JPH01132048A - Manufacture of hydrogen storage alloy electrode - Google Patents
Manufacture of hydrogen storage alloy electrodeInfo
- Publication number
- JPH01132048A JPH01132048A JP62290020A JP29002087A JPH01132048A JP H01132048 A JPH01132048 A JP H01132048A JP 62290020 A JP62290020 A JP 62290020A JP 29002087 A JP29002087 A JP 29002087A JP H01132048 A JPH01132048 A JP H01132048A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- electrode
- sintering
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 238000003860 storage Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract 2
- 229910004269 CaCu5 Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011162 core material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- PDPWTGAGBGEUJL-UHFFFAOYSA-N (8-methyl-8-azabicyclo[3.2.1]octan-3-yl) 3-(4-acetyloxyphenyl)-2-phenylpropanoate;hydrochloride Chemical compound Cl.CN1C(C2)CCC1CC2OC(=O)C(C=1C=CC=CC=1)CC1=CC=C(OC(C)=O)C=C1 PDPWTGAGBGEUJL-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002344 surface layer Substances 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はニッケル・水素蓄電池等のアルカリ蓄電池の負
極に用いる水素吸蔵合金電極の製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a hydrogen storage alloy electrode used as a negative electrode of an alkaline storage battery such as a nickel-hydrogen storage battery.
従来の技術
従来この種の電極はまだ実用化には至っていないが、そ
の製法として次のような方法が提案されている。すなわ
ち、三次元の網目状金属多孔体（発泡メタル）に水素吸
蔵合金粉末と結着剤を混練したペーストを充填、乾燥後
、加圧操作を施すことによシ水素吸蔵合金電極を作製す
る方法が提案（特公昭５７−３４６７８号公報）されて
いる。BACKGROUND OF THE INVENTION Although this type of electrode has not yet been put into practical use, the following methods have been proposed for its production. That is, a method of producing a hydrogen storage alloy electrode by filling a three-dimensional mesh porous metal body (foamed metal) with a paste made by kneading hydrogen storage alloy powder and a binder, drying it, and applying pressure. has been proposed (Japanese Patent Publication No. 57-34678).
また、水素吸蔵合金の粉末をポリテトラフルオロエチレ
ン（ＰＴＦＫ ）と均一に混合すると同時にＰＴＦＫを
１維化し、ニッケルネット等の芯材の両面にこれらを塗
着、加圧し水素吸蔵合金電極を作製する方法も提案（特
公昭８１−８６３７２号公報）されている。In addition, a hydrogen storage alloy powder is uniformly mixed with polytetrafluoroethylene (PTFK), PTFK is made into a single fiber, and these are applied to both sides of a core material such as nickel net and pressure is applied to produce a hydrogen storage alloy electrode. A method has also been proposed (Japanese Patent Publication No. 86372/1981).
発明が解決しようとする問題点
このような従来の調法では、Ｐ Ｔ Ｆ−Ｅが水素吸蔵
合金粉末の重量に対して１〜５％含有されている。した
がって、このような製造法で作製された負極を用論て密
閉形二ソケル・水素蓄電池を構成した場合、合金粒子表
面がＰＴＦＥに被覆されているだめ、粒子間の導電性や
反応面積が低下し、高率放電特性が劣るという問題があ
った。また、芯材に発泡メタルを用いた場合は、電池の
特性面では特に問題を生じないが、ニッケルネットやパ
ンチングメタル等の芯材と比較するとコスト高になると
いう問題点があった。Problems to be Solved by the Invention In such conventional preparation methods, P T F-E is contained in an amount of 1 to 5% based on the weight of the hydrogen storage alloy powder. Therefore, when a sealed two-sokel hydrogen storage battery is constructed using a negative electrode manufactured by this manufacturing method, the conductivity and reaction area between particles will decrease because the surfaces of the alloy particles are coated with PTFE. However, there was a problem that the high rate discharge characteristics were inferior. Further, when foamed metal is used as the core material, there is no particular problem in terms of battery characteristics, but there is a problem in that the cost is higher compared to core materials such as nickel net or punched metal.
