JP2005248252A - Hydrogen storage alloy for alkaline storage battery, and alkaline storage battery - Google Patents

Hydrogen storage alloy for alkaline storage battery, and alkaline storage battery Download PDF

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JP2005248252A
JP2005248252A JP2004060292A JP2004060292A JP2005248252A JP 2005248252 A JP2005248252 A JP 2005248252A JP 2004060292 A JP2004060292 A JP 2004060292A JP 2004060292 A JP2004060292 A JP 2004060292A JP 2005248252 A JP2005248252 A JP 2005248252A
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hydrogen storage
alkaline
storage alloy
storage battery
rare earth
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JP2005248252A5 (en
JP4514477B2 (en
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Tetsuyuki Murata
徹行 村田
Shigekazu Yasuoka
茂和 安岡
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Sanyo Electric Co Ltd
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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
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Abstract

<P>PROBLEM TO BE SOLVED: To extend the cycle life of an alkaline storage battery using a hydrogen storage alloy containing at least a rare earth element, magnesium, nickel and aluminum for a negative electrode, by inhibiting the hydrogen storage alloy used in the negative electrode from being pulverized when discharge and charge are repeated, and from being oxidized due to a reaction with an alkaline electrolytic solution. <P>SOLUTION: The hydrogen storage alloy used in the negative electrode of the alkaline storage battery provided with a positive electrode 1, the negative electrode 2 using the hydrogen storage alloy and the alkaline electrolytic solution comprises at least rare earth element, magnesium, nickel and aluminum, wherein the rare earth elements include at least lanthanum, and the amount of lanthanum exceeds 50 atomic% of the total rare earth elements. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

この発明は、アルカリ蓄電池及びこのアルカリ蓄電池の負極に使用されるアルカリ蓄電池用水素吸蔵合金に係り、特に、アルカリ蓄電池の負極に水素吸蔵能力の高い水素吸蔵合金を用いて、アルカリ蓄電池の容量を高めると共に、充放電によりこの水素吸蔵合金が微粉化されてアルカリ電解液によって酸化されるのを防止し、アルカリ蓄電池におけるサイクル寿命を向上させるようにした点に特徴を有するものである。   The present invention relates to an alkaline storage battery and a hydrogen storage alloy for an alkaline storage battery used for the negative electrode of the alkaline storage battery, and in particular, to increase the capacity of the alkaline storage battery by using a hydrogen storage alloy having a high hydrogen storage capacity for the negative electrode of the alkaline storage battery. At the same time, the hydrogen storage alloy is prevented from being pulverized by charge / discharge and being oxidized by the alkaline electrolyte, thereby improving the cycle life of the alkaline storage battery.

近年、アルカリ蓄電池としては、ニッケル・カドミウム蓄電池に比べて高容量であり、カドミウムを使用しないため環境安全性にも優れているという点から、負極の材料に水素吸蔵合金を用いたニッケル・水素蓄電池が広く用いられるようになった。   In recent years, nickel-hydrogen storage batteries using a hydrogen storage alloy as the negative electrode material have a higher capacity than nickel-cadmium storage batteries and are superior in environmental safety because they do not use cadmium. Became widely used.

そして、このようなニッケル・水素蓄電池が各種のポータブル機器に使用されるようになり、このニッケル・水素蓄電池をさらに高性能化させることが期待されている。   Such nickel / hydrogen storage batteries are used in various portable devices, and it is expected that the nickel / hydrogen storage batteries will have higher performance.

ここで、このニッケル・水素蓄電池においては、その負極に使用する水素吸蔵合金として、ＣａＣｕ5型の結晶を主相とする希土類−ニッケル系水素吸蔵合金や、Ｔｉ，Ｚｒ，Ｖ及びＮｉを含むラーベス相系の水素吸蔵合金等が一般に使用されていた。 Here, in this nickel-hydrogen storage battery, as a hydrogen storage alloy used for the negative electrode, a rare earth-nickel hydrogen storage alloy having a CaCu 5 type crystal as a main phase, or Laves containing Ti, Zr, V and Ni. A phase-type hydrogen storage alloy or the like has been generally used.

しかし、これらの水素吸蔵合金は、水素吸蔵能力が必ずしも十分であるとはいえず、ニッケル・水素蓄電池の容量をさらに高めることが困難であった。   However, these hydrogen storage alloys do not necessarily have sufficient hydrogen storage capacity, and it has been difficult to further increase the capacity of the nickel-hydrogen storage battery.

