JPS63264869A - Manufacture of hydrogen storage electrode - Google Patents
Manufacture of hydrogen storage electrodeInfo
- Publication number
- JPS63264869A JPS63264869A JP62098933A JP9893387A JPS63264869A JP S63264869 A JPS63264869 A JP S63264869A JP 62098933 A JP62098933 A JP 62098933A JP 9893387 A JP9893387 A JP 9893387A JP S63264869 A JPS63264869 A JP S63264869A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- hydrogen
- alloy
- electrode
- storage 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.)
- Granted
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000003860 storage Methods 0.000 title claims abstract description 77
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 48
- 239000000956 alloy Substances 0.000 claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 abstract description 31
- 238000010298 pulverizing process Methods 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910000905 alloy phase Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018561 MmNi5 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent 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
- 238000006243 chemical reaction Methods 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
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 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
- H01M4/36—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
-
- 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
-
- 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。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a hydrogen storage electrode using a hydrogen storage alloy that reversibly stores and releases hydrogen.
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.
そのうちアルカリ蓄電池には１、ニッケルーカドミウム
蓄電池が大半を占め、焼結式ニッケル極の実用化が利用
の範囲を大きく広げた。Of these, nickel-cadmium storage batteries account for the majority of alkaline storage batteries, and the practical application of sintered nickel electrodes has greatly expanded the scope of their use.
この電池は放電特性の点で優れ、高率放電を行なっても
電圧や容量の低下が少ない。また、寿命も長く、過充電
など苛酷な条件にも耐え、低温での性能もよい。This battery has excellent discharge characteristics, with little drop in voltage or capacity even during high rate discharge. They also have a long lifespan, can withstand harsh conditions such as overcharging, and have good performance at low temperatures.
ところが高エネルギー密度に対する対応には、なお相当
の努力が必要である。正極については、例えば、発泡状
ニッケル極などが実用化されたが、負極のカドミウム極
については、現在のところあまり顕著な進歩はない。However, considerable efforts are still required to cope with high energy densities. As for positive electrodes, for example, foamed nickel electrodes have been put into practical use, but as of now there has not been much significant progress on cadmium negative electrodes.
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
上げられている。−次電池用としては成功しているが、
よく知られているように充放電時での変形、樹枝状析出
などによる寿命の問題があるので特殊用の域を出ていな
い。For example, zinc is being used instead of cadmium in the negative electrode. -Although it has been successful for secondary batteries,
As is well known, there are problems with life expectancy due to deformation during charging and discharging, dendritic precipitation, etc., so they are still limited to special use.
そこで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用いた水素極である。宇宙用に採
用されている水素ガス拡散電極方式と興なり、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。Therefore, hydrogen electrodes using hydrogen storage alloys that reversibly absorb and release hydrogen have been attracting attention recently. This is based on the hydrogen gas diffusion electrode system used for space applications.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. Because there is no formation of dendrites or changes in the shape of the electrodes, it is promising as a high-energy 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法として
は、従来から水素吸蔵合金を多孔性導電体と共に焼結し
て電極を得る焼結式や発泡金属や金属繊維、パンチング
メタルやエキスバンドメタル、金属ネットなどの多孔性
導電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（用いられていた。これらに用いられる水素吸蔵合
金は、粉末状であり、一般には機械的な粉砕で粉末化さ
れている。一方この粉砕を水素ガスでの水素化と脱水素
化で行なう例も特開昭５３−１０３９１０号公報などで
知られている。Conventional methods for manufacturing hydrogen storage electrodes using this hydrogen storage alloy include a sintering method in which the hydrogen storage alloy is sintered with a porous conductor to obtain an electrode, a method using foamed metal, metal fiber, punched metal, and expanded metal. , a method in which a porous conductor such as a metal net is filled with a hydrogen storage alloy along with a binder is commonly used.The hydrogen storage alloy used in these materials is in powder form and is generally mechanically crushed On the other hand, an example in which this pulverization is carried out by hydrogenation and dehydrogenation with hydrogen gas is also known, such as in JP-A-53-103910.