さらに、これらの製造法のように、合金を粉砕した後に
結着剤と混練し、芯材に塗着あるいは充填して作裂した
水素吸蔵合金負極は、密閉形電池内で過充電時にニアケ
ル正極から発生する酸素ガスにより合金表面が酸化され
、充放電サイクル寿命が短いという間頂があった。Furthermore, as in these manufacturing methods, the hydrogen storage alloy negative electrode, which is produced by crushing the alloy, kneading it with a binder, and applying or filling it to the core material to rupture, can be used as a nickel positive electrode when overcharged in a sealed battery. The alloy surface was oxidized by the oxygen gas generated, resulting in a short charge-discharge cycle life.
本発明はこのような問題点を解決するもので、高率放電
特性とサイクル寿命特性に優れ、比較的低コストの水素
吸蔵合金電極を提供することを目的とするものである。The present invention solves these problems and aims to provide a relatively low-cost hydrogen storage alloy electrode that has excellent high rate discharge characteristics and cycle life characteristics.
問題点を解決するための手段
この問題点を解決するために本発明は、可逆的に水素を
吸蔵・放出する水素吸蔵合金の粉末を酸またはアルカリ
性の溶液に浸漬する工程と、水洗乾燥の後、粉末と結着
剤の混練物を芯金に塗着。Means for Solving the Problem In order to solve this problem, the present invention provides a step of immersing a powder of a hydrogen storage alloy that reversibly stores and releases hydrogen in an acid or alkaline solution, and a process of immersing the powder of a hydrogen storage alloy that reversibly stores and releases hydrogen, and after washing and drying with water. , apply a mixture of powder and binder to the core metal.
乾燥し加圧操作を施す工程と、真空中、不活性ガス中も
しくは水素ガス中で合金の融点以下の温度１、で焼結す
る工程を有する水素吸蔵合金電極の製造法としたもので
ある。This is a method for producing a hydrogen storage alloy electrode, which includes a step of drying and applying pressure, and a step of sintering at a temperature 1 below the melting point of the alloy in vacuum, inert gas, or hydrogen gas.
作用
酸またはアルカリ性の溶液に浸漬する工程を有する製造
法により、合金粒子表面から一部金属が廖解し耐酸化性
皮膜を粒子表面に形成する結果、密閉電池内でニッケル
正極から発生する酸素による酸化が抑制され、サイクル
寿命特性が向上することとなる。さらに、酸またはアル
カリ性の溶液に浸漬後、焼結する工程を有する製造法に
より、合金表面に凹凸が形成されるため、反応表面積が
増大し、さらに焼結性が向上することと、芯金に塗着す
る工程で用いた結着剤は分解され電極中にはほとんど残
存しない。その結果、粒子と粒子間の導電性および表面
積は低下せず、高率放電特性は向上することとなる。Due to the manufacturing method that involves immersion in a working acid or alkaline solution, some of the metal from the surface of the alloy particles is dissolved and an oxidation-resistant film is formed on the particle surface. Oxidation is suppressed and cycle life characteristics are improved. Furthermore, the manufacturing method, which involves sintering after immersion in an acid or alkaline solution, forms irregularities on the alloy surface, which increases the reaction surface area and further improves sinterability. The binder used in the coating process is decomposed and hardly remains in the electrode. As a result, the conductivity between particles and the surface area do not decrease, and the high rate discharge characteristics improve.
実施例
以下、本発明の一実施例を第１図と第２図によシ説明す
る。市販のミツシュメタルＭｍ （希土類元素の混合
物）、例えばＣａ４５ｗｔ％ 、Ｌａ３０ｗｔ％Ｎｄ５
ｗｔ％、他の希土類元素約２０Ｗｔチ）とＮｉ。EXAMPLE Hereinafter, an example of the present invention will be explained with reference to FIGS. 1 and 2. Commercially available Mitsushmetal Mm (mixture of rare earth elements), e.g. Ca45wt%, La30wt%Nd5
wt%, other rare earth elements (approximately 20 Wt) and Ni.
