JPH0729568A - Manufacturing method of hydrogen storage alloy electrode - Google Patents
Manufacturing method of hydrogen storage alloy electrodeInfo
- Publication number
- JPH0729568A JPH0729568A JP5198918A JP19891893A JPH0729568A JP H0729568 A JPH0729568 A JP H0729568A JP 5198918 A JP5198918 A JP 5198918A JP 19891893 A JP19891893 A JP 19891893A JP H0729568 A JPH0729568 A JP H0729568A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- electrode
- battery
- solution
- 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.)
- Pending
Links
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、密閉形ニッケル−水素
蓄電池などに用いる水素吸蔵合金電極の製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogen storage alloy electrode used in a sealed nickel-hydrogen storage battery or the like.
【０００２】[0002]
【従来の技術】各種の電源として広く使われているアル
カリ蓄電池は、高信頼性が期待でき、小形軽量化も可能
であるなどの理由から、小形電池は各種ポ−タブル機器
用に、また大形電池は産業用にそれぞれ使われてきた。
このアルカリ蓄電池において、正極としては一部空気極
や酸化銀極なども取り上げられているが、ほとんどの場
合はニッケル電極である。ニッケル電極は、ポケット式
から焼結式に代わって特性が向上し、さらに密閉化が可
能になるとともに用途も広がった。一方、負極としては
カドミウムの他に亜鉛、鉄、水素などが対象となってい
る。しかし、現在のところカドミウム電極が主体であ
る。ところが、一層の高エネルギ−密度を達成するため
に、金属水素化物つまり水素吸蔵合金を負極を使ったニ
ッケル−水素蓄電池が注目され、水素吸蔵合金電極につ
いて製法などに多くの提案がされている。たとえば、水
素吸蔵合金粉末の酸化や成型性を改善するために、この
合金粉末の表面にニッケルや銅をメッキして表面に多孔
性の金属層を形成する技術がよく知られている。さら
に、合金製造後に合金の均質化のために高温で熱処理す
る方法、あるいは合金粉末中の完全な合金になっていな
いアルカリ溶液に可溶性の金属を溶解除去することによ
り長寿命化を図る目的で、合金粉末またはこれを組み込
んだ電極をアルカリにより処理する方法などがある。そ
のほかにも各種の添加剤など、性能の安定性や寿命向上
のための手段が種々講じられている。2. Description of the Related Art Alkaline storage batteries that are widely used as various power sources are expected to have high reliability and can be made compact and lightweight. Shape batteries have been used for industrial purposes.
In this alkaline storage battery, an air electrode, a silver oxide electrode, and the like are partially taken as the positive electrode, but in most cases, the nickel electrode is used. Nickel electrode has improved its characteristics from the pocket type to the sintered type, and has become possible to be hermetically sealed and expanded its applications. On the other hand, as the negative electrode, in addition to cadmium, zinc, iron, hydrogen, etc. are targeted. However, at present, the cadmium electrode is mainly used. However, in order to achieve an even higher energy density, a nickel-hydrogen storage battery using a metal hydride, that is, a hydrogen storage alloy as a negative electrode has been receiving attention, and many proposals have been made for a method for manufacturing a hydrogen storage alloy electrode. For example, in order to improve the oxidization and moldability of the hydrogen storage alloy powder, a technique of plating nickel or copper on the surface of the alloy powder to form a porous metal layer on the surface is well known. Furthermore, a method of heat treatment at a high temperature for homogenizing the alloy after manufacturing the alloy, or for the purpose of prolonging the life by dissolving and removing the soluble metal in the alkaline solution which is not a complete alloy in the alloy powder, There is a method of treating the alloy powder or the electrode incorporating the alloy powder with an alkali. In addition to this, various means such as various additives have been taken to improve the stability of the performance and the life.