発明が解決しようとする問題点
水素吸蔵合金を用いた水素吸蔵電極はこのように高エネ
ルギー密度の向上には有効であるが、これまでのところ
、アルカリ蓄電池の水素吸蔵合金負極に使用する際にと
き次のような問題があった。すなわち、水素の吸蔵と放
出、つまり充電と放電を繰返すと、合金粉末の微粉化が
進み電極が変形したり、粉末の脱落が生じたりする。こ
のことによって、電極の性能低下を招（ことがある。Problems to be Solved by the Invention Hydrogen storage electrodes using hydrogen storage alloys are effective in improving high energy density as described above, but so far, when used as hydrogen storage alloy negative electrodes for alkaline storage batteries, I had the following problem: That is, when hydrogen storage and release, that is, charging and discharging, are repeated, the alloy powder becomes finer and the electrode deforms or the powder falls off. This may lead to a decrease in electrode performance.
また、粉砕した合金粉末中に電極として有効に作用する
合金相以外の不純物相ががなり含まれており、これが電
解液中で溶解して性能を低下させることがあった。In addition, the pulverized alloy powder contains impurity phases other than the alloy phase that effectively acts as an electrode, and these may dissolve in the electrolyte and degrade performance.
本発明はこの水素吸蔵合金をアルカリ蓄電池の水素吸蔵
合金負極に使用する際に、これまで問題であった微粉化
や溶解などを解決し、長寿命化を図ると同時に水素吸蔵
電極の簡易な製造方法を提供することを目的にする。The present invention solves the problems of pulverization and dissolution that have hitherto been a problem when using this hydrogen storage alloy as a hydrogen storage alloy negative electrode of an alkaline storage battery, and at the same time aims to extend the life of the hydrogen storage alloy and simplify the production of the hydrogen storage electrode. The purpose is to provide a method.
問題点を解決するための手段
本発明は、水素吸蔵合金を圧力容器に収納し、水素ガス
での水素化と、脱水素化を行ない、前記水素化と、脱水
素化により微粉末化していない部分だけを分離し、残り
をその後水素吸蔵電極用として用いることを特徴とする
水素吸蔵電極の製造方法である。Means for Solving the Problems The present invention stores a hydrogen storage alloy in a pressure vessel and performs hydrogenation with hydrogen gas and dehydrogenation, and the hydrogen storage alloy is not pulverized by the hydrogenation and dehydrogenation. This is a method for manufacturing a hydrogen storage electrode, which is characterized in that only a portion is separated and the remainder is used as a hydrogen storage electrode.
さらに、好ましくは篩分により粒径が１００ミクロン以
下の粒径のみを分離して使用するものである。また微粉
化を十分行なうために水素ガスでの水素化と、脱水素化
は２回以上行ない、さらに酸化を抑制するためにその水
素化を行なった圧力容器内で、その後微粉末化していな
い部分だけを分離することが良い。Further, it is preferable that only particles having a particle size of 100 microns or less be separated and used by sieving. In addition, to ensure sufficient pulverization, hydrogenation with hydrogen gas and dehydrogenation are performed two or more times, and in order to further suppress oxidation, the parts that have not been pulverized in the pressure vessel after hydrogenation are It is better to separate only the
作用
水素ガスでの水素化と、脱水素化を行ない、水素化と、
脱水素化により微粉末化していない部分だけを分離除去
し、残りを、その後水素吸蔵電極用として用いることに
より微粉化の問題を解決する。すなわち、水素ガスでの
水素化は機械的粉砕と比較して、より微細な粉末を簡単
に得られ、そのことによって水素吸蔵電極で充放電を繰
返してもそれ以上微粉化が進みにくい。また溶解につい
ては、有効合金相だけが選択的に微粉化し合金中の不純
物相は十分に微粉化していないためその部分だけ篩分な
どにより分離できることにより不純物の溶解を防ぐこと
ができる。Hydrogenation with working hydrogen gas and dehydrogenation are performed.
The problem of pulverization is solved by separating and removing only the portion that has not been pulverized by dehydrogenation, and then using the remainder as a hydrogen storage electrode. That is, hydrogenation with hydrogen gas can easily obtain finer powder than mechanical pulverization, and as a result, even if the hydrogen storage electrode is repeatedly charged and discharged, further pulverization is difficult to proceed. Regarding dissolution, only the effective alloy phase is selectively pulverized, and since the impurity phase in the alloy is not sufficiently pulverized, only that portion can be separated by sieving, etc., thereby preventing the impurities from dissolving.
