JPH0639647B2 - Hydrogen storage Ni-Zr alloy and sealed Ni-hydrogen storage battery - Google Patents
Hydrogen storage Ni-Zr alloy and sealed Ni-hydrogen storage batteryInfo
- Publication number
- JPH0639647B2 JPH0639647B2 JP1273407A JP27340789A JPH0639647B2 JP H0639647 B2 JPH0639647 B2 JP H0639647B2 JP 1273407 A JP1273407 A JP 1273407A JP 27340789 A JP27340789 A JP 27340789A JP H0639647 B2 JPH0639647 B2 JP H0639647B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- alloy
- storage battery
- negative electrode
- sealed
- Prior art date
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- 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
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、ＭｇＺｎ２型結晶構造、すなわち六方晶Ｃ
14型結晶構造をもった水素吸蔵Ｎi −Ｚr 系合金、並び
にこの水素吸蔵Ｎi−Ｚr系合金を負極活物質として用い
てなる密閉型Ｎi−水素蓄電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a MgZn 2 type crystal structure, that is, hexagonal C
The present invention relates to a hydrogen storage Ni-Zr-based alloy having a 14-type crystal structure, and a sealed Ni-hydrogen storage battery using this hydrogen storage Ni-Zr-based alloy as a negative electrode active material.
一般に、密閉型Ｎi−水素蓄電池が、水素吸蔵合金を活
性物として用いてなる負極と、Ｎi正極と、さらにセパ
レータおよびアルカリ電解液で構成され、かつ前記負極
を構成する水素吸蔵合金には、 (a) 室温付近での水素吸蔵・放出能が大きい。Generally, a sealed Ni-hydrogen storage battery is composed of a negative electrode using a hydrogen storage alloy as an active material, a Ni positive electrode, a separator and an alkaline electrolyte, and the hydrogen storage alloy constituting the negative electrode includes: a) Hydrogen storage / release capacity is high near room temperature.
(b) ＰＣＴ曲線における室温付近の温度でのプラトー
圧に相当する平衡水素解離圧が比較的低い（５気圧以
下）。(b) The equilibrium hydrogen dissociation pressure corresponding to the plateau pressure at a temperature near room temperature in the PCT curve is relatively low (5 atm or less).
(c) アルカリ電解液中で耐食性および耐久性（耐劣化
性）がある。(c) Corrosion resistance and durability (deterioration resistance) in alkaline electrolyte.
(d) 水素酸化能（触媒作用）が大きい。(d) Hydrogen oxidization capacity (catalysis) is large.
(e) 水素の吸蔵・放出の繰返しに伴う微粉化が起り難
い。(e) It is difficult for pulverization to occur due to repeated storage and release of hydrogen.
(f) 無（低）公害である。(f) No (low) pollution.
(g) 低コストである。(g) Low cost.
以上(a)〜(g)の性質を具備することが望まれ、さらにこ
のような性質を具備した水素吸蔵合金を負極の活物質と
して用いてなる密閉型Ｎi−水素蓄電池は、大きな放電
容量、長い充・放電サイクル寿命、すぐれた急速充・放
電特性、および低自己放電などの好ましい性能を発揮す
るようになることも良く知られるところである。It is desired to have the above-mentioned properties (a) to (g), and further, a sealed Ni-hydrogen storage battery using a hydrogen storage alloy having such properties as an active material of a negative electrode has a large discharge capacity, It is also well known that favorable characteristics such as long charge / discharge cycle life, excellent rapid charge / discharge characteristics, and low self-discharge will be exhibited.
したがって、特に密閉型Ｎi−水素蓄電池の負極を構成
する活物質として用いるのに適した水素吸蔵合金の開発
が盛んに行なわれ、例えば特開昭61−45563号公報に記
載されるＭgＺn２型結晶構造、すなわち六方晶Ｃ14型結
晶構造をもった水素吸蔵合金はじめ、多数の水素吸蔵合
金が提案されている。Therefore, particularly, a hydrogen storage alloy suitable for use as an active material constituting a negative electrode of a sealed Ni-hydrogen storage battery has been actively developed, and for example, MgZn 2 type crystal described in JP-A-61-45563. A number of hydrogen storage alloys have been proposed, including a hydrogen storage alloy having a structure, that is, a hexagonal C14 type crystal structure.
