JPH1027605A - Hydrogen storage electrode - Google Patents
Hydrogen storage electrodeInfo
- Publication number
- JPH1027605A JPH1027605A JP8181075A JP18107596A JPH1027605A JP H1027605 A JPH1027605 A JP H1027605A JP 8181075 A JP8181075 A JP 8181075A JP 18107596 A JP18107596 A JP 18107596A JP H1027605 A JPH1027605 A JP H1027605A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- alloy
- electrode
- rare earth
- 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
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水素吸蔵合金を用い
た水素吸蔵電極に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage electrode using a hydrogen storage alloy.
【０００２】[0002]
【従来の技術】水素吸蔵合金を負極材料として用いるニ
ッケル−水素化物二次電池は低公害性で高エネルギー密
度であることから、ニッケル−カドミウム電池に代わる
電源としてポータブル機器や電気自動車などに用いら
れ、研究開発が盛んに行われている。2. Description of the Related Art Nickel-hydride secondary batteries using a hydrogen storage alloy as a negative electrode material have low pollution properties and a high energy density. Therefore, they are used in portable devices and electric vehicles as a power source in place of nickel-cadmium batteries. R & D is actively conducted.
【０００３】[0003]
【発明が解決しようとする課題】このニッケル−水素化
物二次電池は密閉式電池として使用されており、その場
合、負極容量は正極容量よりも大きく設計されているた
め、過充電時に正極から発生する酸素ガスは負極で吸収
・消費される。しかし、充電・放電サイクルの繰り返し
による水素吸蔵合金の酸化等が原因となって負極でのガ
ス吸収性能や充電効率が低下する。このため電池の内部
圧力の上昇を引き起し、電解液の損失から内部抵抗が上
昇し、電池性能が低下するという問題があった。This nickel-hydride secondary battery is used as a sealed battery. In this case, since the negative electrode capacity is designed to be larger than the positive electrode capacity, it is generated from the positive electrode during overcharge. The generated oxygen gas is absorbed and consumed by the negative electrode. However, gas absorption performance and charging efficiency at the negative electrode are reduced due to oxidation of the hydrogen storage alloy due to repeated charge / discharge cycles. For this reason, there has been a problem that the internal pressure of the battery increases, the internal resistance increases due to the loss of the electrolyte, and the battery performance decreases.
【０００４】これら劣化した電池の負極に用いた水素吸
蔵合金を調べてみると、電極作製時に用いた粒子よりも
小さく微粉化しており、その合金表面は多量の針状生成
物で覆われており、それらは希土類元素の水酸化物等で
あることが判明した。この合金粒子の微粉化と針状生成
物は充放電サイクルに伴い増加する傾向があり、合金粒
子間の導電性の低下を引き起して負極容量の利用率低下
につながると考えられる。[0004] Examination of the hydrogen storage alloy used for the negative electrode of these deteriorated batteries reveals that the particles are smaller and finer than the particles used in the fabrication of the electrode, and that the surface of the alloy is covered with a large amount of acicular products. , They were found to be rare earth element hydroxides and the like. The pulverization of the alloy particles and the acicular products tend to increase with the charge-discharge cycle, which is considered to cause a decrease in the conductivity between the alloy particles, leading to a reduction in the utilization of the negative electrode capacity.