このように篩分により選択的に微粉化した有効合金相だ
けが利用でき電解液中で溶解しやすい合金中の不純物相
を粗い粒子として分離することができるので水素吸蔵電
極の長寿命化に有効であることがわかった。In this way, only the effective alloy phase that is selectively pulverized by sieving can be used, and the impurity phase in the alloy that is easily dissolved in the electrolyte can be separated as coarse particles, which is effective for extending the life of the hydrogen storage electrode. It turned out to be.
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ＭｍＮｉ５．ａＣＯ
ｏ、ｓＭｎｏ、ａＡｔｏ、ｓの組成を有する合金の製造
をめざした。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、図に示すような装置に収
納した。図は本発明の水素吸蔵電極の一製造装置である
。１〜１０ｃｍ角程度の塊状の水素吸蔵合金１は、圧力
容器２の上部の粗い金属メツシュ３上に収納した。この
圧力容器２はガスバルブ４を有し、また容器内部に篩分
のためのメツシュ篩５が収納された密閉が可能な構造で
ある。ガスバルブ４は、真空引きや水素ガス導入、さら
には不活性ガスの導入に用いる。Commercially available hydrogen storage alloys Mm (Mitshu Metal), N
The raw materials MmNi5. aCO
The aim was to produce an alloy having the following compositions: o, sMno, aAto, s. This alloy was then heat treated in a vacuum heat treatment furnace according to a known method, and then placed in an apparatus as shown in the figure. The figure shows an apparatus for manufacturing a hydrogen storage electrode of the present invention. A hydrogen storage alloy 1 in the form of a block of about 1 to 10 cm square was housed on a coarse metal mesh 3 at the top of a pressure vessel 2 . This pressure vessel 2 has a gas valve 4, and has a sealable structure in which a mesh sieve 5 for sieving is housed inside the vessel. The gas valve 4 is used for evacuation, hydrogen gas introduction, and inert gas introduction.
図をもとに本発明の詳細な説明する。まず水素吸蔵合金
１を収納した圧力容器２内をガスバルブ４を介して真空
ポンプにより脱ガスした。そして次に同じバルブ４から
市販の水素ガスを導入し、約３０気圧まで加圧した。こ
れにより水素吸蔵合金１はまちな（水素吸蔵反応を開始
した。この水素化を充分行なった後、バルブ４から水素
ガスを放出し、放出を充分行なうために真空ポンプによ
り脱ガスした。この水素化と脱水素化を３回繰返した後
、圧力容器２を振動させ微細化した水素吸蔵合金粉末を
２００メツシユのメツシュ篩５で篩分した。メツシュ篩
５を通過した粉末は、その後バルブ４から導入したアル
ゴンガス中でしばら（放置し、その後圧力容器２から外
へ取り出した。この際の２００メツシユのメツシュ篩を
通過し回収された水素吸蔵合金粉末量は当初仕込んだ合
金量のほぼ９６％であった。一方残り約４％のメツシュ
篩を通過できなかった粉末や粒子を調べてみた結果、こ
れらは水素吸蔵のための有効合金相とは幾分相が異なっ
ていることがＸ線回折によって確認できた。またこの粗
い粉末や粒子はその後、水素ガスでの水素化を行なった
ところ水素化特性は先の２００メツシユのメツシュ篩を
通過し回収された水素吸蔵合金粉末と比較するとかなり
悪い性能であった。The present invention will be explained in detail based on the drawings. First, the inside of the pressure vessel 2 containing the hydrogen storage alloy 1 was degassed by a vacuum pump via the gas valve 4. Next, commercially available hydrogen gas was introduced through the same valve 4, and the pressure was increased to about 30 atmospheres. As a result, the hydrogen storage alloy 1 started a hydrogen storage reaction. After this hydrogenation was sufficiently performed, hydrogen gas was released from the valve 4, and degassed using a vacuum pump to ensure sufficient release. After repeating dehydrogenation three times, the pressure vessel 2 was vibrated and the fine hydrogen storage alloy powder was sieved through a 200-mesh mesh sieve 5.The powder that passed through the mesh sieve 5 was then introduced through a valve 4. The hydrogen storage alloy powder was left for a while in a heated argon gas, and then taken out from the pressure vessel 2. At this time, the amount of hydrogen-absorbing alloy powder that passed through a 200-mesh sieve and was recovered was approximately 96% of the amount of alloy initially charged. On the other hand, as a result of examining the remaining approximately 4% of powders and particles that did not pass through the mesh sieve, X-ray diffraction revealed that these had a phase that was somewhat different from the effective alloy phase for hydrogen storage. This was confirmed.Also, when this coarse powder and particles were subsequently hydrogenated with hydrogen gas, the hydrogenation properties were considerably poorer than the hydrogen storage alloy powder recovered after passing through a 200-mesh sieve. Met.