そして、近年においては、上記のような希土類−ニッケル系水素吸蔵合金における水素吸蔵能力を向上させるために、上記の希土類−ニッケル系水素吸蔵合金にＭｇ等を含有させた水素吸蔵合金を用いることが提案されている（例えば、特許文献１参照）。   In recent years, in order to improve the hydrogen storage capacity in the rare earth-nickel hydrogen storage alloy as described above, a hydrogen storage alloy containing Mg or the like in the rare earth-nickel hydrogen storage alloy is used. It has been proposed (for example, see Patent Document 1).

しかし、上記のような水素吸蔵合金をアルカリ蓄電池の負極に使用して充放電を繰り返して行った場合、この水素吸蔵合金が微粉化されると共に、この水素吸蔵合金がアルカリ電解液と反応して酸化され、アルカリ蓄電池内におけるアルカリ電解液が次第に消費されて、アルカリ蓄電池内における抵抗が増大し、アルカリ蓄電池のサイクル寿命が低下するという問題があった。特に、最近においては、電池容量をさらに高めるために、正極や負極の活物質量を多くして、電池中におけるアルカリ電解液の量を少なくすることが行われるようになり、このような場合には、アルカリ電解液の消費により、アルカリ蓄電池のサイクル寿命がさらに大きく低下するという問題があった。
特開２００１−３１６７４４号公報 However, when the above-described hydrogen storage alloy is used for the negative electrode of an alkaline storage battery and repeatedly charged and discharged, the hydrogen storage alloy is pulverized and the hydrogen storage alloy reacts with the alkaline electrolyte. Oxidized, and the alkaline electrolyte in the alkaline storage battery is gradually consumed, increasing the resistance in the alkaline storage battery and reducing the cycle life of the alkaline storage battery. Recently, in order to further increase the battery capacity, the amount of the active material of the positive electrode and the negative electrode is increased to reduce the amount of alkaline electrolyte in the battery. However, there is a problem that the cycle life of the alkaline storage battery is further reduced by consumption of the alkaline electrolyte.
JP 2001-316744 A

この発明は、希土類−ニッケル系水素吸蔵合金にＭｇ等を含有させて、水素吸蔵能力を向上させた水素吸蔵合金を負極に使用し、容量を高めるようにしたアルカリ蓄電池における上記のような問題を解決することを課題とするものであり、上記のアルカリ蓄電池を繰り返して充放電させた場合において、負極に使用した水素吸蔵合金が微粉化されて、この水素吸蔵合金がアルカリ電解液と反応して酸化されるのを抑制し、上記のアルカリ蓄電池におけるサイクル寿命を向上させることを課題とするものである。   The present invention has the above-mentioned problems in an alkaline storage battery in which a rare earth-nickel-based hydrogen storage alloy contains Mg or the like and a hydrogen storage alloy with improved hydrogen storage capacity is used for the negative electrode to increase the capacity. In the case where the above alkaline storage battery is repeatedly charged and discharged, the hydrogen storage alloy used for the negative electrode is pulverized, and this hydrogen storage alloy reacts with the alkaline electrolyte. It is an object to suppress oxidation and improve the cycle life of the alkaline storage battery.

この発明におけるアルカリ蓄電池用水素吸蔵合金においては、上記のような課題を解決するため、少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金において、希土類元素として少なくともランタンが含まれるようにし、希土類元素全体中におけるランタンの量が５０原子％を超えるようにした。   In the hydrogen storage alloy for alkaline storage batteries according to the present invention, in order to solve the above-described problems, in the hydrogen storage alloy containing at least a rare earth element, magnesium, nickel, and aluminum, at least lanthanum is included as the rare earth element, The amount of lanthanum in the entire rare earth element was set to exceed 50 atomic%.

また、この発明におけるアルカリ蓄電池においては、正極と、水素吸蔵合金を用いた負極と、アルカリ電解液とを備えたアルカリ蓄電池において、その負極における水素吸蔵合金に、上記のようなアルカリ蓄電池用水素吸蔵合金を用いるようにした。   Further, in the alkaline storage battery according to the present invention, in the alkaline storage battery provided with the positive electrode, the negative electrode using the hydrogen storage alloy, and the alkaline electrolyte, the hydrogen storage alloy for the negative electrode includes the hydrogen storage for alkaline storage battery as described above. An alloy was used.