【０００５】一方、水素吸蔵合金を慣用の高周波溶解炉
を用いて、１００℃／ｓｅｃ以下の冷却速度で凝固させ
て作製すると、Ｍｎ，Ａｌ等の置換元素の偏析が起こ
る。この偏析防止手段として、作製した合金を真空中ま
たは不活性ガス雰囲気中で９００〜１０５０℃の高温で
熱処理して均質化することが提案されている。しかし、
その効果は不十分であり、水素吸蔵放出時の結晶格子の
膨張収縮の繰り返しにより歪みが生じ、クラック発生に
よる微粉化が起こりやすい。このため、微粉化により合
金表面積が増加し、酸化しやすくなる。本発明は上記問
題点に鑑みてなされたものであり、充放電サイクル特性
に優れた水素吸蔵合金電極を提供することを目的とす
る。On the other hand, when a hydrogen storage alloy is produced by solidification using a conventional high-frequency melting furnace at a cooling rate of 100 ° C./sec or less, segregation of substitution elements such as Mn and Al occurs. As a means for preventing this segregation, it has been proposed to heat-treat the produced alloy at a high temperature of 900 to 1050 ° C. in a vacuum or an inert gas atmosphere to homogenize the alloy. But,
The effect is insufficient, and distortion is caused by repetition of expansion and contraction of the crystal lattice at the time of hydrogen storage and release, and fine powder is easily generated due to crack generation. Therefore, the pulverization increases the surface area of the alloy and facilitates oxidation. The present invention has been made in view of the above problems, and has as its object to provide a hydrogen storage alloy electrode having excellent charge / discharge cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】本発明の第１は、水素吸
蔵合金が溶融状態から１０3 ℃／ｓｅｃ以上の冷却速度
で凝固させた後、真空中または不活性ガス雰囲気中で６
００〜９００℃の温度範囲において熱処理して得られた
ものであり、且つ該水素吸蔵合金に希土類元素の単体ま
たは化合物を添加剤として含有させてなることを特徴と
する水素吸蔵電極である。The first aspect of the present invention is that after a hydrogen storage alloy is solidified from a molten state at a cooling rate of 10 3 ° C / sec or more, the hydrogen storage alloy is cooled in a vacuum or in an inert gas atmosphere.
A hydrogen storage electrode obtained by heat treatment in a temperature range of 00 to 900 ° C., wherein the hydrogen storage alloy contains a rare earth element simple substance or a compound as an additive.
【０００７】冷却速度が１０3 ℃／ｓｅｃ以上であるの
は、偏析の少ない均質な合金を得るためである。１０3
℃／ｓｅｃ以上で凝固させると、温度が瞬間的に変化す
るため、特定の組成や元素が凝固することがなく、偏析
の少ない均質な合金が得られる。しかし、この様にして
作製した水素吸蔵合金は、偏析に起因する微粉化の問題
点は解決したものの、歪みが大きく微粉化抑制に対する
効果は不十分である。従って、真空中または不活性ガス
雰囲気中で６００〜９００℃の温度範囲において熱処理
することで急冷凝固歪みを取り除いた。この温度範囲以
外では、合金の歪みの除去が不十分となる。[0007] The reason why the cooling rate is 10 3 ° C / sec or more is to obtain a homogeneous alloy with less segregation. 10 3
When the solidification is performed at a temperature of ° C./sec or more, the temperature changes instantaneously, so that a specific alloy having no specific composition or element is solidified and a homogeneous alloy with less segregation can be obtained. However, although the hydrogen storage alloy produced in this way solves the problem of pulverization due to segregation, it has a large strain, and the effect of suppressing pulverization is insufficient. Therefore, rapid solidification distortion was removed by heat treatment in a temperature range of 600 to 900 ° C. in a vacuum or an inert gas atmosphere. Outside this temperature range, the strain of the alloy is not sufficiently removed.
【０００８】本発明の第２は、前記希土類元素が、Ｌ
ａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｙ，Ｅｒ，Ｔｕ，Ｙｂ，Ｌｕ，Ｓｃの中から
選択される少なくとも１種類である水素吸蔵電極であ
る。A second aspect of the present invention is that the rare earth element is L
a, Ce, Pr, Nd, Sm, Eu, Gd, Tb, D
The hydrogen storage electrode is at least one type selected from the group consisting of y, Ho, Y, Er, Tu, Yb, Lu, and Sc.
【０００９】本発明の第３は、前記希土類元素の化合物
が、酸化物、水酸化物、ハロゲン化物の中から選択され
る少なくとも１種類である水素吸蔵電極である。A third aspect of the present invention is a hydrogen storage electrode in which the compound of the rare earth element is at least one selected from oxides, hydroxides, and halides.
