zinc, and the actual dischargeable capacity density can be higher than that of cadmium. Unlike zinc, there is no formation of dendrites or changes in the shape of the electrodes, so it is possible to construct a battery with high energy. It is promising as a high-density, long-life, pollution-free alkaline storage battery.
この水素吸蔵合金を用いた水素吸蔵電極の製造方法とし
ては、従来から水素吸蔵合金を焼結して電極を得る焼結
式や発泡金属、金属繊維などの金属三次元多孔体に水素
吸蔵合金を結着剤などと共に充填した方式がよく用いら
れていた。Conventional methods for manufacturing hydrogen storage electrodes using this hydrogen storage alloy include a sintering method in which the electrode is obtained by sintering the hydrogen storage alloy, and a method in which the hydrogen storage alloy is made into a three-dimensional porous metal body such as foamed metal or metal fiber. A method in which it was filled with a binder and the like was often used.
しかし、これらの方式による水素吸蔵電極の製造方法は
、材料コストが高くなることや製造工程が複雑であるこ
となどの問題があった。However, these methods of manufacturing hydrogen storage electrodes have problems such as high material costs and complicated manufacturing processes.
一方、水゛素吸蔵合金粉末と結着剤などを予め混練しペ
ーストとし、これをパンチングメタルやエキスパンドメ
タル、金属ネットなどの金属二次元多孔体に塗着しその
後乾燥して得るいわゆるペースト式水素吸蔵電極の製造
方法は、製造方法が簡単であり、金属三次元多孔体のよ
うな高価な材料を使用しないことから安価な電極が得ら
れるという特徴があった。On the other hand, hydrogen storage alloy powder and a binder are kneaded in advance to form a paste, which is applied to a two-dimensional porous metal body such as punched metal, expanded metal, or metal net, and then dried. The method for manufacturing an occlusion electrode has the characteristics that the manufacturing method is simple and that an inexpensive electrode can be obtained because an expensive material such as a metal three-dimensional porous body is not used.
発明が解決しようとする問題点
この水素吸蔵合金粉末と結着剤などを予め混練しペース
トとし、これをパンチングメタルやエキスパンドメタル
、金属ネットなどの金属二次元多孔体に塗着しその後乾
燥して得るペースト式水素吸蔵電極の製造方法は、本来
製造方法が簡単で安価な電極が得られるという特徴があ
るが、この方法で得た電極を用いてアルカリ蓄電池を構
成すると次のような問題がありこれまであまり用いられ
ていなかった。Problem to be solved by the invention This hydrogen-absorbing alloy powder and a binder are kneaded in advance to form a paste, which is applied to a two-dimensional porous metal body such as punched metal, expanded metal, or metal net, and then dried. The method of manufacturing the paste-type hydrogen storage electrode that is obtained has the characteristics of being easy to manufacture and producing an inexpensive electrode, but when an alkaline storage battery is constructed using the electrode obtained using this method, there are the following problems. It has not been used much so far.
すなわち、その主たる問題は、従来の水素吸蔵合金を焼
結して電極を得る焼結式や発泡金属、金属繊維などの金
属三次元多孔体に水素吸蔵合金を結着剤などと共に充填
した方式の電極と比較して電極の導電性が悪（、とくに
大電流充放電特性に難点があった。放電電圧の低下が大
きく実用上大きな問題点であった。In other words, the main problem lies in the conventional sintering method in which electrodes are obtained by sintering a hydrogen storage alloy, and the method in which a three-dimensional porous metal body such as foamed metal or metal fiber is filled with a hydrogen storage alloy together with a binder. Compared to the electrode, the conductivity of the electrode was poor (particularly the large current charging and discharging characteristics were difficult. The drop in discharge voltage was large, which was a major problem in practical use.
本発明は、製造が簡単で低価格化が図れるパンチングメ
タルやエキスパンドメタル、金属ネットなどの金属二次
元多孔体を用いたペースト式水素吸蔵電極の導電性を改
善し、急速な充放電特性に優れた水素吸蔵合金電極の製
造方法を提供することを目的とする。The present invention improves the conductivity of a paste-type hydrogen storage electrode using a two-dimensional porous metal material such as punched metal, expanded metal, or metal net, which is easy to manufacture and can be manufactured at a low cost, and has excellent rapid charging and discharging characteristics. The purpose of the present invention is to provide a method for manufacturing a hydrogen storage alloy electrode.