五ｇ、Ｍｎ、Ｇｏの各試料をＭｍＮｉ ３．５５Ｍｎ０
．４ムロｏ、３Ｃ’ｏ、７ｓの組成比に秤量し混合した
。これらの試料をアーク溶解炉に入れて、１０−４〜１
Ｏ−５Ｔｏｒｒまで真空状態にしだ後、アルゴンガス雰
囲気中でアーク放電し、加熱溶解させた。試料の均質化
を図るために数回反転させてアーク溶解を行い、０ＩＬ
Ｏｕ ５型の結晶構造を有する水素吸蔵合金を得た。こ
れと同様な方法で、組成がＭｍＮｉ４，５Ｍｎｏ、４五
ｌａ、ｓである水素吸蔵合金を作製した。次に、これら
の合金の均質性をさらに良好にし、水素吸蔵量を増大さ
せるだめに、アルゴンガス雰囲気中にて１０５０゜Ｃで
６時間熱処理を行った。これらの合金を粗粉砕後、ボー
ルミルで機械的に３８μｍ以下の粉末に微粉砕した。MmNi 3.55Mn0 each sample of 5g, Mn, Go
．． They were weighed and mixed to have a composition ratio of 4Mroo, 3C'o, and 7s. These samples were placed in an arc melting furnace and heated to 10-4 to 1
After vacuuming to O-5 Torr, arc discharge was performed in an argon gas atmosphere to heat and melt. Arc melting was performed by inverting the sample several times to homogenize the sample, and the sample was melted at 0IL.
A hydrogen storage alloy having an Ou 5 type crystal structure was obtained. A hydrogen storage alloy having a composition of MmNi4,5Mno,45la,s was prepared in a similar manner. Next, in order to further improve the homogeneity of these alloys and increase their hydrogen storage capacity, heat treatment was performed at 1050° C. for 6 hours in an argon gas atmosphere. After coarsely pulverizing these alloys, they were mechanically pulverized into powders of 38 μm or less using a ball mill.
次に、これらの粉末を８０’Ｃの水酸化カリウム水溶液
（比重１．３０）中で１２時間処理（以下、アルカリ処
理と称す）した後、水洗・乾燥し、負極に用いる水素吸
蔵合金粉末を得た。Next, these powders were treated in a potassium hydroxide aqueous solution (specific gravity 1.30) at 80'C for 12 hours (hereinafter referred to as alkali treatment), washed with water and dried, and the hydrogen storage alloy powder used for the negative electrode was prepared. Obtained.
これらの粉末１ｏＯｆに対してポリビニルアルコール６
胃ｔ、％ の水溶液２３ｇとポリエチレン粉末を２２添
加して練合を行い、ペースト状態とした。ついで、これ
らのペーストをパンチングメタルに塗着し、１２０′Ｃ
で乾燥後、加圧を施してペースト式電極を得た。さらに
、これらのペースト式電極をアルゴンガス雰囲気中で８
００−１２００゜Ｃの各温度で１時間焼結を行い、本発
明の水素吸蔵合金電極を得た。本実施例に用いた電極の
合金組成と各焼結温度、アルカリ処理の有無を表に示す
。比紋例として、合金粉末を前記と同様な結着剤を用い
てペースト状態として、パンチングメタルに塗着後、乾
燥、加圧を施したペースト式電極Ｈを用いた。6 polyvinyl alcohol per 1oOf these powders
23 g of an aqueous solution of 10% and 22 g of polyethylene powder were added and kneaded to form a paste. Next, apply these pastes to punched metal and heat at 120'C.
After drying, a paste type electrode was obtained by applying pressure. Furthermore, these paste-type electrodes were heated for 8 hours in an argon gas atmosphere.
Sintering was performed at each temperature of 00-1200°C for 1 hour to obtain a hydrogen storage alloy electrode of the present invention. The alloy composition, each sintering temperature, and presence or absence of alkali treatment of the electrodes used in this example are shown in the table. As a comparative example, a paste-type electrode H was used in which alloy powder was made into a paste using the same binder as described above, applied to a punched metal, dried, and pressurized.