次に、２００メツシユのメツシュ篩を通過し回収された
水素吸蔵合金粉末を水素吸蔵電極とし、さらに密閉形ニ
ッケルー水素二次電池を構成して評価した結果について
説明する。Next, the results of evaluating a sealed nickel-metal hydride secondary battery using the hydrogen storage alloy powder recovered after passing through a 200-mesh sieve as a hydrogen storage electrode will be described.
まず２００メツシユ通過の水素吸蔵合金粉末をポリビニ
ルアルコールの５％（重量）のエチレングリニ１−ル溶
液、さらに重量比で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
加えてペースト状にし十分混練し、厚さ０．１５ａｍ、
孔径１．８ｍ＋ａ、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、０．６＋ｍｓ
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。このようにして得た水
素吸蔵電極を電極Ａとする。First, hydrogen storage alloy powder that has passed through 200 meshes is added to a 5% (by weight) ethylene glycol solution of polyvinyl alcohol, then 0.8% (by weight) polyethylene fine powder, and the same (0.5% vinyl chloride-acrylonitrile solution). Add short fibers to make a paste, knead thoroughly, and make a paste with a thickness of 0.15 am.
Painted on a punched metal plate made of iron and nickel plated with a hole diameter of 1.8m+a and a porosity of 50%, 0.6+ms
It was smoothed through a wide slit and then dried at 120° C. for 1 hour to obtain a hydrogen storage electrode. The hydrogen storage electrode thus obtained is referred to as electrode A.
比較のために、水素ガスでの水素化と脱水素化は同様に
行なうが、水素吸蔵合金粉末を２００メツシユのメツシ
ュ篩５で篩分をしないで同様に水素吸蔵電極にしたもの
を電極Ｂとする。さらに、水素ガスでの水素化と脱水素
化をしないで水素吸蔵合金をボールミルによる機械的な
粉砕法によって２００メツシユのメツシュ篩を通過する
まで粉砕して得た水素吸蔵合金粉末を同様に水素吸蔵電
極にしたものを電極Ｃとして加えた。For comparison, hydrogenation and dehydrogenation using hydrogen gas were performed in the same way, but the hydrogen storage alloy powder was made into a hydrogen storage electrode in the same manner without being sieved through a 200-mesh sieve 5, and electrode B was used. do. Furthermore, a hydrogen-absorbing alloy powder obtained by mechanically crushing a hydrogen-absorbing alloy using a ball mill without hydrogenation and dehydrogenation until it passes through a 200-mesh sieve was also used as a hydrogen-absorbing alloy powder. The electrode was added as electrode C.
このようにして得た水素吸蔵電極Ａ−Ｃ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。The thus obtained hydrogen storage electrodes A-C 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
６Ｃ１１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２２ｃｍ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 to 6C11, 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
３０ｇ／ｅ溶解して用いた。公称容量は３．０Ａｈであ
る。A polyamide nonwoven fabric was used as the separator, and 30 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 3.0 Ah.
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１５０％まで、放電は
０．５Ｃ（２時間率〉で終止電圧０゜８Ｖとし充放電サ
イクルを繰り返し行なった。Charging was carried out at 0.2 C (5 hour rate) to 150%, and discharging was carried out at 0.5 C (2 hour rate) with a final voltage of 0.8 V, and charge and discharge cycles were repeated.
その結果、電極Ａを用いて構成した単２形密閉形ニッケ
ルー水素二次電池は、１００サイクルの放電容量が３．
１５Ａｈ、３００サイクルで３゜１４Ａｈ、６００サイ
クルで３．１３Ａｈであり寿命性能は、極めて優れてい
た。As a result, the AA sealed type nickel-metal hydride secondary battery constructed using electrode A had a discharge capacity of 3.2 mm over 100 cycles.