問題点を解決するための手段
本発明は、水素吸蔵合金粉末と結着剤、ペースト粘度調
整剤などを予め混練しペーストとし、これをパンチング
メタルやエキスパンドメタル、金属ネットなどの金属二
次元多孔体に塗着しその後乾燥して得た極板の表面に、
さらに多孔性の導電性層を形成したことを特徴とする水
素吸蔵電極の製造方法である。Means for Solving the Problems The present invention involves pre-kneading hydrogen-absorbing alloy powder, a binder, a paste viscosity modifier, etc. to form a paste, and applying the paste to two-dimensional metal porous bodies such as punched metal, expanded metal, and metal net. On the surface of the electrode plate obtained by applying it to and then drying it,
This method of manufacturing a hydrogen storage electrode is further characterized in that a porous conductive layer is formed.
作用
通常パンチングメタルやエキスパンドメタル、金属ネッ
トなどの金属二次元多孔体を芯材として用いたペースト
式水素吸蔵電極は、焼結式や発泡金属、金属繊維などの
金属三次元多孔体に水素吸蔵合金を結着剤などと共に充
填した方式の電極と比較して明らかに電極の導電性が悪
い。しかし、本発明はこの極板の表面に、さらに多孔性
の導電性層を形成することにより金属二次元多孔体を芯
材として用いたペースト式水素吸蔵電極でも電極の導電
性を向上することが可能になり、急速な充放電を行なっ
ても特性に優れたアルカリ蓄電池用の水素吸蔵合金電極
が得られる。またこれらの導電性層は多孔性であること
から、水素吸蔵合金粉末相互の電子伝導を向上させつつ
、イオン伝導への悪影響は少ない。さらに水素吸蔵電極
で重要な特性である密閉形アルカリ蓄電池の過充電時に
発生す、る酸素ガスを吸収する能力が一段と向上し、充
放電サイクル寿命の向上が図られる。Paste-type hydrogen storage electrodes that use a two-dimensional porous metal material such as punched metal, expanded metal, or metal net as the core material are usually made using a hydrogen-absorbing alloy that uses a three-dimensional porous metal material such as sintered metal, foamed metal, or metal fiber as the core material. The conductivity of the electrode is clearly poorer than that of an electrode filled with a binder or the like. However, in the present invention, by further forming a porous conductive layer on the surface of this electrode plate, it is possible to improve the conductivity of the electrode even in a paste-type hydrogen storage electrode using a two-dimensional porous metal material as the core material. This makes it possible to obtain hydrogen storage alloy electrodes for alkaline storage batteries that have excellent characteristics even when rapidly charged and discharged. Moreover, since these conductive layers are porous, they improve the electron conduction between the hydrogen storage alloy powders and have little adverse effect on the ion conduction. Furthermore, the ability to absorb oxygen gas generated during overcharging of sealed alkaline storage batteries, which is an important characteristic of hydrogen storage electrodes, is further improved, and the charge/discharge cycle life is improved.
実施例 以下、本発明の実施例について説明する。Example Examples of the present invention will be described below.
水素吸蔵合金として市販のＭｍ（ミツシュメタル）、Ｎ
ｉ、Ｃｏ、Ｍｎ、ＡＩの各原材料を一定の組成比に秤量
してアルゴンアーク溶解炉によってＭｍＮ ｉｓ、５Ｃ
Ｏｏ、ａＭｎｏ、４Ａ＋ｏ、ｓ合金を製造した。ついで
この合金を公知の方法に従って真空熱処理炉で熱処理し
その後、この合金試料を４００メツシユ以下の粒径にな
るように粉砕した。Commercially available hydrogen storage alloys Mm (Mitshu Metal), N
The raw materials of I, Co, Mn, and AI were weighed to a certain composition ratio and melted into MmN is, 5C using an argon arc melting furnace.
Oo, aMno, 4A+o,s alloys were manufactured. This alloy was then heat treated in a vacuum heat treatment furnace according to a known method, and then the alloy sample was ground to a particle size of 400 mesh or less.
このようにして得られた水素吸蔵合金にポリビニルアル
コールの５％（重量）のエチレングリコール溶液、重量
比で０．８％のポリエチレン微粉末、同じ（０，５％の
塩化ビニル−アクリロニトリル短繊維を加えて混練しペ
ーストとした。このペーストを厚さ０．１５ｍ、孔径１
．８ｍｍ、開孔度５０％の鉄製でニッケルメッキを施し
たパンチングメタル板に塗着し、０．６ｍ幅のスリット
を通して平滑化し、その後１２０℃で１時間乾燥して水
素吸蔵電極を得た。To the hydrogen storage alloy thus obtained, a 5% (by weight) ethylene glycol solution of polyvinyl alcohol, 0.8% (by weight) polyethylene fine powder, and the same (0.5% (by weight) vinyl chloride-acrylonitrile short fibers) were added. and kneaded to make a paste.This paste was made into a paste with a thickness of 0.15m and a pore diameter of 1.