【０００３】水素吸蔵合金電極の製法としては、合金粉
末を焼結する方式と、発泡状もしくは繊維状の金属多孔
体またはパンチングメタルなどに合金粉末のペーストを
充填または塗着する方式のペ−スト式がある。用いる水
素吸蔵合金としては、希土類系のＭｍＮｉ5をベースと
した多元系合金が主である。これについてはさらに高容
量にすることが望まれている。また、Ｚｒ（Ｔｉ）−Ｎ
ｉをベースとするＡＢ2系合金は、最終的には高容量に
なるが、充放電サイクルの初期における放電特性にやや
問題を残しいてる。そのほかに密閉形電池で要求される
充放電サイクル初期における水素吸蔵合金電極の放電特
性と充電時におけるガス吸収性が重要である。As a method for producing a hydrogen storage alloy electrode, a method of sintering alloy powder and a method of filling or coating a paste of alloy powder on a foamed or fibrous porous metal body or punching metal or the like. There is a formula. The hydrogen storage alloy used is mainly a multi-element alloy based on rare earth MmNi 5 . Regarding this, it is desired to further increase the capacity. In addition, Zr (Ti) -N
The AB2-based alloy based on i has a high capacity in the end, but it has some problems in the discharge characteristics in the initial stage of the charge / discharge cycle. In addition, the discharge characteristics of the hydrogen storage alloy electrode at the beginning of the charge / discharge cycle and the gas absorption at the time of charging, which are required for the sealed battery, are important.
【０００４】[0004]
【発明が解決しようとする課題】水素吸蔵合金電極の容
量向上、性能の安定性や寿命向上のための手段として、
水素吸蔵合金粉末を苛性カリ、苛性ソ−ダ、水酸化リチ
ウムなどのアルカリ溶液に浸漬するアルカリ処理が行わ
れる場合がある。その主な目的は、合金製造時に偏析な
どで所望の合金になっていない金属で、電極構成後電池
内で溶解する可能性のある金属をあらかじめ除去するこ
とである。また、高温におけるアルカリ処理があり、た
とえばＺｒ（Ｔｉ）−ＮｉをベースとするＡＢ2系合金
の場合、この処理により表面は金属色から完全に黒褐色
に変化する。この処理によると、従来のアルカリ処理に
よる場合はほとんど期待できなかった充放電サイクル初
期における放電特性改良の効果が得られる。その理由と
して、合金のアルカリに対する濡れ易さがいちじるしく
向上することがあげられる。一方、初期特性の比較的優
れたＭｍ−Ｎｉ系合金の場合も高温におけるアルカリ処
理により黒褐色となり、利用率が向上し、不純物の除去
効果も加算されてガス吸収性も改善される。DISCLOSURE OF INVENTION Problems to be Solved by the Invention As means for improving the capacity, stability of performance and life of hydrogen storage alloy electrodes,
Alkaline treatment may be carried out by immersing the hydrogen storage alloy powder in an alkaline solution such as caustic potash, caustic soda, or lithium hydroxide. Its main purpose is to remove in advance a metal that has not been formed into a desired alloy due to segregation or the like at the time of alloy production and may dissolve in the battery after the electrode is formed. Further, there is an alkali treatment at a high temperature, for example, in the case of an AB 2 alloy based on Zr (Ti) —Ni, this treatment changes the surface from a metallic color to a completely blackish brown. According to this treatment, it is possible to obtain the effect of improving the discharge characteristics in the initial stage of the charge / discharge cycle, which was hardly expected in the conventional alkali treatment. The reason for this is that the wettability of the alloy with alkali is significantly improved. On the other hand, even in the case of the Mm-Ni alloy having relatively excellent initial characteristics, it becomes blackish brown due to the alkali treatment at high temperature, the utilization factor is improved, and the effect of removing impurities is also added to improve the gas absorbability.
【０００５】しかし、最近実用化されたいわゆるリチウ
ムイオン二次電池に匹敵する高いエネルギ−密度にする
ために電池内の水素吸蔵合金量を減少させると、水素吸
蔵合金の容量、寿命、ガス吸収性などに問題が生ずる。
本発明は、水素吸蔵合金電極の初期特性、充電時におけ
るガス吸収性、利用率およびサイクル寿命などを大幅に
改善することを目的とする。However, if the amount of hydrogen storage alloy in the battery is reduced in order to achieve a high energy density comparable to that of a so-called lithium ion secondary battery that has recently been put into practical use, the capacity, life and gas absorbability of the hydrogen storage alloy are reduced. Etc. will cause problems.