そして、この発明におけるアルカリ蓄電池のように、その負極に、少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金であって、希土類元素として少なくともランタンが含まれ、希土類元素全体中におけるランタンの量が５０原子％を超えるものを用いると、この水素吸蔵合金の水素吸蔵能力が高くて、高容量のアルカリ蓄電池が得られると共に、このアルカリ蓄電池を繰り返して充放電させた場合に、この水素吸蔵合金が微粉化するのが抑制され、この水素吸蔵合金がアルカリ電解液と反応して酸化されるのも防止されるようになる。   And, like the alkaline storage battery in this invention, the negative electrode is a hydrogen storage alloy containing at least a rare earth element, magnesium, nickel and aluminum, and at least lanthanum is contained as the rare earth element, and lanthanum in the entire rare earth element If the amount exceeds 50 atomic%, the hydrogen storage alloy has a high hydrogen storage capacity and a high-capacity alkaline storage battery is obtained, and when the alkaline storage battery is repeatedly charged and discharged, The alloy is prevented from being pulverized, and the hydrogen storage alloy is prevented from reacting with the alkaline electrolyte and being oxidized.

ここで、上記の少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金としては、一般式Ｌｎ1-xＭｇxＮｉy-aＡｌa（式中、Ｌｎは希土類元素から選択される少なくとも１種の元素であり、０．０５≦ｘ＜０．２０、２．８≦ｙ≦３．９、０．１０≦ａ≦０．２５の条件を満たす。）で表わされるものを用いることが好ましい。ここで、０．０５≦ｘ＜０．２０の条件を満たすようにしたのは、ｘが０．０５未満になると、水素吸蔵合金における水素吸蔵能力が低下する一方、ｘが０．２０以上になると、酸化されやすいＭｇが増加して、水素吸蔵合金が酸化されやすくなるためである。また、２．８≦ｙ≦３．９の条件を満たすようにしたのは、ｙが２．８未満になると、水素吸蔵合金において目的の合金相と異なる合金相が増大し、水素吸蔵放出に伴う残留水素が増加して、水素放出量が著しく低下する一方、ｙが３．９を超えると、水素吸蔵量が著しく低下するのためである。また、０．１０≦ａ≦０．２５の条件を満たすようにしたのは、ａが１．０未満になると、水素吸蔵合金が酸化されやすくなる一方、ａが０．２５を超えると、水素吸蔵合金における水素吸蔵能力が低下するためである。 Examples of the hydrogen-absorbing alloy containing at least a rare-earth element, magnesium, nickel and aluminum of the above, in the general formula Ln 1-x Mg x Ni ya Al a ( wherein, at least one Ln is selected from rare earth elements Elements satisfying the following conditions: 0.05 ≦ x <0.20, 2.8 ≦ y ≦ 3.9, and 0.10 ≦ a ≦ 0.25. Here, the condition of 0.05 ≦ x <0.20 is set so that when x is less than 0.05, the hydrogen storage capacity of the hydrogen storage alloy decreases, while x is 0.20 or more. This is because Mg which is easily oxidized increases and the hydrogen storage alloy is easily oxidized. In addition, the condition of 2.8 ≦ y ≦ 3.9 is set so that when y is less than 2.8, the alloy phase different from the target alloy phase increases in the hydrogen storage alloy, and the hydrogen storage and release occurs. This is because the accompanying hydrogen increases and the hydrogen release amount is remarkably lowered, while when y exceeds 3.9, the hydrogen storage amount is remarkably lowered. Further, the condition of 0.10 ≦ a ≦ 0.25 is set such that when a is less than 1.0, the hydrogen storage alloy is easily oxidized, whereas when a exceeds 0.25, hydrogen is absorbed. This is because the hydrogen storage capacity of the storage alloy decreases.

また、上記の水素吸蔵合金において、希土類元素としてジルコニウムを含有させると共に、上記のマグネシウムとニッケルとアルミニウムとの他にコバルトを含有させると、水素吸蔵合金がアルカリ電解液によって酸化されるのが一層防止されるようになる。   In addition, when the above hydrogen storage alloy contains zirconium as a rare earth element and cobalt in addition to the above magnesium, nickel and aluminum, the hydrogen storage alloy is further prevented from being oxidized by an alkaline electrolyte. Will come to be.

この発明においては、正極と、水素吸蔵合金を用いた負極と、アルカリ電解液とを備えたアルカリ蓄電池において、その負極に、少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金を用いるようにしたため、この水素吸蔵合金の水素吸蔵能力が高く、高容量のアルカリ蓄電池が得られる。   In the present invention, in an alkaline storage battery including a positive electrode, a negative electrode using a hydrogen storage alloy, and an alkaline electrolyte, a hydrogen storage alloy containing at least a rare earth element, magnesium, nickel, and aluminum is used for the negative electrode. Therefore, the hydrogen storage capacity of the hydrogen storage alloy is high, and a high capacity alkaline storage battery can be obtained.