．． It was applied to a nickel-plated punched metal plate made of iron with a diameter of 8 mm and a porosity of 50%, smoothed through a 0.6 m wide slit, and then dried at 120° C. for 1 hour to obtain a hydrogen storage electrode.
このようにして作った水素吸蔵電極を、さらに加圧プレ
ス処理を行なった後、水素吸蔵電極の表面に以下の様に
水素吸蔵電極Ａ−Ｌとして各種の多孔性の導電性層を形
成した。また比較のために多孔性の導電性層を形成しな
い水素吸蔵電極Ｍを加えた。The thus produced hydrogen storage electrode was further subjected to pressure pressing treatment, and then various porous conductive layers were formed on the surface of the hydrogen storage electrode as hydrogen storage electrodes A-L as described below. Further, for comparison, a hydrogen storage electrode M without forming a porous conductive layer was added.
水素吸蔵電極Ａ−無無電銅鋼メッ
キ素吸蔵電極Ｂ−−電解ニッケルメッキ水素吸蔵電極Ｃ
−電気銅メッキ
水素吸蔵電極り一電気ニッケルメッキ
水素吸蔵電極Ｅ−電気（鋼＋ニッケル）メッキ水素吸蔵
電極Ｆ−ニッケル粉末塗布
水素吸蔵電極Ｇ−炭素粉末塗布
水素吸蔵電極Ｈ−（炭素子パラジウム）粉末塗布
水素吸蔵電極■−パラジウム析出
水素吸蔵電極Ｊ−−金析出
水素吸蔵電極に一ニッケル蒸着
水素吸蔵電極り一銅蒸着
水素吸蔵電極Ｍ−一孔性の導電性層なしこのようにして
得た水素吸蔵電極Ａ−Ｍは、その後密閉形ニッケルー水
素二次電池として単２形で評価を行なった。Hydrogen storage electrode A--electroless copper steel plating element storage electrode B--electrolytic nickel plating hydrogen storage electrode C
- Electrolytic copper plated hydrogen storage electrode - Electrolytic nickel plated hydrogen storage electrode E - Electric (steel + nickel) plated hydrogen storage electrode F - Nickel powder coated hydrogen storage electrode G - Carbon powder coated hydrogen storage electrode H - (carbon palladium) Powder-coated hydrogen storage electrode■ - Palladium-deposited hydrogen storage electrode J--Gold-precipitated hydrogen storage electrode, one nickel vapor-deposited hydrogen storage electrode, copper vapor-deposited hydrogen storage electrode M-no porous conductive layer thus obtained The hydrogen storage electrodes A-M were then evaluated as AA sealed nickel-metal hydride secondary batteries.
すなわち、先の水素吸蔵電極を各々幅３．９ｃｍ長さ２
６ＣＩｌに裁断し、リード板を所定の２カ所にスポット
溶接により取り付けた。相手径としては、公知の発泡式
ニッケル極を選び、幅３．９ｃｍ＋長さ２２ｃｎとして
用いた。この場合もリード板を２カ所取り付けた。In other words, the hydrogen storage electrodes are each 3.9 cm wide and 2 cm long.
It was cut into 6CIl pieces, and lead plates were attached to two predetermined locations by spot welding. As the mating diameter, a known foamed nickel electrode was selected and used with a width of 3.9 cm and a length of 22 cm. In this case as well, lead plates were attached at two locations.
セパレータとしては、ボリアミド不織布、電解液として
は、比重１．２０の苛性カリ水溶液に水酸化リチウムを
２０ ｇ／ｅ溶解して用いた。公称容量は３．ＯＡｈで
ある。A polyamide nonwoven fabric was used as the separator, and 20 g/e of lithium hydroxide was dissolved in a caustic potassium aqueous solution having a specific gravity of 1.20 as the electrolyte. The nominal capacity is 3. It is OAh.
これらの電池を通常の充放電サイクル試験によって２０
℃で評価した結果を説明する。These batteries were subjected to a normal charge/discharge cycle test for 20
The results of evaluation at °C will be explained.