It is an object of the present invention to significantly improve the initial characteristics of a hydrogen storage alloy electrode, the gas absorption during charging, the utilization rate, the cycle life, and the like.
【０００６】[0006]
【課題を解決するための手段】本発明は、水素吸蔵合金
粉末、あるいはこれを主材料として電極とした後、煮沸
している水酸化カリウム溶液あるいは水酸化ナトリウム
溶液に水酸化リチウムを好ましくは飽和量に溶解した溶
液に浸漬することを特徴とする。本発明はまた、水素吸
蔵合金粉末、あるいは前記合金粉末を含む電極を煮沸し
ている水酸化リチウム水溶液、好ましくは飽和溶液に浸
漬することを特徴とする。なお、上記のアルカリ溶液へ
の浸漬時間は０．３〜２時間程度でよい。さらに、ガス
吸収特性の向上を目的に、煮沸している水酸化リチウム
を含む溶液に浸漬した後、水素吸蔵合金電極の表面に撥
水性樹脂粉末を塗着するのが好ましい。According to the present invention, a hydrogen storage alloy powder, or an electrode using this as a main material, and then saturated with lithium hydroxide is preferably added to a boiling potassium hydroxide solution or sodium hydroxide solution. It is characterized by being immersed in a solution dissolved in a quantity. The present invention is also characterized in that the hydrogen storage alloy powder or the electrode containing the alloy powder is immersed in a boiling lithium hydroxide aqueous solution, preferably a saturated solution. The immersion time in the above alkaline solution may be about 0.3 to 2 hours. Further, for the purpose of improving gas absorption characteristics, it is preferable to immerse in a boiling solution containing lithium hydroxide and then coat the surface of the hydrogen storage alloy electrode with a water repellent resin powder.
【０００７】[0007]
【作用】本発明者らは、水酸化カリウム溶液もしくは水
酸化ナトリウム溶液に水酸化リチウムを好ましくは飽和
量溶解した溶液、あるいは水酸化リチウムを好ましくは
飽和量溶解した溶液を用い、しかもこれらを最も高温で
ある煮沸して用いることで、水素吸蔵合金電極の初期特
性の改善、充電時におけるガス吸収性、利用率の向上、
サイクル寿命の向上など、水素吸蔵合金電極の特性を大
幅に改善できることを見出した。電極特性が改善される
理由ははっきりしないが、最も高温にしてのリチウムイ
オンが水素吸蔵合金表面の改質に貢献しているものと思
われる。なお、アルカリ処理後、電極の表面に撥水性樹
脂粉末を塗着すると、アルカリ処理との相乗効果が得ら
れ、充電時におけるガス吸収性の向上にきわめて有効で
ある。The inventors of the present invention have used a solution in which lithium hydroxide is preferably dissolved in a potassium hydroxide solution or a sodium hydroxide solution in a saturated amount, or a solution in which lithium hydroxide is dissolved in a saturated amount is preferably used. By boiling at high temperature and using it, the initial characteristics of the hydrogen storage alloy electrode are improved, the gas absorption during charging, and the utilization rate are improved.
It has been found that the characteristics of the hydrogen storage alloy electrode can be significantly improved such as the improvement of cycle life. The reason why the electrode characteristics are improved is not clear, but it is considered that lithium ions at the highest temperature contribute to the modification of the surface of the hydrogen storage alloy. In addition, when the surface of the electrode is coated with the water-repellent resin powder after the alkali treatment, a synergistic effect with the alkali treatment is obtained, which is extremely effective in improving the gas absorbability during charging.
【０００８】[0008]
【実施例】以下、本発明の実施例を説明する。 ［実施例１］水素吸蔵合金としてＡＢ2系合金の一つで
あるＺｒＭｎ0.5Ｃｒ0.2Ｖ0.1Ｎｉ1.2を粉砕し、３６０
メッシュのふるいを通過する粉末にポリビニルアルコ−
ルの２重量％水溶液を加えてペーストを作り、このペ−
ストを多孔度９５％、厚さ１．０ｍｍの発泡状ニッケル
板に充填する。この電極を幅３３ｍｍ、長さ２００ｍｍ
に裁断し、リ−ド板をスポット溶接により取り付けた
後、１００トンの加圧機で加圧し、さらにロ−ラプレス
機を通して厚さ０．５２ｍｍに調整する。EXAMPLES Examples of the present invention will be described below. [Example 1] was ground ZrMn 0.5 Cr 0.2 V 0.1 Ni 1. 2 is one of the AB 2 type alloy as a hydrogen absorbing alloy, 360
Polyvinyl alcohol is added to the powder that passes through the mesh sieve.