しかし、すでに提案されているいずれの水素吸蔵合金も
密閉型Ｎi−水素蓄電池の負極活物質として用いる場合
に要求される上記の性質をすべて満足して具備するもの
ではなく、より一層の開発が望まれているのが現状であ
る。However, none of the hydrogen storage alloys that have already been proposed satisfy the above properties required when used as a negative electrode active material of a sealed Ni-hydrogen storage battery, and further development is desired. The current situation is that it is rare.
そこで、本発明者等は、上述のような観点から、特に密
閉型Ｎｉ−水素蓄電池の負極活物質として用いるのに適
した水素吸蔵合金を開発すべく研究を行なった結果、重
量％で（以下％は重量％を示す）、 Ｚr：10〜37％、Ｔi：５〜25％、 Ｍn：４〜20％、Ｗ ：0.01〜13％、 Ｖ ：0.1〜15％、Ｃu：0.1〜７％、 Ｆe：0.01〜５％、Ａl：0.01〜4.5％、 を含有し、さらに必要に応じて、 Ｃr：0.05〜６％、 を含有し、残りがＮiと不可避不純物からなる組成を有
する水素吸蔵Ｎi−Ｚr系合金は、ＭgＺn２型結晶構造
（六方晶Ｃ14型結晶構造）をもち、密閉型Ｎi−水素蓄
電池の負極活物質として用い場合に要求される上記(a)
〜(g)の性質を十分満足した状態で具備し、したがって
これを負極活物質として用いてなる密閉型Ｎi−水素蓄
電池は、大きなエネルギー密度と電気容量をもち、かつ
長いサイクル寿命を示すようになるほか、自己放電が小
さくなり、さらに高率充・放電特性にもすぐれ、無公害
および低コストと合わせて、すぐれた性能を発揮するよ
うになるという知見を得たのである。Therefore, the present inventors conducted research to develop a hydrogen storage alloy that is particularly suitable for use as a negative electrode active material of a sealed Ni-hydrogen storage battery from the above viewpoints, and as a result, % Represents% by weight), Zr: 10 to 37%, Ti: 5 to 25%, Mn: 4 to 20%, W: 0.01 to 13%, V: 0.1 to 15%, Cu: 0.1 to 7%, Fe: 0.01 to 5%, Al: 0.01 to 4.5%, and, if necessary, Cr: 0.05 to 6%, with the balance being Ni and unavoidable impurities. The Zr-based alloy has a MgZn 2 type crystal structure (hexagonal C14 type crystal structure) and is required when used as a negative electrode active material of a sealed Ni-hydrogen storage battery (a).
The sealed Ni-hydrogen storage battery, which has the properties (1) to (g) described above in a sufficiently satisfied state, has a large energy density and electric capacity and a long cycle life. In addition, we have obtained the knowledge that self-discharge becomes smaller, and it has excellent high-rate charge / discharge characteristics, and that it exhibits excellent performance in combination with pollution-free and low cost.