また、上記の少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金において、希土類元素として少なくともランタンが含まれると共に、希土類元素全体中におけるランタンの量が５０原子％を超える水素吸蔵合金を用いるようにしたため、このアルカリ蓄電池を繰り返して充放電した場合に、この水素吸蔵合金が微粉化するのが抑制され、この水素吸蔵合金がアルカリ電解液と反応して酸化されるのも防止され、アルカリ蓄電池内におけるアルカリ電解液が次第に消費されて、アルカリ蓄電池のサイクル寿命が低下するのが抑制されるようになる。特に、電池容量をさらに高めるために、正極や負極の活物質量を多くして、電池中におけるアルカリ電解液の量を少なくした場合、例えば、アルカリ電解液の量を電池の理論容量に対して１．２ｇ／Ａｈ以下にした場合においては、アルカリ電解液の消費によるアルカリ蓄電池のサイクル寿命の低下が一層抑制されるようになる。   Further, in the hydrogen storage alloy including at least the rare earth element, magnesium, nickel, and aluminum, a hydrogen storage alloy that includes at least lanthanum as the rare earth element and the amount of lanthanum in the entire rare earth element exceeds 50 atomic% is used. Therefore, when the alkaline storage battery is repeatedly charged and discharged, the hydrogen storage alloy is suppressed from being pulverized, and the hydrogen storage alloy is prevented from reacting with the alkaline electrolyte and being oxidized. It is suppressed that the alkaline electrolyte in a storage battery is consumed gradually, and the cycle life of an alkaline storage battery falls. In particular, in order to further increase the battery capacity, when the amount of the active material of the positive electrode or the negative electrode is increased to reduce the amount of the alkaline electrolyte in the battery, for example, the amount of the alkaline electrolyte is reduced with respect to the theoretical capacity of the battery. In the case of 1.2 g / Ah or less, a decrease in the cycle life of the alkaline storage battery due to consumption of the alkaline electrolyte is further suppressed.

以下、この発明の実施例に係るアルカリ蓄電池用水素吸蔵合金電極及びアルカリ蓄電池について具体的に説明すると共に、比較例を挙げ、この発明の実施例に係るアルカリ蓄電池においては、充放電を繰り返して行った場合に、その負極に用いた水素吸蔵合金が微粉化されたり、酸化されたりするのが抑制されて、アルカリ蓄電池のサイクル寿命が低下するのが防止されることを明らかにする。なお、この発明におけるアルカリ蓄電池用水素吸蔵合金及電極及びアルカリ蓄電池は、下記の実施例に示したものに限定されず、その要旨を変更しない範囲において適宜変更して実施できるものである。   Hereinafter, the hydrogen storage alloy electrode for alkaline storage battery and the alkaline storage battery according to the embodiment of the present invention will be specifically described, and a comparative example will be given. In the alkaline storage battery according to the embodiment of the present invention, charging and discharging are repeated. In this case, it is clarified that the hydrogen storage alloy used for the negative electrode is prevented from being pulverized or oxidized, thereby preventing the cycle life of the alkaline storage battery from being lowered. In addition, the hydrogen storage alloy and electrode for alkaline storage batteries and the alkaline storage battery in the present invention are not limited to those shown in the following examples, and can be implemented with appropriate modifications within the scope not changing the gist thereof.

（実施例１）
実施例１においては、負極を作製するにあたり、希土類元素であるＬａ，Ｐｒ，Ｎｄ及びＺｒと、Ｍｇと、Ｎｉと、Ａｌと、Ｃｏとを用い、これらを所定の合金組成になるように混合し、これを高周波誘導溶解させた後、これを冷却させて、組成が（Ｌａ0.592Ｐｒ0.199Ｎｄ0.206Ｚｒ0.004）0.83Ｍｇ0.17Ｎｉ3.15Ａｌ0.15Ｃｏ0.1になった水素吸蔵合金のインゴットを作製した。 (Example 1)
In Example 1, in preparing the negative electrode, rare earth elements such as La, Pr, Nd, and Zr, Mg, Ni, Al, and Co were used and mixed so as to have a predetermined alloy composition. Then, this was melted by induction induction, and then cooled, to prepare a hydrogen storage alloy ingot having a composition of (La 0.592 Pr 0.199 Nd 0.206 Zr 0.004 ) 0.83 Mg 0.17 Ni 3.15 Al 0.15 Co 0.1 .