2% by weight aqueous solution is added to make a paste.
The strike is filled in a foamed nickel plate having a porosity of 95% and a thickness of 1.0 mm. This electrode is 33 mm wide and 200 mm long
It is cut into pieces, and the lead plate is attached by spot welding. Then, pressure is applied with a 100 ton press and the thickness is adjusted to 0.52 mm through a roller press.
【０００９】次に、苛性カリの３０重量％水溶液中に水
酸化リチウム（ＬｉＯＨ・Ｈ2Ｏ）を５５ｇ／ｌ加えた
溶液を煮沸（１１８℃程度）し、これに前記の電極を３
５分間浸漬する。その結果、合金中の完全な合金層を形
成していないと思われるＺｒ、Ｍｎ、Ｖなどが溶液中に
一部溶出し、主に鱗片状の沈澱が認められるとともに電
極面はほぼ黒色となる。電極は、水洗、乾燥した後も金
属光沢はまったくなく黒色のままである。その後、電極
面に市販の４フッ化エチレン−６フッ化プロピレン共重
合樹脂粉末を０．５〜０．６ｍｇ／ｃｍ2の割合で塗着
する。Next, a solution prepared by adding 55 g / l of lithium hydroxide (LiOH.H 2 O) to a 30% by weight aqueous solution of caustic potash is boiled (about 118 ° C.), and the above-mentioned electrode 3
Soak for 5 minutes. As a result, Zr, Mn, V, etc. which do not seem to form a complete alloy layer in the alloy are partially eluted into the solution, and mainly scale-like precipitates are observed and the electrode surface becomes almost black. . The electrode remains black with no metallic luster after washing and drying. Then, commercially available tetrafluoroethylene-6 fluoropropylene copolymer resin powder is applied to the electrode surface at a rate of 0.5 to 0.6 mg / cm 2 .
【００１０】相手極として公知のニッケル電極、親水処
理したポリプロピレン不織布からなるセパレ−タ、およ
び比重１．２５の苛性カリ水溶液に２５ｇ／ｌの水酸化
リチウムを溶解した電解液を用いて密閉形ニッケル−水
素蓄電池を構成する。電池はＳｕｂＣ型とし、公称容量
は３．３Ａｈである。正極に対する負極の容量は１５０
％とする。この電池をＡとする。比較のために、上記と
同じ水素吸蔵合金電極を苛性カリの３２重量％水溶液中
に１０５℃で３５分間浸漬し、水洗、乾燥後、上記と同
様に樹脂粉末を塗着する。こうして得られた電極を用い
た電池をＢとする。A known nickel electrode as a counter electrode, a separator made of hydrophilic polypropylene non-woven fabric, and an electrolytic solution in which 25 g / l of lithium hydroxide is dissolved in a caustic potash aqueous solution having a specific gravity of 1.25 are used to form a sealed nickel- Configure a hydrogen storage battery. The battery is a SubC type and has a nominal capacity of 3.3 Ah. The capacity of the negative electrode with respect to the positive electrode is 150
%. This battery is designated as A. For comparison, the same hydrogen storage alloy electrode as described above is immersed in a 32 wt% aqueous solution of caustic potash at 105 ° C. for 35 minutes, washed with water, dried, and then coated with a resin powder in the same manner as above. A battery using the electrode thus obtained is designated as B.