この発明は上記知見にもとづいてなされたものであっ
て、 Ｚr：10〜37％、Ｔi：５〜25％、 Ｍn：４〜20％、Ｗ ：0.01〜13％、 Ｖ ：0.1〜15％、Ｃu：0.1〜７％、 Ｆe：0.01〜５％、Ａl：0.01〜4.5％、 を含有し、さらに必要に応じて、 Ｃr：0.05〜６％、 を含有し、残りがＮiと不可避不純物からなる組成を有
するＭgＺn２型結晶構造、すなわち六方晶Ｃ14型結晶構
造をもった水素吸蔵Ｎi−Ｚr系合金、およびこの水素吸
蔵Ｎi−Ｚr系合金を負極活物質として用いてなる密閉型
Ｎi−水素蓄電池に特徴を有するものである。The present invention was made based on the above findings, and Zr: 10-37%, Ti: 5-25%, Mn: 4-20%, W: 0.01-13%, V: 0.1-15%, Cu: 0.1 to 7%, Fe: 0.01 to 5%, Al: 0.01 to 4.5%, and if necessary, Cr: 0.05 to 6%, with the balance Ni and inevitable impurities. MgZn 2 type crystal structure having a composition, i.e. a hexagonal C14 type crystal structure having a hydrogen storage Ni-Zr alloy, and sealed Ni- hydride storage battery formed by using the hydrogen absorbing Ni-Zr alloy as a negative electrode active material It is characterized by
つぎに、この発明の水素吸蔵Ｎi−Ｚr系合金において、
成分組成を上記の通りに限定した理由を説明する。Next, in the hydrogen storage Ni--Zr alloy of the present invention,
The reason why the component composition is limited as described above will be described.
(a) ＴiおよびＺr これらの成分には、共存した状態で合金に望ましい水素
吸蔵・放出特性を具備せしめると共に、室温における平
衡水素解離圧（プラトー圧）を、例えば５気圧以下に低
める作用があるが、その含有量がそれぞれＴi：５％未
満およびＺr：10％未満では前記作用に所望が効果が得
られず、一方Ｔiの含有量が25％を越えると、平衡水素
解離圧が例えば５気圧以上に上昇するようになり、大き
な放電容量を確保するためには高い水素解離圧を必要と
するようになって蓄電池として好ましくないものとな
り、またＺｒの含有量が37％を越えると、放電容量の水
素解離圧依存の点では問題はないが、水素吸蔵・放出能
が低下するようになることから、その含有量を、それぞ
れＴi：５〜25％、Ｚr：10〜37％と定めた。(a) Ti and Zr These components have the effect of lowering the equilibrium hydrogen dissociation pressure (plateau pressure) at room temperature to, for example, 5 atm or less, while coexisting to provide the alloy with desirable hydrogen storage / release characteristics. However, if the contents thereof are respectively Ti: less than 5% and Zr: less than 10%, the desired effect cannot be obtained. On the other hand, if the content of Ti exceeds 25%, the equilibrium hydrogen dissociation pressure is, for example, 5 atm. As a result, the high hydrogen dissociation pressure is required to secure a large discharge capacity, which is unfavorable for a storage battery. When the Zr content exceeds 37%, the discharge capacity is increased. Although there is no problem in dependence on the hydrogen dissociation pressure, the hydrogen storage / release capacity decreases, so that the contents were set to Ti: 5 to 25% and Zr: 10 to 37%, respectively.
(b) Ｍｎ Ｍn成分には、水素吸蔵・放出能を向上させ、かつアル
カリ電解液中での合金の耐食性および耐久性を向上させ
るほか、蓄電池の負極活物質としての実用に際して自己
放電を抑制する作用があるが、その含有量が４％未満で
は前記作用に所望の効果が得られず、一方その含有量が
20％を越えると、水素吸蔵・放出特性が損なわれるよう
になることから、その含有量を４〜20％と定めた。(b) Mn Mn component improves hydrogen storage / release capacity and corrosion resistance and durability of the alloy in alkaline electrolyte, and suppresses self-discharge during practical use as a negative electrode active material for storage batteries. There is an action, but if the content is less than 4%, the desired effect cannot be obtained on the above action, while the content is
If it exceeds 20%, the hydrogen storage / release characteristics will be impaired, so the content was defined as 4 to 20%.
(c) Ｗ Ｗ成分には、蓄電池を構成するアルカリ電解液に対する
耐食性を一段と向上させると共に、耐久性も向上させ、
さらに蓄電池の負極活物質としての実用に際して自己放
電を抑制する作用があるが、その含有量が0.01％未満で
は前記作用に所望の効果が得られず、一方、その含有量
が13％を越えると、水素吸蔵・放出特性が損なわれるよ
うになることから、その含有量を0.01〜13％と定めた。(c) In the WW component, the corrosion resistance to the alkaline electrolyte constituting the storage battery is further improved, and the durability is also improved.