The life performance was extremely excellent as it was 15Ah, 3.14Ah for 300 cycles, and 3.13Ah for 600 cycles.
これに対して電極Ｂで構成した電池は、１００サイクル
で３．０８Ａｈであったが、３００サイクルで２．９５
Ａｈと公称容量の３．０Ａｈを下回り、その後急激に放
電容量が低下した。なお、電極Ｂで構成した電池は電極
Ａで構成した電池よりも放電電圧が全体的に低かった。On the other hand, the battery configured with electrode B had 3.08Ah after 100 cycles, but 2.95Ah after 300 cycles.
Ah and the nominal capacity of 3.0 Ah, and thereafter the discharge capacity decreased rapidly. Note that the discharge voltage of the battery configured with electrode B was lower overall than that of the battery configured with electrode A.
さらに電極Ｃで構成した電池は当初公称容量の３．０Ａ
ｈを満たしていたものの１００サイクルでは２．８１Ａ
ｈの放電容量が得られたに過ぎずその後は電極Ｂで構成
した電池と同様に急激に放電容量が低下した。Furthermore, the battery configured with electrode C had an initial nominal capacity of 3.0A.
2.81A for 100 cycles even though h was satisfied.
A discharge capacity of only h was obtained, and after that, the discharge capacity rapidly decreased similarly to the battery constructed with electrode B.
このような電池を構成した充放電試験結果から水素ガス
での水素吸蔵と水素放出を行なった後、水素吸蔵合金粉
末を篩分により有効合金相だけにしたことによる水素吸
蔵電極Ａが、寿命性能に優れていることが確認できた。The results of charging and discharging tests using such a battery show that after hydrogen storage and release using hydrogen gas, the hydrogen storage electrode A, which is made by sieving the hydrogen storage alloy powder to reduce only the effective alloy phase, has a long life performance. It was confirmed that it was excellent.
なお、先の説明以外に本発明に関して種々の検討を行な
った結果、以下のことが重要であった。In addition, as a result of various studies regarding the present invention other than those described above, the following points were found to be important.
まず水素ガスでの水素化と、脱水素化の工程は゛実施例
では３回としたが、２回以上行なうことが電池性能上好
ましい。また篩分により一定の粒径で分離しする工糎の
粒径は２００メツシユすなわち７４ミクロンを用いたが
これは１００ミクロン以下であることが好ましい。さら
に水素ガスでの水素化と、脱水素化を行なった水素吸蔵
合金粉末は非常に活性が高いので実施例の不活性ガスの
他に水素吸蔵合金粉末と反応を起こさない液体などで表
面を覆い、酸化を進めないことも有効な手段である。First, the steps of hydrogenation with hydrogen gas and dehydrogenation were performed three times in the example, but it is preferable to perform them two or more times in terms of battery performance. Further, the particle size of the starch to be separated into a constant particle size by sieving was 200 mesh, that is, 74 microns, but it is preferably 100 microns or less. Furthermore, the hydrogen storage alloy powder that has been hydrogenated with hydrogen gas and dehydrogenated is very active, so in addition to the inert gas used in the example, the surface is covered with a liquid that does not react with the hydrogen storage alloy powder. , it is also an effective means to prevent oxidation from proceeding.
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は、水素
吸蔵合金を圧力容器に収納し、水素ガスでの水素化と、
脱水素化を行ない、前記水素化と、脱水素化により微粉
末化していない部分だけを分離し、残りをその後水素吸
蔵電極用として用いるものであり、水素吸蔵合金をアル
カリ蓄電池の水素吸蔵合金負極に使用すると、これまで
問題であった微粉化や溶解などを解決し長寿命化を図る
とともに水素吸蔵電極の簡易化が可能になる。Effects of the Invention As described above, the method for manufacturing a hydrogen storage electrode of the present invention includes storing a hydrogen storage alloy in a pressure vessel, hydrogenating it with hydrogen gas, and
Dehydrogenation is performed, and only the part that has not been pulverized by the hydrogenation and dehydrogenation is separated, and the remainder is used for a hydrogen storage electrode.The hydrogen storage alloy is used as a hydrogen storage alloy negative electrode for an alkaline storage battery. When used for this purpose, it will solve the problems of pulverization and dissolution that have hitherto been a problem, prolong the life of the hydrogen storage electrode, and make it possible to simplify the hydrogen storage electrode.