（以下余白）
次に、酸化ニッケル正極として、公知の方法で得られた
発泡メタル式ニッケル正極（理論充填電気量１０５０〜
１１００ｍＡｈ）を用い、セＡ レータにはポリアミド
の不織布、電解液に水酸化リチウムを４ｏ１／！ｌ溶解
した比重１．３０のＫＯＨ水溶液を使用し、前記Ａ〜Ｈ
の負極と組み合わせ、公称容量１０００ｔｌｌＡｈの単
３サイズ（ムムサイズ）の各種密閉形ニッケルー水素蓄
電池を構成した。□第１図には、Ｏ’Ｃで種々の放電率
で放電を行った場合の容量比率を示した。容量比率は、
Ｏ’Ｃ。(Left below) Next, as a nickel oxide positive electrode, a foamed metal nickel positive electrode obtained by a known method (theoretical charge amount of electricity 1050~
1100mAh), polyamide non-woven fabric for the serator, and lithium hydroxide for the electrolyte at 4o1/! Using a KOH aqueous solution with a specific gravity of 1.30, the above A to H
In combination with the negative electrode, various sealed nickel-metal hydride storage batteries of AA size (Mumu size) with a nominal capacity of 1000 tllAh were constructed. □Figure 1 shows the capacity ratio when discharge was performed at various discharge rates at O'C. The capacity ratio is
O'C.
０．２０ｍム放電における容量を基準にして計算した。It was calculated based on the capacity at 0.20 mm discharge.
なお、各放電は２０゜Ｃで０．１０ｍムで正極容量に対
し１６０％の充電後、０゜Ｃで２時間放置した後例行っ
た。第１図から明らかなように、比較例のペースト式電
極Ｈを用いた電池は、Ｏ’Ｃ，３Ｃｍ人の容量比率が３
５％であり、高率放電時の特性に劣ることがわかる。こ
れに対し、本発明の電極Ａ。Each discharge was carried out after charging to 160% of the positive electrode capacity at 20° C. and 0.10 mm, and then leaving the battery at 0° C. for 2 hours. As is clear from Fig. 1, the battery using the paste type electrode H of the comparative example has a capacity ratio of O'C, 3Cm of 3
5%, which indicates that the characteristics during high rate discharge are inferior. In contrast, electrode A of the present invention.
Ｂ、Ｄを用いた電池は、０℃、３０ｍム における容量
比率は６３〜７０チであり、電極Ｈを用いた電池に比べ
、放電特性は著しく向上する。これは、９５０’（！で
焼結を施すことによシ、ポリビニルアルコールやポリエ
チレンの結着剤が分解し、負極中に存在しないこと、粒
子−粒子一芯材間の結合が良好で導電性が低下しないこ
とにより、３０ｍ人放電における負極の分極が減少した
ことに起因する。また、アルカリ処理を施していないＦ
は、ムに比べ放電特性が劣る。これは、焼結前に合金粉
末にアルカリ処理を施すことによシ、合金中に含まれる
コバルトが優先的に溶解し、粒子表面に凹凸を形成して
いるため、有効反応表面積が増大したことおよび、凹凸
面での焼結性が良好になり、導電性が向上し、放電特性
が改善された。Batteries using electrodes B and D have a capacity ratio of 63 to 70 at 0° C. and 30 mm, and their discharge characteristics are significantly improved compared to batteries using electrode H. By sintering at 950' (!), the binder of polyvinyl alcohol and polyethylene is decomposed and does not exist in the negative electrode, and the bond between the particles and the core material is good, resulting in conductivity. This is due to the fact that the polarization of the negative electrode in the 30 m discharge was reduced due to the fact that the F
The discharge characteristics are inferior to those of MU. This is because by applying alkali treatment to the alloy powder before sintering, the cobalt contained in the alloy dissolves preferentially and forms irregularities on the particle surface, increasing the effective reaction surface area. In addition, the sinterability on uneven surfaces was improved, the conductivity was improved, and the discharge characteristics were improved.