【００１０】[0010]
【発明の実施の形態】密閉式ニッケル−水素化物蓄電池
において、負極に用いられた水素吸蔵合金は、充放電サ
イクル数に伴い負極表面に希土類水酸化物等の針状生成
物を生ずる。これは合金内部からの希土類元素の溶出が
起こり、負極表面に析出することによるものである。水
素吸蔵放出時の結晶格子の膨張収縮の繰り返しにより歪
みが生じると、水素吸蔵合金にクラックが発生し、微粉
化が起こる。充放電サイクルに伴う微粉化により合金表
面積が増加するため、針状生成物も増加し、負極の容量
低下を引き起こす。そこで、微粉化の少ない冷却速度が
１０3 ℃／ｓｅｃ以上の合金が提案されているが、この
様な水素吸蔵合金は、偏析に起因する微粉化の問題点は
解決したものの、歪みが大きく微粉化抑制に対する効果
は不十分である。このため、真空中または不活性ガス雰
囲気中で６００〜９００℃の温度範囲において、熱処理
することで急冷凝固歪みを取り除き、従来よりも微粉化
を抑制した。DESCRIPTION OF THE PREFERRED EMBODIMENTS In a sealed nickel-hydride battery, the hydrogen storage alloy used for the negative electrode produces needle-like products such as rare earth hydroxides on the surface of the negative electrode with the number of charge / discharge cycles. This is because rare earth elements are eluted from the inside of the alloy and are deposited on the surface of the negative electrode. When distortion occurs due to repeated expansion and contraction of the crystal lattice during hydrogen storage and release, cracks are generated in the hydrogen storage alloy and pulverization occurs. Since the alloy surface area increases due to pulverization accompanying the charge and discharge cycle, the number of needle-like products also increases, causing a decrease in the capacity of the negative electrode. In view of this, alloys having a low cooling rate of less than 10 3 ° C / sec have been proposed. Such a hydrogen storage alloy solves the problem of pulverization caused by segregation, but has a large strain. The effect on the formation suppression is insufficient. Therefore, in a temperature range of 600 to 900 ° C. in a vacuum or an inert gas atmosphere, rapid solidification distortion is removed by heat treatment, and pulverization is suppressed as compared with the related art.
【００１１】更に、合金表面に安定な希土類元素の不動
態皮膜を形成させることにより、希土類元素の溶出を防
止する。即ち、上記水素吸蔵合金とＬａ，Ｃｅ，Ｐｒ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｙ，Ｅ
ｒ，Ｔｕ，Ｙｂ，Ｌｕ，Ｓｃ等の中から選択される少な
くとも１種類の希土類元素の単体または化合物を添加剤
として作製した水素吸蔵電極は、微粉化による合金表面
積の増加が少なく、微粉化して現れる新し合金表面にも
安定な希土類元素の不動態皮膜を形成させるため、水素
吸蔵電極の容量低下に起因する希土類水酸化物等の針状
生成物の増加が抑えられた優れた水素吸蔵電極を得るこ
とができる。Further, by forming a stable rare earth element passive film on the alloy surface, elution of the rare earth element is prevented. That is, the above hydrogen storage alloy and La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, E
A hydrogen storage electrode manufactured using at least one kind of a rare earth element alone or a compound selected from r, Tu, Yb, Lu, Sc and the like as an additive has a small increase in the alloy surface area due to the pulverization. An excellent hydrogen storage electrode that suppresses the increase of needle-like products such as rare earth hydroxides due to a decrease in the capacity of the hydrogen storage electrode in order to form a stable rare earth element passive film on the new alloy surface that appears. Can be obtained.
【００１２】[0012]
【実施例】以下、本発明を実施例により詳細に説明す
る。まず、市販のＬａ、Ｃｅ、Ｐｒ、Ｎｄなどの希土類
元素の複合体であるミッシュメタル（Ｍｍ）、Ｎｉ、Ａ
ｌ、Ｃｏ、Ｍｎを所定量秤量し、不活性雰囲気下で高周
波溶解炉を用いて溶解後、放置冷却してＭｍＮｉ3.8 Ａ
ｌ0.3 Ｃｏ0.7 Ｍｎ0.2 の組成の合金を作製し、アルゴ
ン雰囲気中で１０００℃、３時間熱処理した。この合金
をＡとする。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. First, a commercially available complex of rare earth elements such as La, Ce, Pr, and Nd, which is a misch metal (Mm), Ni, A
l, Co, and Mn are weighed in predetermined amounts, melted in a high-frequency melting furnace under an inert atmosphere, and then left to cool to obtain MmNi 3.8 A
An alloy having a composition of l 0.3 Co 0.7 Mn 0.2 was prepared and heat-treated at 1000 ° C. for 3 hours in an argon atmosphere. This alloy is designated as A.