図は本発明の一実施例の水素吸蔵電極の製造装置断面図
である。
１・・・水素吸蔵合金、２・・・圧力容器、３・・・粗
い金属メツシュ、４・・・ガスバルブ、５・・・メツシ
ュ篩。The figure is a sectional view of an apparatus for manufacturing a hydrogen storage electrode according to an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1...Hydrogen storage alloy, 2...Pressure vessel, 3...Rough metal mesh, 4...Gas valve, 5...Mesh sieve.
Claims (5)
水素化と、脱水素化を行ない、前記水素化と、脱水素化
により微粉末化していない部分だけを分離し、残部をそ
の後水素吸蔵電極用として用いることを特徴とする水素
吸蔵電極の製造法。(1) The hydrogen storage alloy is stored in a pressure vessel, hydrogenated with hydrogen gas and dehydrogenated, and only the portion that has not been pulverized by the hydrogenation and dehydrogenation is separated, and the remainder is removed afterwards. A method for producing a hydrogen storage electrode, characterized in that it is used as a hydrogen storage electrode.
容器内で、その後微粉末化していない部分だけを分離す
ることを特徴とする特許請求の範囲第１項記載の水素吸
蔵電極の製造法。(2) Hydrogen storage electrode according to claim 1, characterized in that only the portion that has not been pulverized afterward is separated in a pressure vessel in which hydrogenation with hydrogen gas and dehydrogenation are performed. manufacturing method.
を特徴とする特許請求の範囲第１項または第２項記載の
水素吸蔵電極の製造法。(3) The method for producing a hydrogen storage electrode according to claim 1 or 2, characterized in that the steps of hydrogenation and dehydrogenation are performed two or more times.
定の粒径での篩分法であることを特徴とする特許請求の
範囲第１項、２項または第３項記載の水素吸蔵電極の製
造法。(4) The hydrogen storage electrode according to claim 1, 2, or 3, wherein the method for separating only the portion that is not pulverized is a sieving method using a constant particle size. manufacturing method.
１００ミクロン以下であることを特徴とする特許請求の
範囲第１項、第２項、第３項または第４項記載の水素吸
蔵電極の製造法。(5) The method according to claim 1, 2, 3, or 4, characterized in that the particle size in the step of separating particles with a constant particle size by sieving is 100 microns or less. Method for manufacturing hydrogen storage electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62098933A JPH0812777B2 (en) | 1987-04-22 | 1987-04-22 | Manufacturing method of hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62098933A JPH0812777B2 (en) | 1987-04-22 | 1987-04-22 | Manufacturing method of hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264869A true JPS63264869A (en) | 1988-11-01 |
| JPH0812777B2 JPH0812777B2 (en) | 1996-02-07 |
Family
ID=14232925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62098933A Expired - Lifetime JPH0812777B2 (en) | 1987-04-22 | 1987-04-22 | Manufacturing method of hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812777B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524819A (en) * | 1998-08-27 | 2002-08-06 | オヴォニック バッテリー カンパニー インコーポレイテッド | Method for producing powder of hydrogen storage alloy |
| JP2020004508A (en) * | 2018-06-25 | 2020-01-09 | 凸版印刷株式会社 | Negative electrode composition for alkaline secondary battery and negative electrode for alkaline secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103910A (en) * | 1977-02-23 | 1978-09-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen occluded electrode |
-
1987
- 1987-04-22 JP JP62098933A patent/JPH0812777B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103910A (en) * | 1977-02-23 | 1978-09-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen occluded electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524819A (en) * | 1998-08-27 | 2002-08-06 | オヴォニック バッテリー カンパニー インコーポレイテッド | Method for producing powder of hydrogen storage alloy |
| JP2020004508A (en) * | 2018-06-25 | 2020-01-09 | 凸版印刷株式会社 | Negative electrode composition for alkaline secondary battery and negative electrode for alkaline secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0812777B2 (en) | 1996-02-07 |
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