充電は、０．２Ｃ（５時間率）で１３０％まで、放電は
０．５Ｃ（２時間率）で終止電圧０゜８Ｖとし充放電サ
イクルを１０サイクルまで繰り返し、その後は、充電を
、Ｃ）、５Ｃ（２時間率）で１５０％まで、放電は１．
０Ｃ（１時間率）で同様の試験を行なった。Charge at 0.2C (5 hour rate) to 130%, discharge at 0.5C (2 hour rate) with a final voltage of 0°8V, repeat the charge/discharge cycle up to 10 cycles, then continue charging.C) , 5C (2 hour rate) to 150%, discharge 1.
A similar test was conducted at 0C (1 hour rate).
その結果の中から、単２形密閉形ニッケルー水素二次電
池を構成するのに使用した水素吸蔵電極Ａ−Ｍと２０サ
イクル、２００サイクルでの充放電サイクル試験での電
池放電容量と中間放電電位の関係をまとめて表に示す。Among the results, the hydrogen storage electrode A-M used to construct the AA sealed type nickel-metal hydride secondary battery, the battery discharge capacity and intermediate discharge potential in the charge/discharge cycle test at 20 cycles and 200 cycles. The relationship is summarized in the table.
表から明らかな様に、多孔性の導電性層を形成しない水
素吸蔵電極Ｍは、２００サイクルで電池の放電容量は公
称容量の３．ＯＡｈを大幅に下回り、また中間放電電位
の低下も大きかった。さらにこの電池の充電時の電池内
圧を調べたところ、最高内圧は１０ｋｇ／ｃ−以上を示
し、ガス吸収能力も不足していることが認められた。As is clear from the table, the hydrogen storage electrode M that does not form a porous conductive layer has a battery discharge capacity of 3.0% of the nominal capacity after 200 cycles. It was significantly lower than OAh, and the intermediate discharge potential also decreased significantly. Furthermore, when the internal pressure of this battery during charging was examined, the maximum internal pressure was 10 kg/c- or more, and it was recognized that the gas absorption capacity was insufficient.
表
これに対して水素吸蔵電極Ａ−Ｌで構成した電池は、放
電容量、中間放電電位とも非常に優れており、従来の発
泡金属、金属繊維などの金属三次元多孔体に水素吸蔵合
金を結着剤などと共に充填した方式で得た電極と比較し
ても全く遜色のない性能を有していた。またこれらの電
池の充電時の電池内圧は、最高時でもいずれも３．２〜
８．７ｋｇ／−であり高いガス吸収能力を有していたが
、その中でも多孔性の導電性層を銅もしくはニッケルの
電気メッキまたは無電解メッキにより形成したものが特
に優れていた。In contrast, a battery constructed with hydrogen storage electrodes A-L has excellent discharge capacity and intermediate discharge potential, and has a hydrogen storage alloy bonded to a conventional three-dimensional porous metal body such as metal foam or metal fiber. Even when compared with electrodes obtained by filling with adhesive etc., the performance was comparable. In addition, the internal pressure of these batteries during charging is 3.2~3.2 at the maximum.
It had a high gas absorption capacity of 8.7 kg/-, and among them, those in which the porous conductive layer was formed by copper or nickel electroplating or electroless plating were particularly excellent.
そして多孔性の導電性層としては銅、ニッケル、炭素、
パラジウム、白金などが適当であり、多孔性の導電性層
の形成には、メッキ法、塗布法、吹き付は法、蒸着法、
スパッター法などが適応できる。この中で最も有効な方
法としては、多孔性の導電性層を特に鋼もしくはニッケ
ルの電−気メッキまたは無電解メッキにより形成する。The porous conductive layer includes copper, nickel, carbon,
Palladium, platinum, etc. are suitable, and plating methods, coating methods, spraying methods, vapor deposition methods, etc. are suitable for forming the porous conductive layer.
Sputtering method etc. can be applied. The most effective method is to form the porous conductive layer by electroplating or electroless plating, especially of steel or nickel.
発明の効果
以上のように本発明の水素吸蔵電極の製造方法では、密
閉電池を構成した場合、本来の特徴である製造が簡単で
低価格化が図れることとともに、導電性やガス吸収能の
向上が図られ合わせて電極強度も向上することから、高
容量で長寿命、かつ急速充放電特性に優れた電池を提供
できる。Effects of the Invention As described above, in the method for manufacturing a hydrogen storage electrode of the present invention, when a sealed battery is configured, the original feature of manufacturing is simple and low cost can be achieved, and the conductivity and gas absorption capacity are improved. Since the electrode strength is also improved, it is possible to provide a battery with high capacity, long life, and excellent rapid charging and discharging characteristics.