そして、この水素吸蔵合金のインゴットをアルゴン雰囲気中において９５０℃で熱処理して均質化させた後、この水素吸蔵合金のインゴットを不活性雰囲気中において機械的に粉砕し、これを分級して、体積平均粒径が６５μｍになった上記の水素吸蔵合金の粉末を得た。なお、水素吸蔵合金の粉末の体積平均粒径は、レーザー回折式粒度分布測定装置（島津製作所社製：ＳＡＬＤ−２０００）を用いて測定した。   Then, the hydrogen storage alloy ingot was heat treated in an argon atmosphere at 950 ° C. to homogenize, and then the hydrogen storage alloy ingot was mechanically pulverized in an inert atmosphere, and this was classified into a volume. A powder of the above hydrogen storage alloy having an average particle size of 65 μm was obtained. The volume average particle size of the hydrogen storage alloy powder was measured using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation: SALD-2000).

そして、上記の水素吸蔵合金の粉末１００重量部に対して、結着剤のポリエチレンオキシドを０．５重量部、ポリビニルピロリドンを０．６重量部加え、これらを均一に混合してスラリーを調製し、このスラリーをニッケルめっきしたパンチングメタルからなる集電体の両面に均一に塗布し、これを乾燥し圧延させた後、所定の寸法に切断して、上記の水素吸蔵合金を含む負極を作製した。   Then, with respect to 100 parts by weight of the hydrogen storage alloy powder, 0.5 parts by weight of polyethylene oxide as a binder and 0.6 parts by weight of polyvinyl pyrrolidone are added and mixed uniformly to prepare a slurry. The slurry was uniformly applied to both surfaces of a nickel-plated punching metal current collector, dried and rolled, and then cut into predetermined dimensions to produce a negative electrode containing the above hydrogen storage alloy. .

一方、正極を作製するにあたっては、活物質の水酸化ニッケル１００重量部に対して、０．２重量％のヒドロキシプロピルセルロース水溶液を５０重量部加え、これらを混合させてスラリーを調製し、このスラリーをニッケル発泡体に充填し、これを乾燥させて圧延させた後、所定の寸法に切断して非焼結式ニッケル極からなる正極を作製した。   On the other hand, in preparing the positive electrode, 50 parts by weight of a 0.2% by weight hydroxypropylcellulose aqueous solution is added to 100 parts by weight of nickel hydroxide as an active material, and these are mixed to prepare a slurry. Was filled in a nickel foam, dried and rolled, and then cut into predetermined dimensions to produce a positive electrode composed of a non-sintered nickel electrode.

また、セパレータとしてはポリプロピレン製の不織布を使用し、アルカリ電解液としては、ＫＯＨとＮａＯＨとＬｉＯＨとを合計で３０重量％含むアルカリ電解液を使用した。   Moreover, the nonwoven fabric made from a polypropylene was used as a separator, and the alkaline electrolyte containing 30 weight% of KOH, NaOH, and LiOH in total was used as alkaline electrolyte.

そして、これらを使用して、理論容量が１５００ｍＡｈになった、図１に示すような円筒型になった実施例１のアルカリ蓄電池を作製した。   Then, using these, an alkaline storage battery of Example 1 having a theoretical capacity of 1500 mAh and having a cylindrical shape as shown in FIG. 1 was produced.

ここで、実施例１のアルカリ蓄電池を作製するにあたっては、図１に示すように、正極１と負極２との間にセパレータ３を介在させ、これらをスパイラル状に巻いて電池缶４内に収容させると共に、この電池缶４内に上記のアルカリ電解液を２．０ｇ注液させた。なお、このアルカリ蓄電池の理論容量に対するアルカリ電解液の量は１．３３ｇ／Ａｈである。そして、上記の正極１を正極リード５を介して正極蓋６に接続させると共に、負極２を負極リード７を介して電池缶４に接続させ、電池缶４の周囲に絶縁パッキン８を介して正極蓋６を取り付け、電池缶４の開口部を封口すると共に、上記の絶縁パッキン８により電池缶４と正極蓋６とを電気的に分離させた。また、上記の正極蓋６に正極外部端子９を設け、この正極蓋６に正極外部端子９との間にコイルスプリング１０を配し、電池の内圧が異常に上昇した場合には、このコイルスプリング１０が圧縮されて電池内部のガスが大気中に放出されるようにした。   Here, in producing the alkaline storage battery of Example 1, as shown in FIG. 1, the separator 3 is interposed between the positive electrode 1 and the negative electrode 2, and these are spirally wound and accommodated in the battery can 4. In addition, 2.0 g of the alkaline electrolyte was poured into the battery can 4. In addition, the quantity of the alkaline electrolyte with respect to the theoretical capacity of this alkaline storage battery is 1.33 g / Ah. The positive electrode 1 is connected to the positive electrode lid 6 via the positive electrode lead 5, and the negative electrode 2 is connected to the battery can 4 via the negative electrode lead 7, and the positive electrode via the insulating packing 8 around the battery can 4. The lid 6 was attached to seal the opening of the battery can 4, and the battery can 4 and the positive electrode lid 6 were electrically separated by the insulating packing 8. Further, the positive electrode external terminal 9 is provided on the positive electrode lid 6, and the coil spring 10 is disposed between the positive electrode cover 6 and the positive electrode external terminal 9. When the internal pressure of the battery rises abnormally, the coil spring 10 is provided. 10 was compressed so that the gas inside the battery was released into the atmosphere.