第２図には、２０℃における充放電サイクル寿命特性を
示した。充放電条件は、充電が％ＣｍＡＸ４．５ ｈｒ
、放電が１０ｍムで終止電圧は０，８ Ｖである。本発
明の電極人、Ｂ 、Ｄを用いた電池は、６００サイクル
の充放電を繰シ返しても容量はほとんど低下しない。こ
れに対して、比較例のＨを用いた電池は、８０サイクル
程度で劣化する。また、焼結を施した電極２を用いた電
池も、８０サイクル程度で容量低下をきたす。Ｆ、Ｈの
ようにアルカリ処理を施していない電極を用いた電池は
、過充電時に正極から発生する酸素ガスにより合金が酸
化されて容量低下をきたす。また、アルカリ処理を施し
ていない合金粉末を焼結した場合、合金表面から蒸気圧
の低いＭｎが一部蒸発することにより、表面層の組成が
変化し、負極の充電効率の低下によっても容量が低下す
る。FIG. 2 shows the charge/discharge cycle life characteristics at 20°C. The charging and discharging conditions are %CmAX4.5 hr
, the discharge is 10 mm and the final voltage is 0.8 V. Batteries using electrodes B and D of the present invention show almost no decrease in capacity even after 600 charging and discharging cycles. On the other hand, the battery using H in the comparative example deteriorates after about 80 cycles. Further, a battery using a sintered electrode 2 also suffers a capacity drop after about 80 cycles. In batteries such as F and H that use electrodes that have not been subjected to alkali treatment, the alloy is oxidized by oxygen gas generated from the positive electrode during overcharging, resulting in a decrease in capacity. In addition, when alloy powder that has not been subjected to alkali treatment is sintered, some of the Mn with low vapor pressure evaporates from the alloy surface, resulting in a change in the composition of the surface layer, and a decrease in the charging efficiency of the negative electrode, resulting in a decrease in capacity. descend.
次に、コバルトを含有しない電極Ｇを用いた電池は、７
０サイクル程度で容量が劣化する。また、焼結における
最適な温度範囲は、８６０〜１１００゜Ｃである。これ
は、８６０゜Ｃ以下の温度では焼結が不可能であｆｉ、
１１００’Ｃ以上になると焼結が進行しすぎ電池構成が
不可能となる。本実施例では、アルゴンガス雰囲気中で
焼結を施したが、Ｎ２ガスやＮ２ガス中およびＮ２とＮ
２等の混合ガス中あるいは真空中で焼結を施しても同様
な効果が得られた。また、アルカリ処理を施した場合の
一実施例を示したが、アルカリ処理温度は４５〜９０″
Ｃ処理時間が０．５〜２０時間であれば同様な効果が得
られる。さらに、塩酸等の酸中で処理を施しても同様な
効果が得られる。本実施例ではアルカリ処理を施した後
に焼結する工程で電極を作製したが、焼結を行った後、
アルカリ処理または酸処理を施して電極を作製しても同
様な効果が得られる。Next, a battery using electrode G that does not contain cobalt is 7
Capacity deteriorates after about 0 cycles. Further, the optimum temperature range for sintering is 860 to 1100°C. This is because sintering is impossible at temperatures below 860°C.
When the temperature exceeds 1100'C, sintering progresses too much and it becomes impossible to construct a battery. In this example, sintering was performed in an argon gas atmosphere, but in N2 gas, N2 gas, and N2 and N2 gas.
Similar effects were obtained even when sintering was performed in a mixed gas such as No. 2 or in vacuum. In addition, an example in which alkali treatment was performed was shown, but the alkali treatment temperature was 45 to 90''.
Similar effects can be obtained if the C treatment time is 0.5 to 20 hours. Furthermore, the same effect can be obtained even if the treatment is performed in an acid such as hydrochloric acid. In this example, the electrode was fabricated in the process of sintering after alkali treatment, but after sintering,
A similar effect can be obtained even if the electrode is prepared by performing an alkali treatment or an acid treatment.
なお、芯材に発泡状ニッケルに比べ安価なパンチングメ
タルを用いることができ、負極のコストダウンが図れる
。Note that punching metal, which is cheaper than foamed nickel, can be used as the core material, and the cost of the negative electrode can be reduced.