【００１１】まず、各電池それぞれ１０セルを用い、サ
イクル初期の放電電圧と容量を比較した。８時間率で容
量の１５０％定電流充電し、０．５Ａで０．９Ｖまで定
電流放電する充放電サイクルを繰り返したところ、電池
Ａは１サイクル目で平均電圧は１．２４Ｖであり、２サ
イクル以降１．２５Ｖ、放電容量は２サイクル以後ほぼ
一定で３．００〜３．０５Ａｈであった。ところが、電
池Ｂは、やや劣り、１サイクル目の平均電圧は１．２２
Ｖであり、放電容量が向上してほぼ一定になるまでに３
サイクルを要した。First, 10 cells of each battery were used, and the discharge voltage and capacity at the beginning of the cycle were compared. When the charge and discharge cycle of constant current charging at a capacity of 150% of capacity for 8 hours and constant current discharging at 0.5 A to 0.9 V was repeated, the average voltage of Battery A was 1.24 V at the first cycle, and 2 After the cycle, the discharge capacity was 1.25 V, and after 2 cycles, the discharge capacity was 3.00 to 3.05 Ah, which was almost constant. However, Battery B was slightly inferior and the average voltage in the first cycle was 1.22.
V, which is 3 before the discharge capacity improves and becomes almost constant.
It took a cycle.
【００１２】つぎに、各電池それぞれ１０セルを用い、
本発明の最も有効な急速充電特性を調べた。周囲温度０
℃において、１．０Ｃ充電を行ったところ、容量の１５
０％充電時における電池内圧力は、電池Ａは平均１．６
ｋｇ／ｃｍ2、電池Ｂは平均２．８ｋｇ／ｃｍ2であり、
１．５Ｃ充電による１５０％充電時における電池内圧の
平均は、電池Ａは３．７ｋｇ／ｃｍ2、電池Ｂは６．４
ｋｇ／ｃｍ2であった。最後に、各電池それぞれ１０セ
ルを用い、０．５Ｃで容量の１２０％定電流充電し、
０．５Ｃで０．９Ｖまで定電流放電する条件で寿命特性
を比較した。その結果、放電容量は、４００サイクルで
は電池Ａ、Ｂとも正極律則で初期の９９％を示している
のに対して、６００サイクルで電池Ａは８８％、電池Ｂ
は７９％であった。Next, using 10 cells for each battery,
The most effective rapid charging characteristics of the present invention were investigated. Ambient temperature 0
When it was charged at 1.0C at ℃, the capacity was 15
The average battery pressure at 0% charge was 1.6 for Battery A.
kg / cm 2 , battery B has an average of 2.8 kg / cm 2 ,
The average battery internal pressure at the time of 150% charging by 1.5 C charging was 3.7 kg / cm 2 for battery A and 6.4 for battery B.
It was kg / cm 2 . Finally, using 10 cells of each battery, 120% of the capacity constant current charging at 0.5C,
The life characteristics were compared under the condition of constant current discharge up to 0.9V at 0.5C. As a result, the discharge capacities of the batteries A and B at the 400th cycle showed the initial 99% according to the positive polarity rule, whereas at the 600th cycle, the battery A showed the 88%,
Was 79%.
【００１３】［実施例２］水素吸蔵合金としてＬａＮｉ
5系合金の一つであるＭｍＮｉ3.7Ｍｎ0.4Ａｌ0.3Ｃｏ
0.6を粉砕し、３００メッシュのふるいを通過する粉末
にポリビニルアルコ−ルの２重量％水溶液を加えてペー
ストを作り、このペ−ストを多孔度９５％、厚さ１．０
ｍｍの発泡状ニッケル板に充填する。この電極を幅３３
ｍｍ、長さ２１０ｍｍに裁断し、リ−ド板をスポット溶
接により取り付けた後、１００トンの加圧機で加圧し、
さらにロ−ラプレス機を通して厚さ０．５２ｍｍに調整
する。[Example 2] LaNi as a hydrogen storage alloy
MmNi 3.7 Mn 0.4 Al 0.3 Co which is one of the 5 series alloys
0.6 is crushed, and a 2% by weight aqueous solution of polyvinyl alcohol is added to the powder which passes through a 300-mesh sieve to make a paste. The paste is 95% in porosity and 1.0 in thickness.
mm foamed nickel plate is filled. This electrode has a width of 33
mm, 210 mm in length, and after attaching the lead plate by spot welding, pressurize it with a presser of 100 tons,
Further, the thickness is adjusted to 0.52 mm through a roller press machine.