【００１３】次に、上記合金Ａを高周波溶解炉で加熱溶
解させた後、融液をセラミック単孔ノズルに注ぎ入れ、
アルゴンガス加圧によりノズル下方に設けられた銅性の
回転ロール周面に溶液を噴出させて、冷却速度１０3 ℃
／ｓｅｃで急冷凝固させて、フレーク状の急冷合金を得
た。この合金をＢとする。さらにこの急冷合金を９００
℃５時間の熱処理した。この合金をＣとする。上記合金
作製は、全てアルゴン雰囲気内で行った。Next, after the alloy A is heated and melted in a high-frequency melting furnace, the melt is poured into a ceramic single-hole nozzle.
The solution was jetted onto the peripheral surface of a copper-made rotating roll provided below the nozzle by argon gas pressurization, and the cooling rate was 10 3 ° C.
/ Sec for rapid solidification to obtain a flaky quenched alloy. This alloy is designated as B. In addition, this quenched alloy was added to 900
C. for 5 hours. This alloy is designated as C. All the above alloy preparations were performed in an argon atmosphere.
【００１４】これらの合金をそれぞれ機械粉砕し、得ら
れた合金粉末と増粘剤を加えてペースト状にし、ニッケ
ル繊維基板に充填し、乾燥後プレスして水素吸蔵電極を
得た。これら３種類の合金を用いた電極をそれぞれ比較
電極１、比較電極２、比較電極３とする。合金Ｃを機械
粉砕して得られた合金粉末とYb2O3 粉末０．５％とを乳
鉢でよく混合してから、増粘剤を加えてペースト状に
し、ニッケル繊維基板に充填し、乾燥後プレスして水素
吸蔵電極を得た。これを本発明電極Ａとする。Each of these alloys was mechanically pulverized, and the resulting alloy powder and a thickener were added to form a paste, filled in a nickel fiber substrate, dried and pressed to obtain a hydrogen storage electrode. The electrodes using these three alloys are referred to as Comparative electrode 1, Comparative electrode 2, and Comparative electrode 3, respectively. The alloy powder obtained by mechanically pulverizing Alloy C and Yb 2 O 3 powder 0.5% are mixed well in a mortar, then a thickener is added to form a paste, which is filled in a nickel fiber substrate and dried. Thereafter, pressing was performed to obtain a hydrogen storage electrode. This is designated as electrode A of the present invention.
【００１５】これら４種類の電極を負極とし、高密度粉
末水酸化ニッケル活物質を用いたペースト式ニッケル極
を正極とし、電解液として比重１．２８の水酸化カリウ
ム溶液を用いて、公称容量１１００ｍＡｈのＡＡサイズ
の密閉電池を作製し、充放電サイクルを行った。充電は
０．５ＣｍＡで３時間、放電は０．５ＣｍＡで１．０Ｖ
ｏｌｔまで行い、充電と放電の間の休止時間を１時間と
して行った。These four types of electrodes are used as negative electrodes, a paste-type nickel electrode using a high-density powdered nickel hydroxide active material is used as a positive electrode, and a potassium hydroxide solution having a specific gravity of 1.28 is used as an electrolytic solution, with a nominal capacity of 1100 mAh. AA size sealed battery was manufactured and subjected to a charge / discharge cycle. Charge at 0.5 CmA for 3 hours, Discharge at 0.5 CmA at 1.0 V
lt, and the rest time between charging and discharging was set to 1 hour.
【００１６】充放電試験におけるサイクル数と放電容量
の関係を図１に示す。図１から明らかなように、本発明
電極Ａは、比較電極１、比較電極２および比較電極３に
較べ充放電サイクル特性が優れていることが分かる。FIG. 1 shows the relationship between the number of cycles and the discharge capacity in the charge / discharge test. As is clear from FIG. 1, the electrode A of the present invention has better charge / discharge cycle characteristics than the comparative electrode 1, the comparative electrode 2, and the comparative electrode 3.