（実施例２及び比較例１，２）
実施例２及び比較例１，２においては、上記の実施例１における負極の作製において、負極に用いる水素吸蔵合金の組成だけを変更し、それ以外は、上記の実施例１の場合と同様にして、実施例２及び比較例１，２の各アルカリ蓄電池を作製した。 (Example 2 and Comparative Examples 1 and 2)
In Example 2 and Comparative Examples 1 and 2, only the composition of the hydrogen storage alloy used for the negative electrode was changed in the production of the negative electrode in Example 1 above, and the rest was the same as in Example 1 above. The alkaline storage batteries of Example 2 and Comparative Examples 1 and 2 were produced.

ここで、負極に用いる水素吸蔵合金として、実施例２においては、組成が（Ｌａ0.501Ｐｒ0.233Ｎｄ0.249Ｚｒ0.004Ｙ0.013）0.83Ｍｇ0.17Ｎｉ3.15Ａｌ0.15Ｃｏ0.1になった水素吸蔵合金を、比較例１においては、組成が（Ｌａ0.288Ｐｒ0.347Ｎｄ0.361Ｚｒ0.004）0.83Ｍｇ0.17Ｎｉ3.13Ａｌ0.17Ｃｏ0.1になった水素吸蔵合金を、比較例２においては、組成が（Ｌａ0.188Ｐｒ0.397Ｎｄ0.411Ｚｒ0.004）0.83Ｍｇ0.17Ｎｉ3.03Ａｌ0.17Ｃｏ0.1になった水素吸蔵合金を用いた。 Here, as the hydrogen storage alloy used for the negative electrode, in Example 2, a hydrogen storage alloy having a composition of (La 0.501 Pr 0.233 Nd 0.249 Zr 0.004 Y 0.013 ) 0.83 Mg 0.17 Ni 3.15 Al 0.15 Co 0.1 was used as a comparative example. 1, the composition of (La 0.288 Pr 0.347 Nd 0.361 Zr 0.004 ) 0.83 Mg 0.17 Ni 3.13 Al 0.17 Co 0.1 was used for the hydrogen storage alloy, and in Comparative Example 2, the composition was (La 0.188 Pr 0.397 Nd 0.411 Zr 0.004 ) 0.83 Mg 0.17 Ni 3.03 Al 0.17 Co 0.1 A hydrogen storage alloy was used.

そして、上記の実施例１，２及び比較例１，２の各アルカリ蓄電池を、それぞれ１５０ｍＡの電流で１６時間充電させた後、３００ｍＡの電流で電池電圧が１．０Ｖになるまで放電させて、各アルカリ蓄電池を活性化させた。   And after charging each alkaline storage battery of Examples 1 and 2 and Comparative Examples 1 and 2 with a current of 150 mA for 16 hours, respectively, it was discharged until the battery voltage became 1.0 V with a current of 300 mA, Each alkaline storage battery was activated.

次いで、このように活性化させた実施例１，２及び比較例１，２の各アルカリ蓄電池を、それぞれ１５００ｍＡの電流で電池電圧が最大値に達した後、１０ｍＶ低下するまで充電させて１時間放置した後、１５００ｍＡの電流で電池電圧が１．０Ｖになるまで放電させて１時間放置し、これを１サイクルとして、１５０サイクルの充放電を繰り返して行った。   Next, each of the alkaline storage batteries of Examples 1 and 2 and Comparative Examples 1 and 2 activated in this way was charged until the battery voltage reached the maximum value at a current of 1500 mA until the battery voltage decreased by 10 mV, and then 1 hour. After being allowed to stand, the battery was discharged at a current of 1500 mA until the battery voltage reached 1.0 V and left for 1 hour. This was defined as one cycle, and 150 cycles of charge / discharge were repeated.