【００１４】その後、水酸化リチウム（ＬｉＯＨ・Ｈ2
Ｏ）の２５０ｇ／ｌ水溶液を煮沸（１１２℃程度）し、
これに前記の電極を３５分間浸漬する。その結果、合金
中の完全な合金層を形成していないと思われるＭｎ、Ｃ
ｏ、Ａｌなどが溶液中に一部溶出し、液は青色を呈し、
電極面は薄い黒色になる。電極は水洗、乾燥した後も金
属光沢はまったくない。その後電極面に市販の４フッ化
エチレン−６フッ化プロピレン共重合樹脂粉末を０．５
〜０．６ｍｇ／ｃｍ2の割合で塗着する。After that, lithium hydroxide (LiOH.H 2
B) an aqueous solution of 250 g / l of O) (about 112 ° C.),
The electrode is immersed in this for 35 minutes. As a result, Mn and C which do not seem to form a complete alloy layer in the alloy
o, Al, etc. are partially eluted into the solution, and the solution exhibits a blue color,
The electrode surface becomes light black. The electrode has no metallic luster even after being washed with water and dried. Then, commercially available tetrafluoroethylene-6-fluoropropylene copolymer resin powder 0.5 was applied to the electrode surface.
It is applied at a rate of about 0.6 mg / cm 2 .
【００１５】この電極と、親水性処理をしたポリプロピ
レン不織布からなるセパレ−タ、比重１．２５の苛性カ
リ水溶液に２５ｇ／ｌの水酸化リチウムを溶解した電解
液を用いてＳｕｂＣ型の公称容量２．７Ａｈの電池を構
成する。正極に対する負極の容量は１５０％とする。こ
の電池をＣとする。また、比較のためにアルカリ処理と
して苛性カリの３５重量％水溶液中に１１０〜１１２℃
で３５分間浸漬する他は上記と同様にして得た水素吸蔵
合金電極を用いた電池をＤとする。Using this electrode, a separator made of polypropylene nonwoven fabric subjected to hydrophilic treatment, and an electrolytic solution in which 25 g / l of lithium hydroxide is dissolved in a caustic potash aqueous solution having a specific gravity of 1.25, a Sub C type nominal capacity of 2. Configure a 7 Ah battery. The capacity of the negative electrode with respect to the positive electrode is 150%. This battery is designated as C. For comparison, the alkali treatment was carried out at 110 to 112 ° C. in a 35 wt% aqueous solution of caustic potash.
Let D be a battery using the hydrogen storage alloy electrode obtained in the same manner as above except that it was immersed for 35 minutes.
【００１６】これらの電池各々２０セルを用いて３００
ｍＡで１５時間充電し、３００ｍＡで０．８Ｖまで放電
する化成を３回繰り返した。なお、化成終了時における
平均電圧はいずれも１．２６Ｖ、放電容量は平均２．６
３Ａｈであった。次に、本発明の最も有効な急速充電特
性を比較した。各電池それぞれ１０セルを用い、周囲温
度を０℃とし、１．０Ｃ充電をしたところ、容量の１３
０％充電時における電池内圧力は、電池Ｃは平均１．８
ｋｇ／ｃｍ2であったのに対して、電池Ｄは２．５ｋｇ
／ｃｍ2であり、電池Ａがガス吸収の点で優れていた。
最後に、各電池それぞれ１０セルを用い、０．５Ｃで容
量の１２０％定電流充電し、０．５Ｃで０．９Ｖまで定
電流放電する条件で寿命特性を比較した。その結果、放
電容量は、４００サイクルでは電池Ｃ、Ｄとも正極律則
で初期の９９％を示しているのに対して、８００サイク
ルで電池Ｃは８８％であったのに、電池Ｄは８１％であ
った。300 cells using 20 cells each of these batteries
It was charged for 15 hours at mA, and formed by discharging at 300 mA to 0.8 V three times. The average voltage at the end of formation was 1.26 V, and the discharge capacity was 2.6 on average.
It was 3 Ah. Next, the most effective quick charging characteristics of the present invention were compared. When 10 cells were used for each battery and the ambient temperature was 0 ° C. and the battery was charged at 1.0 C, the capacity was 13
Regarding the internal pressure of the battery at the time of 0% charge, the battery C has an average of 1.8
It was 2.5 kg for Battery D, while it was kg / cm 2.