Claims (3)
剤を予め混練してペーストとし、前記ペーストをパンチ
ングメタル、エキスパンドメタルや金属ネットなどの金
属二次元多孔体に塗着し、乾燥して得た極板の表面に、
さらに多孔性の導電性層を形成したことを特徴とする水
素吸蔵電極の製造方法。(1) A hydrogen-absorbing alloy powder binder and a paste viscosity modifier are kneaded in advance to form a paste, and the paste is applied to a two-dimensional porous metal body such as punched metal, expanded metal, or metal net, and dried to obtain a paste. on the surface of the electrode plate,
A method for producing a hydrogen storage electrode, further comprising forming a porous conductive layer.
ウム、白金の少なくとも１種により形成したことを特徴
とする特許請求の範囲第１項記載の水素吸蔵電極の製造
方法。(2) The method for manufacturing a hydrogen storage electrode according to claim 1, wherein the porous conductive layer is made of at least one of copper, nickel, carbon, palladium, and platinum.
ッキまたは無電解メッキにより形成したことを特徴とす
る特許請求の範囲第１項記載の水素吸蔵電極の製造方法
。(3) The method for manufacturing a hydrogen storage electrode according to claim 1, wherein the porous conductive layer is formed by electroplating or electroless plating of copper or nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100368A JPH0763006B2 (en) | 1987-04-23 | 1987-04-23 | Method for manufacturing hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62100368A JPH0763006B2 (en) | 1987-04-23 | 1987-04-23 | Method for manufacturing hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63266767A true JPS63266767A (en) | 1988-11-02 |
| JPH0763006B2 JPH0763006B2 (en) | 1995-07-05 |
Family
ID=14272112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62100368A Expired - Lifetime JPH0763006B2 (en) | 1987-04-23 | 1987-04-23 | Method for manufacturing hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0763006B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07234200A (en) * | 1994-02-24 | 1995-09-05 | Nec Corp | Flat metal electrode for qualification electrode and its manufacturing method |
| WO1995027315A1 (en) * | 1994-03-31 | 1995-10-12 | Motorola, Inc. | Improved metal hydride hydrogen storage electrodes |
| EP0975034A1 (en) * | 1997-05-19 | 2000-01-26 | Sociedad Espanola Del Acumulador Tudor, S.A. | Procedure for the manufacture of negative electrodes for alkaline storage batteries and electrode so obtained |
| US6579645B2 (en) | 2000-03-28 | 2003-06-17 | Sanyo Electric Co., Ltd. | Hydrogen absorbing alloy for electrode, hydrogen absorbing alloy electrode and alkaline storage battery |
| JP2006196280A (en) * | 2005-01-13 | 2006-07-27 | Univ Of Fukui | Composite sheet body and its manufacturing method |
| JP4552238B2 (en) * | 1999-05-11 | 2010-09-29 | 株式会社Ｇｓユアサ | Method for producing hydrogen storage alloy electrode |
-
1987
- 1987-04-23 JP JP62100368A patent/JPH0763006B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07234200A (en) * | 1994-02-24 | 1995-09-05 | Nec Corp | Flat metal electrode for qualification electrode and its manufacturing method |
| WO1995027315A1 (en) * | 1994-03-31 | 1995-10-12 | Motorola, Inc. | Improved metal hydride hydrogen storage electrodes |
| EP0975034A1 (en) * | 1997-05-19 | 2000-01-26 | Sociedad Espanola Del Acumulador Tudor, S.A. | Procedure for the manufacture of negative electrodes for alkaline storage batteries and electrode so obtained |
| JP4552238B2 (en) * | 1999-05-11 | 2010-09-29 | 株式会社Ｇｓユアサ | Method for producing hydrogen storage alloy electrode |
| US6579645B2 (en) | 2000-03-28 | 2003-06-17 | Sanyo Electric Co., Ltd. | Hydrogen absorbing alloy for electrode, hydrogen absorbing alloy electrode and alkaline storage battery |
| JP2006196280A (en) * | 2005-01-13 | 2006-07-27 | Univ Of Fukui | Composite sheet body and its manufacturing method |
| JP4644801B2 (en) * | 2005-01-13 | 2011-03-09 | 国立大学法人福井大学 | Composite sheet body and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0763006B2 (en) | 1995-07-05 |
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