発明の効果
以上のように、本発明によれば、水素吸蔵合金の粉末を
酸またはアルカリ性の溶液に浸漬する工程と、水洗・乾
燥の後、粉末と結着剤との混合物を芯金に塗着、乾燥し
加圧操作を施す工程と、真空中、不活性ガス中もしくは
水素ガス中で合金の融点以下の温度で焼結する工程とを
有する水素吸蔵電極の製造法とすることによシ、高率放
電特性に優れ、充放電サイクル寿命の良好な電池を提供
できるという効果が得られる。Effects of the Invention As described above, according to the present invention, the steps of immersing hydrogen storage alloy powder in an acid or alkaline solution, washing with water and drying, and then applying a mixture of the powder and a binder to the core metal are performed. The method for producing a hydrogen storage electrode includes the steps of depositing, drying, and pressurizing, and sintering at a temperature below the melting point of the alloy in vacuum, inert gas, or hydrogen gas. , it is possible to provide a battery with excellent high rate discharge characteristics and a good charge/discharge cycle life.
第１図は本発明の一実施例における放電率と容量比率の
関係を示す図、第２図は充放電サイクル数と放電容量の
関係を示す図である。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
炙 贋ζ 率 （Ｃ請杓FIG. 1 is a diagram showing the relationship between the discharge rate and the capacity ratio in one embodiment of the present invention, and FIG. 2 is a diagram showing the relationship between the number of charge/discharge cycles and the discharge capacity. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Diagram fake ζ rate (C claim rate
Claims (3)
末を酸またはアルカリ性の溶液に浸漬する工程と、水洗
乾燥の後、粉末と結着剤の混練物を芯金に塗着、乾燥し
加圧操作を施す工程と、合金の融点以下の温度で焼結す
る工程とを有することを特徴とする水素吸蔵合金電極の
製造法。(1) The process of immersing the powder of a hydrogen storage alloy that reversibly stores and releases hydrogen in an acid or alkaline solution, washing with water and drying, then applying a mixture of powder and binder to the core metal and drying. 1. A method for producing a hydrogen storage alloy electrode, comprising the steps of applying pressure and sintering at a temperature below the melting point of the alloy.
造を有し、焼結を施す温度が８５０〜１１００゜Ｃの範
囲であることを特徴とする特許請求の範囲第１項記載の
水素吸蔵合金電極の製造法。(2) The hydrogen storage alloy according to claim 1, wherein the hydrogen storage alloy powder has a CaCu_5 type crystal structure, and the sintering temperature is in the range of 850 to 1100°C. Method for manufacturing alloy electrodes.
いたことを特徴とする特許請求の範囲第１項記載の水素
吸蔵合金電極の製造法。(3) A method for manufacturing a hydrogen storage alloy electrode according to claim 1, characterized in that a hydrogen storage alloy containing at least cobalt is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62290020A JP2733231B2 (en) | 1987-11-17 | 1987-11-17 | Manufacturing method of hydrogen storage alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62290020A JP2733231B2 (en) | 1987-11-17 | 1987-11-17 | Manufacturing method of hydrogen storage alloy electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01132048A true JPH01132048A (en) | 1989-05-24 |
| JP2733231B2 JP2733231B2 (en) | 1998-03-30 |
Family
ID=17750749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62290020A Expired - Fee Related JP2733231B2 (en) | 1987-11-17 | 1987-11-17 | Manufacturing method of hydrogen storage alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2733231B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0645833A1 (en) * | 1993-08-31 | 1995-03-29 | SANYO ELECTRIC Co., Ltd. | Method for producing a hydrogen absorbing alloy electrode |
| EP0696823A1 (en) * | 1994-02-25 | 1996-02-14 | Yuasa Corporation | Hydrogen absorbing electrode and production method thereof |
| EP0975033A1 (en) * | 1997-01-31 | 2000-01-26 | SANYO ELECTRIC Co., Ltd. | Hydrogen storage alloy powder ane method of manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4925135A (en) * | 1972-06-29 | 1974-03-06 | ||
| JPS5416632A (en) * | 1977-07-07 | 1979-02-07 | Matsushita Electric Ind Co Ltd | Method of making hydrogen occlusion electrode |