/ Cm 2 , and Battery A was excellent in terms of gas absorption.
Finally, using 10 cells of each battery, the life characteristics were compared under the conditions of constant-current charging at 0.5 C and 120% of capacity, and constant-current discharging at 0.5 C to 0.9 V. As a result, the discharge capacities of the batteries C and D at the 400th cycle were the initial 99% according to the positive polarity rule, whereas the battery C was 88% at the 800th cycle, but the battery D was 81%. %Met.
【００１７】[0017]
【発明の効果】以上のように本発明によれば、水素吸蔵
合金表面の改良された改質効果によって、初期特性、ガ
ス吸収性、寿命などの特性に優れた水素吸蔵合金電極を
得ることができる。As described above, according to the present invention, it is possible to obtain a hydrogen storage alloy electrode having excellent characteristics such as initial characteristics, gas absorption and life due to the improved effect of modifying the surface of the hydrogen storage alloy. it can.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 辻 庸一郎 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 前川 奈緒子 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoichiro Tsuji 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Naoko Maekawa 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.
Claims (3)
含む水素吸蔵合金電極を煮沸している水酸化リチウムを
含む水酸化カリウム水溶液もしくは水酸化ナトリウム水
溶液に浸漬する工程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. Hydrogen comprising a step of immersing a hydrogen storage alloy powder or a hydrogen storage alloy electrode containing the alloy powder in a boiling potassium hydroxide aqueous solution or sodium hydroxide aqueous solution containing lithium hydroxide. Manufacturing method of storage alloy electrode.
含む水素吸蔵合金電極を煮沸している水酸化リチウム水
溶液に浸漬する工程を有することを特徴とする水素吸蔵
合金電極の製造法。2. A method for producing a hydrogen storage alloy electrode, comprising the step of immersing the hydrogen storage alloy powder or the hydrogen storage alloy electrode containing the alloy powder in a boiling lithium hydroxide aqueous solution.
ている請求項１または２記載の水素吸蔵合金電極の製造
法。3. The method for producing a hydrogen storage alloy electrode according to claim 1, wherein the aqueous solution is saturated with lithium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198918A JPH0729568A (en) | 1993-07-15 | 1993-07-15 | Manufacturing method of hydrogen storage alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198918A JPH0729568A (en) | 1993-07-15 | 1993-07-15 | Manufacturing method of hydrogen storage alloy electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0729568A true JPH0729568A (en) | 1995-01-31 |
Family
ID=16399127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5198918A Pending JPH0729568A (en) | 1993-07-15 | 1993-07-15 | Manufacturing method of hydrogen storage alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729568A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004068625A1 (en) * | 2003-01-31 | 2004-08-12 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure thereof, charging method and charger for sealed alkaline storage battery |
| WO2016157672A1 (en) * | 2015-03-31 | 2016-10-06 | パナソニックＩｐマネジメント株式会社 | Alloy powder for electrodes, negative electrode for nickel-hydrogen storage batteries using same and nickel-hydrogen storage battery |
| WO2018155399A1 (en) * | 2017-02-23 | 2018-08-30 | 愛知製鋼株式会社 | Alkaline storage battery negative electrode, production method for same, and alkaline storage battery |
-
1993
- 1993-07-15 JP JP5198918A patent/JPH0729568A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004068625A1 (en) * | 2003-01-31 | 2004-08-12 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure thereof, charging method and charger for sealed alkaline storage battery |
| US7527890B2 (en) | 2003-01-31 | 2009-05-05 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure and charging method for the same, and charger for sealed alkaline storage battery |
| WO2016157672A1 (en) * | 2015-03-31 | 2016-10-06 | パナソニックＩｐマネジメント株式会社 | Alloy powder for electrodes, negative electrode for nickel-hydrogen storage batteries using same and nickel-hydrogen storage battery |
| WO2018155399A1 (en) * | 2017-02-23 | 2018-08-30 | 愛知製鋼株式会社 | Alkaline storage battery negative electrode, production method for same, and alkaline storage battery |
| JPWO2018155399A1 (en) * | 2017-02-23 | 2019-11-07 | 愛知製鋼株式会社 | Negative electrode for alkaline storage battery, method for producing the same, and alkaline storage battery |
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