そして、上記のように１５０サイクルの充放電を行った後、実施例１，２及び比較例１，２の各アルカリ蓄電池を分解して、各負極における水素吸蔵合金粉末を取り出して、その体積平均粒径を、レーザー回折式粒度分布測定装置（島津製作所社製：ＳＡＬＤ−２０００）を用いて測定し、比較例２のアルカリ蓄電池における水素吸蔵合金粉末の体積平均粒径を１００とした指数で、各アルカリ蓄電池における水素吸蔵合金粉末の体積平均粒径を求め、その結果を下記の表１に示した。   And after performing 150 cycles of charge and discharge as described above, the alkaline storage batteries of Examples 1 and 2 and Comparative Examples 1 and 2 were disassembled, the hydrogen storage alloy powder in each negative electrode was taken out, and its volume average The particle diameter was measured using a laser diffraction particle size distribution measuring apparatus (Salazu 2000 manufactured by Shimadzu Corporation), and an index with the volume average particle diameter of the hydrogen storage alloy powder in the alkaline storage battery of Comparative Example 2 as 100, The volume average particle diameter of the hydrogen storage alloy powder in each alkaline storage battery was determined, and the results are shown in Table 1 below.

また、上記のようにして実施例１，２及び比較例１，２の各アルカリ蓄電池に対して１５０サイクルの充放電を行った後、各アルカリ蓄電池を完全に放電させ、その後、各アルカリ蓄電池を分解して、各負極における水素吸蔵合金粉末を取り出し、これを水洗して結着剤を取り除き、乾燥させた後、各水素吸蔵合金粉末中における酸素濃度（重量％）を、酸素分析装置（ＬＥＣＯ社製）を用い、不活性ガス中において融解抽出法により測定し、比較例２のアルカリ蓄電池における水素吸蔵合金粉末の酸素濃度を１００とした指数で、各アルカリ蓄電池における水素吸蔵合金粉末の酸素濃度を求め、その結果を下記の表１に示した。   Moreover, after performing 150 cycles of charging / discharging each alkaline storage battery of Examples 1 and 2 and Comparative Examples 1 and 2 as described above, each alkaline storage battery was completely discharged, and then each alkaline storage battery was After decomposition, the hydrogen storage alloy powder in each negative electrode is taken out, washed with water to remove the binder, and dried, and then the oxygen concentration (wt%) in each hydrogen storage alloy powder is measured with an oxygen analyzer (LECO). The oxygen concentration of the hydrogen storage alloy powder in each alkaline storage battery is an index measured by the melt extraction method in an inert gas and the oxygen concentration of the hydrogen storage alloy powder in the alkaline storage battery of Comparative Example 2 is taken as 100. The results are shown in Table 1 below.

また、上記のように活性化させた実施例１，２及び比較例１，２の各アルカリ蓄電池を、上記のように１５００ｍＡの電流で電池電圧が最大値に達した後、１０ｍＶ低下するまで充電させて１時間放置した後、１５００ｍＡの電流で電池電圧が１．０Ｖになるまで放電させて１時間放置し、これを１サイクルとして充放電を繰り返して行い、サイクル寿命として、それぞれ放電容量が１サイクル目の放電容量の６０％になるまでのサイクル回数を求め、比較例２のアルカリ蓄電池におけるサイクル寿命を１００とした指数で、各アルカリ蓄電池におけるサイクル寿命を求め、その結果を下記の表１に示した。   In addition, the alkaline storage batteries of Examples 1 and 2 and Comparative Examples 1 and 2 activated as described above were charged until the battery voltage reached the maximum value at a current of 1500 mA as described above and decreased to 10 mV. Then, the battery is discharged at a current of 1500 mA until the battery voltage reaches 1.0 V, and left for 1 hour. This is repeated as charge and discharge as one cycle. The number of cycles until 60% of the discharge capacity at the cycle was obtained, and the cycle life in each alkaline storage battery was determined by an index with the cycle life in the alkaline storage battery of Comparative Example 2 as 100. The results are shown in Table 1 below. Indicated.