Further, it has an effect of suppressing self-discharge in practical use as a negative electrode active material of a storage battery, but if its content is less than 0.01%, the desired effect cannot be obtained, while if its content exceeds 13%. Since the hydrogen absorption / desorption characteristics will be impaired, the content was set to 0.01-13%.
(d) Ｖ 上記のように密閉型Ｎi−水素蓄電池には、室温におけ
る平衡水素解離圧が過度に高くなく（例えば５気圧以
下）、かつ水素吸蔵・放出量ができるだけ大きいことが
望まれるが、Ｖ成分には、このような水素吸蔵・放出量
の増大および平衡水素圧の適正化に寄与する作用がある
が、その含有量が 0.1％未満では前記作用に所望の効果
が得られず、一方その含有量が15％を越えると、平衡水
素圧が高すなりすぎるようになるほか、電解液中に溶け
出して、自己放電が助長されるようになることから、そ
の含有量を 0.1〜15％と定めた。(d) V As described above, in the sealed Ni-hydrogen storage battery, it is desired that the equilibrium hydrogen dissociation pressure at room temperature is not excessively high (for example, 5 atm or less) and the hydrogen storage / release amount is as large as possible. The V component has an action of contributing to such an increase in hydrogen storage / release amount and optimization of the equilibrium hydrogen pressure, but if the content thereof is less than 0.1%, the desired effect cannot be obtained in the above action. If the content exceeds 15%, the equilibrium hydrogen pressure will become too high, and it will leach into the electrolyte and promote self-discharge. Defined as%.
(e) Ｃu Ｃu成分には、Ｖとの共存において、水素吸蔵・放出量
の増大および平衡水素圧の適正化を一段と促進する作用
があるが、その含有量が0.1％未満では前記作用に所望
の効果が得られず、一方その含有量が７％を越えると、
水素吸蔵・放出量の低下を招き、放電容量が低下するよ
うになることから、その含有量を 0.1〜７％と定めた。(e) The Cu-Cu component has the action of further promoting the increase in hydrogen storage / release amount and the optimization of the equilibrium hydrogen pressure in the coexistence with V, but if the content is less than 0.1%, it is desirable for the above action. If the content exceeds 7%, the effect of
Since the hydrogen storage / release amount is reduced and the discharge capacity is reduced, the content thereof is set to 0.1 to 7%.
(f) Ｆe Ｆｅ成分には、蓄電池の負極活物質として用いる場合な
どの粉末化に際して、形成された粉末を整粒化する作用
があるが、その含有量が0.01％未満では前記作用に所望
の効果が得られず、一方その含有量が５％を越えると耐
食性が低下し、蓄電池の自己放電が促進するようになる
ことから、その含有量を0.01〜５％と定めた。(f) The Fe Fe component has a function of sizing the formed powder when powdered such as when it is used as a negative electrode active material of a storage battery, but if the content is less than 0.01%, it is desirable for the above-mentioned action. The effect is not obtained, and on the other hand, if the content exceeds 5%, the corrosion resistance decreases and the self-discharge of the storage battery is promoted. Therefore, the content is set to 0.01 to 5%.
(g) Ａl Ａl成分には、水素吸蔵・放出能を低下させることな
く、合金の耐食性を一段と向上させ、もって蓄電池の自
己放電を一層抑制する作用があるが、その含有量が0.01
％未満では前記作用に所望の効果が得られず、一方その
含有量が 4.5％を越えると、水素吸蔵・放出能が目立っ
て低下するようになることから、その含有量を0.01〜4.
5％と定めた。(g) Al The Al component has the effect of further improving the corrosion resistance of the alloy without lowering the hydrogen storage / release capacity and thus further suppressing the self-discharge of the storage battery, but its content is 0.01
When the content is less than 4.5%, the desired effect cannot be obtained, while when the content exceeds 4.5%, the hydrogen storage / release capacity is conspicuously reduced, so the content is 0.01 to 4.
It was set at 5%.
(h) Ｃr Ｃr成分には、特にＡlとの共存において、合金の耐食性
を一段と向上させる作用があるので、必要に応じて含有
されるが、その含有量が0.05％未満では所望の耐食性向
上効果が得られず、一方その含有量が６％を越えると、
水素吸蔵・放出能が低下するようになることから、その
含有量を0.05〜６％と定めた。(h) The Cr Cr component has a function of further improving the corrosion resistance of the alloy, especially in the coexistence with Al, so it is contained as necessary, but if the content is less than 0.05%, the desired corrosion resistance improving effect is obtained. However, if the content exceeds 6%,
Since the hydrogen storage / release capacity decreases, the content thereof is set to 0.05 to 6%.
つぎに、この発明の水素吸蔵Ｎi−Ｚr系合金を実施例に
より具体的に説明する。Next, the hydrogen storage Ni--Zr alloy of the present invention will be specifically described with reference to examples.
通常の高周波誘導溶解炉を用い、Ａr雰囲気中にてそれ
ぞれ第１表に示される成分組成のＮi−Ｚr系合金溶湯を
調製し、銅鋳型に鋳造してインゴットとした後、このイ
ンゴットをＡr雰囲気中、900〜1000℃の範囲内の所定温
度に５時間保持の条件で焼鈍し、ついでジョークラッシ
ャを用い、粗粉砕して直径：２mm以下の粗粒とし、さら
にボールミルを用いて微粉砕して350mesh以下の粒度と
することによりいずれもＭgＺn２型結晶構造をもった本
発明水素吸蔵合金１〜21、比較水素吸蔵合金１〜14、お
よび従来水素吸蔵合金をそれぞれ製造した。Using a normal high-frequency induction melting furnace, a Ni-Zr alloy melt having the composition shown in Table 1 was prepared in an Ar atmosphere, cast into a copper mold to form an ingot, and the ingot was then placed in an Ar atmosphere. Medium, annealed at a predetermined temperature within the range of 900 to 1000 ° C for 5 hours, then coarsely crushed using a jaw crusher to obtain coarse particles with a diameter of 2 mm or less, and then finely crushed using a ball mill. The hydrogen storage alloys 1 to 21 of the present invention, the comparative hydrogen storage alloys 1 to 14 and the conventional hydrogen storage alloys each having the MgZn 2 type crystal structure were manufactured by setting the grain size to 350 mesh or less.
ついで、この結果得られた各種の粉末状水素吸蔵合金を
活物質として用い、まず、これにポリビニールアルコー
ル（ＰＶＡ）の２％水溶液を添加してペースト化した
後、95％の多孔度を有する市販のＮiウイスカー不織布
に充填し、乾燥し、さらに加圧して、平面寸法：42mm×
35mmにして、厚さ：0.60〜0.65mmの形状（活物質充填
量：約2.8ｇ）とし、これの一辺にリードとなるＮｉ薄
板を溶接により取付けて負極を製造し、一方正極として
同寸法のＮｉ焼結板を２枚用意し、これを前記負極の両
側に配置し、30％ＫＯＨ水溶液を装入することにより密
閉型Ｎi−水素蓄電池を製造した。Then, various powdered hydrogen storage alloys obtained as a result were used as an active material, and first, a 2% aqueous solution of polyvinyl alcohol (PVA) was added to form a paste, which had a porosity of 95%. Fill a commercially available Ni whisker non-woven fabric, dry, pressurize, plane dimension: 42mm ×
The shape is 35 mm and the thickness is 0.60 to 0.65 mm (active material filling amount: about 2.8 g), and a Ni thin plate serving as a lead is attached to one side of this by welding to manufacture a negative electrode. Two Ni sintered plates were prepared, placed on both sides of the negative electrode, and charged with a 30% KOH aqueous solution to manufacture a sealed Ni-hydrogen storage battery.
なお、この結果得られた各種の蓄電池を、いずれも開放
電池とし、かつ正極の容易を負極の容量より著しく大き
くすることにより負極の容量を 測定できるようにした。In addition, the various storage batteries obtained as a result are all open batteries, and the capacity of the negative electrode is increased by making the ease of the positive electrode significantly larger than the capacity of the negative electrode. I was able to measure.
また、上記比較水素吸蔵合金１〜14は、これを構成する
成分含有量（第１表に※印を付したもの）が、この発明
の範囲から外れたものである。Further, in the above comparative hydrogen storage alloys 1 to 14, the content of the constituent components thereof (marked with * in Table 1) is out of the range of the present invention.
つぎに、これらの各種の蓄電池について、充・放電速
度：0.2Ｃ、充電電気量：負極容量の130 ％の条件で充
・放電試験を行ない、１回の充電と放電を１サイクルと
し、120サイクル後、240サイクル後、および360サイク
ル後における放電容量をそれぞれ測定し、さらに上記の
各種粉末状水素吸蔵Ｎｉ基合金を負極として用い、いず
れも正極規制のＡＡサイズ（容量：1000mAh）の密閉型
Ｎｉ−水素蓄電池をそれぞれ組立て、これについて自己
放電試験を行ない、その結果を第１表に示した。Next, for each of these storage batteries, a charge / discharge test was conducted under the conditions of charge / discharge speed: 0.2 C, quantity of electricity charged: 130% of the negative electrode capacity, and one cycle of charge and discharge was 120 cycles. After that, the discharge capacity after 240 cycles and after 360 cycles was measured, and the above-mentioned various powdery hydrogen-absorbing Ni-based alloys were used as the negative electrode, and all were AA size (capacity: 1000 mAh) closed-type Ni regulated by the positive electrode. -Each hydrogen storage battery was assembled, and a self-discharge test was performed on the assembled hydrogen storage battery. The results are shown in Table 1.
さらに、詳述すれば第１表に示される粉末状水素吸蔵合
金粉末を用い、平面サイズを90mm×40mm、厚さ：0.60〜
0.65mmとして、容量：1450〜1500mAh（活物質充填量：
約６ｇ）とする以外は、上記の充・放電試験で用いた蓄
電池の負極板と同一の条件で負極板を製造し、一方正極
板は、95％の多孔度を有するＮｉウイスカー不織布に水
酸化ニッケル〔Ｎｉ（ＯＨ）２〕を活物質として充填
し、乾燥し、さらにプレス加工した後、リードを取付け
て、平面寸法：70mm×40mm、厚さ：0.65〜0.70mmの形状
（容量：1000〜1050mAh）とすることにより製造し、こ
の結果得られた負極板と正極板を、セパレータを介して
うず巻き状にした状態で、電解液と共にケース（これは
端子と兼用）の中に収容した構造の密閉型Ｎｉ−水素
蓄電池を製造した。Furthermore, in detail, the powdery hydrogen storage alloy powder shown in Table 1 is used, the plane size is 90 mm × 40 mm, the thickness: 0.60 ~
As 0.65 mm, capacity: 1450 to 1500 mAh (active material filling amount:
A negative electrode plate was manufactured under the same conditions as the negative electrode plate of the storage battery used in the above charge / discharge test, except that the amount was about 6 g), while the positive electrode plate was hydrated with Ni whisker nonwoven fabric having a porosity of 95%. Nickel [Ni (OH) 2 ] is filled as an active material, dried, and further pressed, and then a lead is attached, and a plane dimension: 70 mm × 40 mm, thickness: 0.65 to 0.70 mm (capacity: 1000 to 1050 mAh), and the negative electrode plate and positive electrode plate obtained as a result are wound in a spiral shape with a separator between them and housed in a case (also used as a terminal) together with an electrolytic solution. A sealed Ni-hydrogen storage battery was manufactured.
なお、上記の各種密閉型Ｎｉ−水素蓄電池において、正
極容量より負極容量を大きくしたのは、正極律則の蓄電
池を構成するためである。In addition, in the above various sealed Ni-hydrogen storage batteries, the reason why the negative electrode capacity was made larger than the positive electrode capacity was to configure a storage battery of positive electrode law.
また、自己放電試験は、まず室温で 0.2Ｃ（200mA）で
７時間充電し、ついで蓄電池を45℃に温度をセットして
ある恒温槽中に開路状態（電池に負荷をかけない状態）
で、１週間放置および２週間放置し、放置後、とり出し
て、室温で 0.2Ｃ（200mA）放電を行ない、容量残存率
を求めることにより行なった。In the self-discharge test, first charge at room temperature 0.2C (200mA) for 7 hours, then open the storage battery in the thermostat with the temperature set to 45 ° C (no load on the battery).
The sample was left for 1 week and 2 weeks, taken out, discharged at 0.2 C (200 mA) at room temperature, and the residual capacity ratio was determined.
さらに、上記の各種の水素吸蔵合金について、一般にＨ
uey試験と呼ばれている方法を用い、試験片を上記のイ
ンゴットより切り出してプラスチック樹脂に埋め込み、
腐食面をエメリーペーパー＃600 で研磨仕上げした状態
で、コールドフィンガー型コンデンサー付三角フラスコ
に装入し、沸騰した30％ＫＯＨ水溶液中に 244時間保持
の条件でアルカリ電解液腐食試験を行ない、試験後の腐
食減量を測定した。これらの測定結果も第１表に示し
た。Furthermore, regarding the above various hydrogen storage alloys, in general, H
Using a method called uey test, cut out the test piece from the above ingot and embed it in plastic resin,
With the polished surface of the corroded surface polished with Emery Paper # 600, insert it into an Erlenmeyer flask with a cold finger type condenser and perform an alkaline electrolyte corrosion test under the condition of holding it in a boiling 30% KOH aqueous solution for 244 hours. The corrosion weight loss was measured. The results of these measurements are also shown in Table 1.
第１表に示される結果から、本発明水素吸蔵合金１〜21
は、いずれも従来水素吸蔵合金に比して、アルカリ電解
液に対してすぐれた耐食性を示し、さらにこれを負極活
物質として用いてなる蓄電池は、いずれも高容量であ
り、かつ従来水素吸蔵合金を用いた蓄電池に比して充・
放電サイクルを繰り返した場合の容量低下が著しく小さ
いという好ましい結果を示すのに対して、比較水素吸蔵
合金１〜14に見られるように、構成成分のうちのいずれ
かの含有量でもこの発明の範囲から外れると、アルカリ
電解液に対する耐食性が低下したり、またこれを蓄電池
の負極活物質として用いた場合には、蓄電池の放電容量
や自己放電に劣化傾向が現われるようになることが明ら
かです。From the results shown in Table 1, the present hydrogen storage alloys 1 to 21
Are both excellent in corrosion resistance to alkaline electrolytes as compared with conventional hydrogen storage alloys, and storage batteries using this as a negative electrode active material are both high-capacity and conventional hydrogen storage alloys. Compared to storage batteries using
While showing the preferable result that the capacity decrease when the discharge cycle is repeated is significantly small, as seen in Comparative Hydrogen Storage Alloys 1 to 14, the content of any of the constituent components is within the scope of the present invention. If it is out of the range, it is clear that the corrosion resistance to the alkaline electrolyte decreases, and that if it is used as the negative electrode active material of the storage battery, the discharge capacity and self-discharge of the storage battery will tend to deteriorate.