【００１７】上記電池を解体して、充放電サイクル後の
電極から水素吸蔵合金を取り出し、合金平均粒子径を測
定すると、合金平均粒子の大きい順に本発明電極Ａ＝比
較電極３＞比較電極２＞比較電極１であった。この結果
より合金Ｃの微粉化が抑制されていることが分かる。更
に、取り出した水素吸蔵合金のＸ線回折を行った。希土
類水酸化物のピークを比較すると、本発明電極Ａは、比
較電極１、２、３に比べて、その生成量は少なく、合金
腐食を抑制していることが分かった。After disassembling the battery and taking out the hydrogen storage alloy from the electrode after the charge / discharge cycle and measuring the average particle diameter of the alloy, the electrode A of the present invention = comparative electrode 3> comparative electrode 2> Comparative electrode 1 was obtained. From this result, it can be seen that pulverization of the alloy C is suppressed. Further, the extracted hydrogen storage alloy was subjected to X-ray diffraction. Comparing the peaks of the rare earth hydroxides, it was found that the electrode A of the present invention produced a smaller amount than the comparative electrodes 1, 2, and 3 and suppressed alloy corrosion.
【００１８】[0018]
【発明の効果】上記のように、本発明の水素吸蔵電極で
は、微粉化による合金表面積増加の抑制と合金腐食を抑
制し、充放電サイクル特性に優れた効果が得られるた
め、その工業的価値は大きい。As described above, in the hydrogen storage electrode of the present invention, the effect of suppressing the increase in the alloy surface area due to the pulverization and the alloy corrosion can be obtained, and the effect excellent in the charge / discharge cycle characteristics can be obtained. Is big.
【図１】放電容量とサイクル数との関係図である。FIG. 1 is a relationship diagram between a discharge capacity and the number of cycles.
Claims (3)
／ｓｅｃ以上の冷却速度で凝固させた後、真空中または
不活性ガス雰囲気中で６００〜９００℃の温度範囲にお
いて熱処理して得られたものであり、且つ該水素吸蔵合
金に希土類元素の単体または化合物を添加剤として含有
させてなることを特徴とする水素吸蔵電極。1. The hydrogen storage alloy is heated to a temperature of 10 3 ° C. from a molten state.
/ Sec and then heat-treated in a vacuum or an inert gas atmosphere at a temperature in the range of 600 to 900 ° C., and the hydrogen-absorbing alloy is made of a single element of rare earth element or A hydrogen storage electrode comprising a compound as an additive.
Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｙ，Ｅ
ｒ，Ｔｕ，Ｙｂ，Ｌｕ，Ｓｃの中から選択される少なく
とも１種類である請求項１記載の水素吸蔵電極。2. The method according to claim 1, wherein the rare earth element is La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, E
The hydrogen storage electrode according to claim 1, wherein the hydrogen storage electrode is at least one selected from the group consisting of r, Tu, Yb, Lu, and Sc.
酸化物、ハロゲン化物の中から選択される少なくとも１
種類である請求項１記載の水素吸蔵電極。3. The method according to claim 1, wherein the rare earth compound is at least one selected from oxides, hydroxides, and halides.
The hydrogen storage electrode according to claim 1, wherein the hydrogen storage electrode is of a kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18107596A JP3678281B2 (en) | 1996-07-11 | 1996-07-11 | Hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18107596A JP3678281B2 (en) | 1996-07-11 | 1996-07-11 | Hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1027605A true JPH1027605A (en) | 1998-01-27 |
| JP3678281B2 JP3678281B2 (en) | 2005-08-03 |
Family
ID=16094376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18107596A Expired - Fee Related JP3678281B2 (en) | 1996-07-11 | 1996-07-11 | Hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3678281B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307721A (en) * | 2000-04-24 | 2001-11-02 | Toshiba Corp | Hydrogen-storage alloy electrode, alkaline secondary battery, hybrid car and electric vehicle |
-
1996
- 1996-07-11 JP JP18107596A patent/JP3678281B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307721A (en) * | 2000-04-24 | 2001-11-02 | Toshiba Corp | Hydrogen-storage alloy electrode, alkaline secondary battery, hybrid car and electric vehicle |
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| JP3678281B2 (en) | 2005-08-03 |
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