Figure 2005248252
Figure 2005248252

この結果、ランタンを含む希土類元素と、マグネシウムと、ニッケルと、アルミニウムとを含み、希土類元素全体中におけるランタンの量が５０原子％を超える水素吸蔵合金を用いた実施例１，２のアルカリ蓄電池においては、希土類元素全体中におけるランタンの量が５０原子％以下になった水素吸蔵合金を用いた比較例１，２のアルカリ蓄電池に比べて、充放電による水素吸蔵合金粉末の粒径の低下が少なく、充放電によって水素吸蔵合金粉末が微粉化するのが抑制されると共に、水素吸蔵合金粉末中における酸素濃度の増加も少なく、充放電による水素吸蔵合金の酸化も抑制され、結果としてサイクル寿命が向上していた。   As a result, in the alkaline storage batteries of Examples 1 and 2 using the hydrogen storage alloy containing the rare earth element containing lanthanum, magnesium, nickel, and aluminum, and the amount of lanthanum in the whole rare earth element exceeds 50 atomic%. Compared to the alkaline storage batteries of Comparative Examples 1 and 2 using a hydrogen storage alloy in which the amount of lanthanum in the entire rare earth element is 50 atomic% or less, the decrease in the particle size of the hydrogen storage alloy powder due to charge and discharge is small. In addition, the hydrogen storage alloy powder is prevented from being pulverized by charging and discharging, and the increase in oxygen concentration in the hydrogen storage alloy powder is suppressed, and the oxidation of the hydrogen storage alloy due to charging and discharging is suppressed, resulting in improved cycle life. Was.

この発明の実施例１，２及び比較例１，２において作製したアルカリ蓄電池の概略断面図である。It is a schematic sectional drawing of the alkaline storage battery produced in Examples 1, 2 and Comparative Examples 1, 2 of this invention.

符号の説明Explanation of symbols

１ 正極
２ 負極
３ セパレータ
４ 電池缶
５ 正極リード
６ 正極蓋
７ 負極リード
８ 絶縁パッキン
９ 正極外部端子
１０ コイルスプリング DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Battery can 5 Positive electrode lead 6 Positive electrode lid 7 Negative electrode lead 8 Insulation packing 9 Positive electrode external terminal 10 Coil spring

Claims (4)

少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金において、希土類元素として少なくともランタンを含み、希土類元素全体中におけるランタンの量が５０原子％を超えていることを特徴とするアルカリ蓄電池用水素吸蔵合金。   A hydrogen storage alloy containing at least a rare earth element, magnesium, nickel, and aluminum, wherein the rare earth element contains at least lanthanum, and the amount of lanthanum in the entire rare earth element exceeds 50 atomic%. Occlusion alloy. 請求項１に記載したアルカリ蓄電池用水素吸蔵合金において、上記の少なくとも希土類元素とマグネシウムとニッケルとアルミニウムとを含む水素吸蔵合金として、一般式Ｌｎ1-xＭｇxＮｉy-aＡｌa（式中、Ｌｎは希土類元素から選択される少なくとも１種の元素であり、０．０５≦ｘ＜０．２０、２．８≦ｙ≦３．９、０．１０≦ａ≦０．２５の条件を満たす。）で表わされるものを用いたことを特徴とするアルカリ蓄電池用水素吸蔵合金。 The hydrogen storage alloy for an alkaline storage battery according to claim 1, wherein the hydrogen storage alloy containing at least the rare earth element, magnesium, nickel and aluminum is represented by the general formula Ln 1-x Mg x Ni ya Al a (where Ln Is at least one element selected from rare earth elements and satisfies the conditions of 0.05 ≦ x <0.20, 2.8 ≦ y ≦ 3.9, and 0.10 ≦ a ≦ 0.25.) The hydrogen storage alloy for alkaline storage batteries characterized by using what is represented by these. 請求項１又は請求項２に記載したアルカリ蓄電池用水素吸蔵合金において、上記の希土類元素としてジルコニウムを含むと共に、上記のマグネシウムとニッケルとアルミニウムとの他にコバルトを含有していることを特徴とするアルカリ蓄電池用水素吸蔵合金。   The hydrogen storage alloy for an alkaline storage battery according to claim 1 or 2, characterized in that it contains zirconium as the rare earth element and contains cobalt in addition to the magnesium, nickel and aluminum. Hydrogen storage alloy for alkaline storage batteries. 正極と、水素吸蔵合金を用いた負極と、アルカリ電解液とを備えたアルカリ蓄電池において、上記の負極における水素吸蔵合金に、請求項１〜請求項３の何れか１項に記載したアルカリ蓄電池用水素吸蔵合金を用いたことを特徴とするアルカリ蓄電池。   An alkaline storage battery comprising a positive electrode, a negative electrode using a hydrogen storage alloy, and an alkaline electrolyte, wherein the hydrogen storage alloy in the negative electrode is an alkaline storage battery according to any one of claims 1 to 3. An alkaline storage battery using a hydrogen storage alloy.
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JP2003017115A (en) * 2001-07-04 2003-01-17 Matsushita Electric Ind Co Ltd Sealed secondary cell

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JP2003017115A (en) * 2001-07-04 2003-01-17 Matsushita Electric Ind Co Ltd Sealed secondary cell

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WO2007034760A1 (en) * 2005-09-21 2007-03-29 Sanyo Electric Co., Ltd. Alkaline storage battery
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