上述のように、この発明の水素吸蔵Ｎi−Ｚr系合金は、
アルカリ電解液に対する耐食性にすぐれているほか、特
に密閉型Ｎi−水素蓄電池の負極活物質として用いた場
合に、負極活物質に要求される特性をすべて十分満足す
る状態で具備しているので、蓄電池の自己放電が著しく
低減し、さらに長いサイクル寿命に亘って大きな放電容
量が確保されるようになると共に、高価なＶ成分の含有
量が相対的に低いので、コスト低減に寄与するなど工業
上有用な特性を有するのである。As described above, the hydrogen storage Ni--Zr alloy of the present invention is
In addition to being excellent in corrosion resistance to alkaline electrolytes, especially when used as a negative electrode active material of a sealed Ni-hydrogen storage battery, it has all the characteristics required for a negative electrode active material in a state of being sufficiently satisfied. Self-discharge is significantly reduced, a large discharge capacity is secured over a longer cycle life, and the content of expensive V component is relatively low, which contributes to cost reduction and is industrially useful. It has various characteristics.
Claims (4)
上重量％）を有することを特徴とするＭｇＺｎ２型結晶
構造をもった水素吸蔵Ｎi −Ｚr 系合金。1. Zr: 10 to 37%, Ti: 5 to 25%, Mn: 4 to 20%, W: 0.01 to 13%, V: 0.1 to 15%, Cu: 0.1 to 7%, Fe: 0.01 Hydrogen storage Ni-Zr system having a MgZn 2 type crystal structure, characterized in that it contains Al: 0.01% to 4.5%, and the balance is Ni (Nr) and inevitable impurities. alloy.
上重量％）を有するＭｇＺｎ２型結晶構造をもった水素
吸蔵Ｎi −Ｚr 系合金を負極活物質として用いてなる密
閉型Ｎi −水素蓄電池。2. Zr: 10-37%, Ti: 5-25%, Mn: 4-20%, W: 0.01-13%, V: 0.1-15%, Cu: 0.1-7%, Fe: 0.01 ˜5%, Al: 0.01-4.5%, and the balance of NiZn-based alloy having a composition of MgZn 2 type crystal structure with Ni and unavoidable impurities in the balance (above wt%). A sealed Ni-hydrogen storage battery used as.
上重量％）を有することを特徴とするＭｇＺｎ２型結晶
構造をもった水素吸蔵Ｎi −Ｚr 系合金。3. Zr: 10 to 37%, Ti: 5 to 25%, Mn: 4 to 20%, W: 0.01 to 13%, V: 0.1 to 15%, Cu: 0.1 to 7%, Fe: 0.01. .About.5%, Al: 0.01-4.5%, Cr: 0.05-6%, and a balance of Ni and unavoidable impurities (more than wt%). Hydrogen storage Ni-Zr based alloy with a 2 type crystal structure.
上重量％）を有するＭｇＺｎ２型結晶構造をもった水素
吸蔵Ｎi −Ｚr 系合金を負極活物質として用いてなる密
閉型Ｎi −水素蓄電池。4. Zr: 10-37%, Ti: 5-25%, Mn: 4-20%, W: 0.01-13%, V: 0.1-15%, Cu: 0.1-7%, Fe: 0.01 to 5%, Al: 0.01 to 4.5%, contains further, Cr: 0.05 to 6%, containing a MgZn 2 type crystal structure having a composition balance being Ni and inevitable impurities (% by weight or more) A sealed Ni-hydrogen storage battery using the hydrogen storage Ni-Zr alloy as a negative electrode active material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-10447 | 1989-01-19 | ||
| JP1044789 | 1989-01-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02277739A JPH02277739A (en) | 1990-11-14 |
| JPH0639647B2 true JPH0639647B2 (en) | 1994-05-25 |
Family
ID=11750402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1273407A Expired - Lifetime JPH0639647B2 (en) | 1989-01-19 | 1989-10-20 | Hydrogen storage Ni-Zr alloy and sealed Ni-hydrogen storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639647B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293660B1 (en) * | 1987-05-15 | 1993-06-16 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage electrodes |
-
1989
- 1989-10-20 JP JP1273407A patent/JPH0639647B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293660B1 (en) * | 1987-05-15 | 1993-06-16 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage electrodes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02277739A (en) | 1990-11-14 |
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