| JPS61285658A (en) * | 1985-06-12 | 1986-12-16 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen occlusion electrode |
-
1987
- 1987-11-17 JP JP62290020A patent/JP2733231B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4925135A (en) * | 1972-06-29 | 1974-03-06 | ||
| JPS5416632A (en) * | 1977-07-07 | 1979-02-07 | Matsushita Electric Ind Co Ltd | Method of making hydrogen occlusion electrode |
| JPS61285658A (en) * | 1985-06-12 | 1986-12-16 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen occlusion electrode |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0645833A1 (en) * | 1993-08-31 | 1995-03-29 | SANYO ELECTRIC Co., Ltd. | Method for producing a hydrogen absorbing alloy electrode |
| EP0696823A1 (en) * | 1994-02-25 | 1996-02-14 | Yuasa Corporation | Hydrogen absorbing electrode and production method thereof |
| EP0696823A4 (en) * | 1994-02-25 | 1996-04-24 | Yuasa Battery Co Ltd | Hydrogen absorbing electrode and production method thereof |
| US5935732A (en) * | 1994-02-25 | 1999-08-10 | Yuasa Corporation | Hydrogen absorbing electrode and its manufacturing method |
| EP0975033A1 (en) * | 1997-01-31 | 2000-01-26 | SANYO ELECTRIC Co., Ltd. | Hydrogen storage alloy powder ane method of manufacturing the same |
| EP0975033A4 (en) * | 1997-01-31 | 2006-05-24 | Sanyo Electric Co | Hydrogen storage alloy powder ane method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2733231B2 (en) | 1998-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109830676A (en) | Rechargeable uses for nickel-hydrogen battery high capacity and long-life La-Mg-Ni type cathode hydrogen storage material and preparation method thereof | |
| JPH01132048A (en) | Manufacture of hydrogen storage alloy electrode | |
| JP2982199B2 (en) | Hydrogen storage alloy electrode, method for producing the same, and sealed alkaline storage battery using the electrode | |
| JP3279994B2 (en) | Hydrogen storage alloy powder and negative electrode for alkaline storage battery | |
| JP4743997B2 (en) | Hydrogen storage alloy electrode | |
| JP3432870B2 (en) | Method for producing metal hydride electrode | |
| JP2792955B2 (en) | Hydrogen storage alloy for hydrogen electrode | |
| JPH06223827A (en) | Manufacture of hydrogen storage alloy powder for battery | |
| JP3639494B2 (en) | Nickel-hydrogen storage battery | |
| JPH11269501A (en) | Manufacture of hydrogen occlusion alloy powder, and hydrogen occlusion alloy electrode | |
| JP3098940B2 (en) | Method for producing hydrogen storage alloy powder for electrode | |
| JP3387314B2 (en) | Manufacturing method of hydrogen storage alloy electrode | |
| JPS63264867A (en) | Manufacture of hydrogen storage electrode | |
| JPS61233966A (en) | Manufacture of sealed nickel-hydrogen storage battery | |
| JP3516312B2 (en) | Method for producing hydrogen storage alloy electrode | |
| JP3098948B2 (en) | Hydrogen storage alloy-containing composition and electrode using the same | |
| JPH10255775A (en) | Hydrogen storage alloy electrode and its manufacture | |
| JPH0815078B2 (en) | Method for manufacturing hydrogen storage electrode | |
| JPH1167264A (en) | Manufacture of nickel-hydrogen storage battery | |
| JPH097591A (en) | Hydrogen absorbing alloy, its manufacture and hydrogen absorbing alloy electrode using this hydrogen absorbing alloy | |
| JP3746086B2 (en) | Method for manufacturing nickel-metal hydride battery | |
| JP2929716B2 (en) | Hydrogen storage alloy electrode | |
| JP3322449B2 (en) | Method for producing metal hydride electrode | |
| JP3010989B2 (en) | Hydrogen storage electrode and method for producing the same | |
| JP2586752B2 (en) | Hydrogen storage alloy electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |