JP2001316744A - Hydrogen storage alloy and alkali secondary battery - Google Patents
Hydrogen storage alloy and alkali secondary batteryInfo
- Publication number
- JP2001316744A JP2001316744A JP2000137202A JP2000137202A JP2001316744A JP 2001316744 A JP2001316744 A JP 2001316744A JP 2000137202 A JP2000137202 A JP 2000137202A JP 2000137202 A JP2000137202 A JP 2000137202A JP 2001316744 A JP2001316744 A JP 2001316744A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- secondary battery
- negative electrode
- capacity
- 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.)
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Classifications
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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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素を電気化学的
に吸蔵・放出する水素吸蔵合金およびこの水素吸蔵合金
を含む負極を改良したアルカリ二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy for electrochemically storing and releasing hydrogen and an alkaline secondary battery having an improved negative electrode containing the hydrogen storage alloy.
【０００２】[0002]
【従来の技術】高容量二次電池としては、ニッケル・カ
ドミウム二次電池やニッケル水素二次電池が知られてい
る。このうち、水素を吸蔵・放出する水素吸蔵合金を含
む負極を備えたニッケル水素二次電池は環境適合性に優
れた小型密閉二次電池としてポータブル電子機器等に広
く用いられている。2. Description of the Related Art Nickel-cadmium secondary batteries and nickel-metal hydride secondary batteries are known as high-capacity secondary batteries. Among them, nickel-metal hydride secondary batteries provided with a negative electrode containing a hydrogen storage alloy that stores and releases hydrogen are widely used in portable electronic devices and the like as small sealed secondary batteries having excellent environmental compatibility.
【０００３】前記ニッケル水素二次電池において、正極
活物質として水酸化ニッケルに少量の水酸化コバルト又
は酸化コバルトを混合したものが用いられている。ま
た、負極活物質として重要な役割を果たす水素吸蔵合金
としては主にＭｍＮｉ5 系（Ｍｍ；ミッシュメタル）や
ＴｉＭｎ2系の合金が用いられている。In the nickel-metal hydride secondary battery, a mixture of nickel hydroxide and a small amount of cobalt hydroxide or cobalt oxide is used as a positive electrode active material. Further, as a hydrogen storage alloy that plays an important role as a negative electrode active material, an MmNi 5 -based (Mm: misch metal) or TiMn 2 -based alloy is mainly used.
【０００４】ところで、ニッケル・水素二次電池におい
ては、この二次電池を組み込むポータブル機器の性能向
上の点からより一層の高容量化、長寿命化が求められて
いる。このような高容量化の要求に対して、正極の理論
容量に対する実際の放電容量（利用率）を向上させるこ
とや、正極活物質量を多くするなどの方法が従来より採
用されてきた。しかしながら、利用率を向上させる方法
において現状、ほぼ理論容量に達しているため、更なる
高容量化は困難である。また、正極活物質量を多くする
場合、正極および負極間にセパレータを介在して例えば
渦巻き状に捲回下電極群を一定の体積の電池容器内に収
めるためには、相対的に負極活物質の占める体積を小さ
くする必要があり、より大きな放電容量を持つ水素吸蔵
合金が望まれている。[0004] In the nickel-hydrogen secondary battery, further higher capacity and longer life are required from the viewpoint of improving the performance of portable equipment incorporating the secondary battery. In response to such a demand for higher capacity, methods such as improving the actual discharge capacity (utilization rate) with respect to the theoretical capacity of the positive electrode and increasing the amount of the positive electrode active material have conventionally been adopted. However, the method of improving the utilization rate has almost reached the theoretical capacity at present, and it is difficult to further increase the capacity. In addition, when the amount of the positive electrode active material is increased, in order to place the lower electrode group in a fixed volume in a battery container with a separator interposed between the positive electrode and the negative electrode, for example, the negative electrode active material is relatively increased. It is necessary to reduce the volume occupied by the alloy, and a hydrogen storage alloy having a larger discharge capacity is desired.
【０００５】しかしながら、前述したＭｍＮｉ5 系（Ｍ
ｍ；ミッシュメタル）やＴｉＭｎ2系の水素吸蔵合金を
含む負極を備えたニッケル水素二次電池では前記水素吸
蔵合金の持つ水素吸蔵能力に限界があり、より一層の高
容量化が困難であった。However, the aforementioned MmNi 5 series (M
m; misch metal) or a nickel hydride secondary battery provided with a negative electrode containing a TiMn 2 -based hydrogen storage alloy, the hydrogen storage alloy has a limited hydrogen storage capacity, and it is difficult to further increase the capacity. .
【０００６】このようなことから、Ｖ−Ｔｉ系、ＴｉＦ
ｅ系、Ｔｉ2Ｎｉ系の水素吸蔵合金が開発されている。
しかしながら、これらの水素吸蔵合金は高温下での水素
ガスとの直接反応性が優れているものの、常温常圧下で
の水素との反応性が乏しく、初期活性化が困難であると
いう問題があった。For these reasons, V-Ti, TiF
e-based and Ti 2 Ni-based hydrogen storage alloys have been developed.
However, although these hydrogen storage alloys have excellent direct reactivity with hydrogen gas at high temperatures, they have poor reactivity with hydrogen at normal temperature and normal pressure, and have a problem that initial activation is difficult. .
【０００７】これに対し、マグネシウム、ニッケルおよ
び希土類元素を主構成元素として含む水素吸蔵合金は、
広く実用化されているＭｍＮｉ5 系合金に比べて体積当
たりの容量密度および質量当たりの容量密度の両方が高
く、ＴｉＭｎ2系合金よりも活性化が速く、かつ高率充
放電特性に優れているという特徴を有する。このため、
前記水素吸蔵合金を含む負極を用いることによって、Ｍ
ｍＮｉ5 系合金を含む負極を用いた場合に比べて高容量
でＴｉＭｎ2系合金を含む負極を用いた場合に比べて高
率充放電特性に優れた二次電池を実現することが可能に
なる。On the other hand, hydrogen storage alloys containing magnesium, nickel and rare earth elements as main constituent elements are:
Both the capacity density per volume and the capacity density per mass are higher than those of widely used MmNi 5 -based alloys, activation is faster than TiMn 2 -based alloys, and excellent in high-rate charge / discharge characteristics. It has the feature of. For this reason,
By using the negative electrode containing the hydrogen storage alloy, M
It is possible to realize a secondary battery having a higher capacity and a higher rate of charge / discharge characteristics than using a negative electrode containing a TiMn 2 -based alloy as compared with a case using a negative electrode containing an mNi 5 -based alloy. .
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、マグネ
シウム、ニッケルおよび希土類元素を主構成元素として
含む水素吸蔵合金を含有する負極を備えたアルカリ二次
電池は、前記水素吸蔵合金が酸化してサイクル寿命が低
下するという問題があった。However, in an alkaline secondary battery provided with a negative electrode containing a hydrogen storage alloy containing magnesium, nickel and a rare earth element as main constituent elements, the hydrogen storage alloy is oxidized and the cycle life is increased. There was a problem of lowering.
【０００９】本発明は、優れた耐酸化性を有し、低温お
よび高温で高い水素吸蔵性を有し、かつ吸蔵・放出の繰
り返しにおいて十分な水素吸蔵量を維持し、さらに高い
水素吸蔵速度を有する水素吸蔵合金を提供しようとする
ものである。The present invention has excellent oxidation resistance, has high hydrogen storage properties at low and high temperatures, maintains a sufficient amount of hydrogen storage during repeated storage and release, and has a higher hydrogen storage rate. It is intended to provide a hydrogen storage alloy having the same.
【００１０】本発明は、前記優れた特性を有する水素吸
蔵合金を含む負極を備え、高容量化を実現しつつ、充放
電サイクル寿命の長いアルカリ二次電池を提供しようと
するものである。An object of the present invention is to provide an alkaline secondary battery having a negative electrode containing a hydrogen storage alloy having the above-mentioned excellent characteristics, realizing a high capacity, and having a long charge-discharge cycle life.
【００１１】[0011]
【課題を解決するための手段】本発明に係る水素吸蔵合
金は、一般式 Ｌｎ1-xＭｇx（Ｎｉ1-yＴy）z（ただ
し、式中のＬｎはランタノイド元素，Ｃａ，Ｓｒ，Ｓ
ｃ，Ｙ，Ｔｉ，ＺｒおよびＨｆから選ばれる少なくとも
１つの元素で、かつＬｎに占めるＬａ量が１０〜５０原
子％であり、ＴはＬｉ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，Ｍｏ，
Ｍｎ，Ｆｅ，Ｃｏ，Ａｌ，Ｇａ，Ｚｎ，Ｓｎ，Ｉｎ，Ｃ
ｕ，Ｓｉ，ＰおよびＢから選ばれる少なくとも１つの元
素、ｘ，ｙ，ｚはそれぞれ０．０５≦ｘ＜０．２０，０
≦ｙ≦０．５，２．８≦ｚ≦３．９を示す）にて表わさ
れる。The hydrogen storage alloy according to the present invention has a general formula Ln 1-x Mg x (Ni 1-y T y ) z (where Ln is a lanthanoid element, Ca, Sr, S
at least one element selected from c, Y, Ti, Zr and Hf, wherein the La content in Ln is 10 to 50 atomic%, and T is Li, V, Nb, Ta, Cr, Mo,
Mn, Fe, Co, Al, Ga, Zn, Sn, In, C
at least one element selected from u, Si, P, and B, x, y, and z are respectively 0.05 ≦ x <0.20, 0
≤ y ≤ 0.5, 2.8 ≤ z ≤ 3.9).
【００１２】本発明に係るアルカリ二次電池は、前述し
た水素吸蔵合金を含む負極を備えたことを特徴とするも
のである。An alkaline secondary battery according to the present invention includes a negative electrode containing the above-mentioned hydrogen storage alloy.
【００１３】[0013]
【発明の実施の形態】以下、本発明に係る水素吸蔵合金
を説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a hydrogen storage alloy according to the present invention will be described.
【００１４】この水素吸蔵合金は、一般式 Ｌｎ1-xＭ
ｇx（Ｎｉ1-yＴy）z（ただし、式中のＬｎはランタノイ
ド元素，Ｃａ，Ｓｒ，Ｓｃ，Ｙ，Ｔｉ，ＺｒおよびＨｆ
から選ばれる少なくとも１つの元素で、かつＬｎに占め
るＬａ量が１０〜５０原子％であり、ＴはＬｉ，Ｖ，Ｎ
ｂ，Ｔａ，Ｃｒ，Ｍｏ，Ｍｎ，Ｆｅ，Ｃｏ，Ａｌ，Ｇ
ａ，Ｚｎ，Ｓｎ，Ｉｎ，Ｃｕ，Ｓｉ，ＰおよびＢから選
ばれる少なくとも１つの元素、ｘ，ｙ，ｚはそれぞれ
０．０５≦ｘ＜０．２０，０≦ｙ≦０．５，２．８≦ｚ
≦３．９を示す）にて表わされる。This hydrogen storage alloy has the general formula Ln 1-x M
g x (Ni 1 -y T y ) z (where Ln is a lanthanoid element, Ca, Sr, Sc, Y, Ti, Zr and Hf
And the amount of La in Ln is 10 to 50 atomic%, and T is Li, V, N
b, Ta, Cr, Mo, Mn, Fe, Co, Al, G
At least one element selected from a, Zn, Sn, In, Cu, Si, P and B, x, y, and z are respectively 0.05 ≦ x <0.20, 0 ≦ y ≦ 0.5, and 2. 8 ≦ z
≤ 3.9).
【００１５】前記一般式のＬｎの中では、特にランタノ
イド元素が好ましい。Among Ln in the above general formula, a lanthanoid element is particularly preferred.
【００１６】前記Ｌｎ中に占めるＬａ量を規定したの
は、Ｌａ量を１０原子％未満にすると高温での水素吸蔵
量が著しく低下する虞がある。一方、Ｌａ量が５０原子
％を超えると均質な組織が得られ難くなり、水素吸蔵合
金の水素吸蔵速度が著しく低下する虞がある。より好ま
しいＬｎ中のＬａ量は２０〜４０原子％である。The reason why the La content in Ln is specified is that if the La content is less than 10 atomic%, the hydrogen storage capacity at high temperatures may be significantly reduced. On the other hand, if the La content exceeds 50 atomic%, it is difficult to obtain a homogeneous structure, and the hydrogen storage rate of the hydrogen storage alloy may be significantly reduced. More preferably, the La content in Ln is 20 to 40 atomic%.
【００１７】前記一般式のｘを規定したのは、ｘを０．
０５未満にすると目的とする合金相と異なる合金相が析
出し易くなって水素吸蔵量が著しく低下する虞がある。
一方、ｘが０．２以上になると，酸化され易い元素であ
るマグネシウムの含有量が増大して水素吸蔵合金の耐酸
化性が著しく低下する虞がある。より好ましいｘは０．
１０≦ｘ＜０．１５である。The reason for defining x in the above general formula is that x is set to 0.
If it is less than 05, an alloy phase different from the target alloy phase is likely to precipitate, and the hydrogen storage amount may be significantly reduced.
On the other hand, when x is 0.2 or more, the content of magnesium, which is an easily oxidizable element, increases, and the oxidation resistance of the hydrogen storage alloy may be significantly reduced. More preferably, x is 0.
10 ≦ x <0.15.
【００１８】前記一般式中のｙを規定したのは、ｙが
０．５を超えると高温での水素吸蔵量が著しく低下する
虞がある。より好ましいｙは、０≦ｙ≦０．２である。The reason for defining y in the above general formula is that if y exceeds 0.5, there is a possibility that the hydrogen storage amount at high temperatures may be significantly reduced. More preferable y is 0 ≦ y ≦ 0.2.
【００１９】前記一般式中のｚを規定したのは、ｚを
２．８未満にすると目的とする合金相と異なる合金相が
増大して水素吸蔵の繰り返しに伴なう残留水素が増加し
て水素吸蔵量が著しく低下する虞がある。一方、ｚが
３．９を超えると高温での水素吸蔵量が著しく低下する
虞がある。より好ましいｚは、３．０≦ｚ≦３．６であ
る。The reason for defining z in the above general formula is that, when z is less than 2.8, the alloy phase different from the target alloy phase increases, and the residual hydrogen accompanying the repetition of hydrogen storage increases. There is a possibility that the hydrogen storage amount may be significantly reduced. On the other hand, if z exceeds 3.9, the amount of hydrogen occlusion at high temperatures may be significantly reduced. More preferred z is 3.0 ≦ z ≦ 3.6.
【００２０】以上説明した本発明に係る水素吸蔵合金
は、一般式Ｌｎ1-xＭｇx（Ｎｉ1-yＴy）zで表わされ、
Ｌｎ中のＬａ量を１０〜５０原子％に規定することによ
り均質な合金組成が得られ、かつ高い水素吸蔵速度を発
揮できる。また、前記一般式のｘを、０．０５≦ｘ＜
０．２０に規定することにより耐酸化性の向上および水
素吸蔵速度の増大を図ることができる。前記一般式中の
ｙを０≦ｙ≦０．５に規定することによって、低温での
水素吸蔵性を高めることができる。さらに、前記一般式
中のｚを２．８≦ｚ≦３．９に規定することによって、
高温での水素吸蔵性を高めることができる共に、水素の
吸蔵・放出の繰り返しにおいて十分な水素吸蔵量を維持
できる。The hydrogen storage alloy according to the present invention described above is represented by the general formula Ln 1-x Mg x (Ni 1-y T y ) z ,
By regulating the La content in Ln to 10 to 50 atomic%, a homogeneous alloy composition can be obtained, and a high hydrogen storage rate can be exhibited. Further, x in the above general formula is expressed as 0.05 ≦ x <
By setting the ratio to 0.20, it is possible to improve the oxidation resistance and increase the hydrogen storage rate. By defining y in the general formula as 0 ≦ y ≦ 0.5, the hydrogen storage ability at low temperatures can be increased. Further, by defining z in the general formula as 2.8 ≦ z ≦ 3.9,
Hydrogen storage at high temperatures can be enhanced, and a sufficient amount of hydrogen storage can be maintained during repeated storage and release of hydrogen.
【００２１】したがって、優れた耐酸化性を有し、低温
および高温で高い水素吸蔵性を有し、かつ吸蔵・放出の
繰り返しにおいて十分な水素吸蔵量を維持し、さらに高
い水素吸蔵速度を有する水素吸蔵合金を得ることができ
る。Therefore, hydrogen which has excellent oxidation resistance, has high hydrogen storage properties at low and high temperatures, maintains a sufficient amount of hydrogen storage in repeated storage and release, and has a higher hydrogen storage rate An occlusion alloy can be obtained.
【００２２】次に、本発明に係わるアルカリ二次電池
（例えば円筒形アルカリ二次電池）を図１を参照して説
明する。Next, an alkaline secondary battery (for example, a cylindrical alkaline secondary battery) according to the present invention will be described with reference to FIG.
【００２３】有底円筒状の容器１内には、正極２とセパ
レータ３と負極４とを積層してスパイラル状に捲回する
ことにより作製された電極群５が収納されている。前記
負極４は、前記電極群５の最外周に配置されて前記容器
１と電気的に接触している。アルカリ電解液は、前記容
器１内に収容されている。An electrode group 5 formed by laminating the positive electrode 2, the separator 3, and the negative electrode 4 and winding them in a spiral shape is accommodated in the bottomed cylindrical container 1. The negative electrode 4 is arranged at the outermost periphery of the electrode group 5 and is in electrical contact with the container 1. The alkaline electrolyte is contained in the container 1.
【００２４】中央に孔６を有する円形の封口板７は、前
記容器１の上部開口部に配置されている。リング状の絶
縁性ガスケット８は、前記封口板７の周縁と前記容器１
の上部開口部内面の間に配置され、前記上部開口部を内
側に縮径するカシメ加工により前記容器１に前記封口板
７を前記ガスケット８を介して気密に固定している。正
極リード９は、一端が前記正極２に接続、他端が前記封
口板７の下面に接続されている。帽子形状をなす正極端
子１０は、前記封口板７上に前記孔６を覆うように取り
付けられている。A circular sealing plate 7 having a hole 6 in the center is arranged at the upper opening of the container 1. The ring-shaped insulating gasket 8 is provided between the periphery of the sealing plate 7 and the container 1.
The sealing plate 7 is air-tightly fixed to the container 1 via the gasket 8 by caulking to reduce the diameter of the upper opening inward. One end of the positive electrode lead 9 is connected to the positive electrode 2, and the other end is connected to the lower surface of the sealing plate 7. The positive electrode terminal 10 having a hat shape is attached on the sealing plate 7 so as to cover the hole 6.
【００２５】ゴム製の安全弁１１は、前記封口板７と前
記正極端子１０で囲まれた空間内に前記孔６を塞ぐよう
に配置されている。中央に穴を有する絶縁材料からなる
円形の押え板１２は、前記正極端子１０上に前記正極端
子１０の突起部がその押え板１２の前記穴から突出され
るように配置されている。外装チューブ１３は、前記押
え板１２の周縁、前記容器１の側面及び前記容器１の底
部周縁を被覆している。A rubber safety valve 11 is disposed in a space surrounded by the sealing plate 7 and the positive electrode terminal 10 so as to close the hole 6. A circular holding plate 12 made of an insulating material having a hole in the center is arranged on the positive electrode terminal 10 such that a protrusion of the positive electrode terminal 10 projects from the hole of the holding plate 12. The outer tube 13 covers the periphery of the holding plate 12, the side surface of the container 1, and the periphery of the bottom of the container 1.
【００２６】次に、前記正極２、負極４、セパレータ３
および電解液について説明する。Next, the positive electrode 2, the negative electrode 4, the separator 3
And the electrolyte will be described.
【００２７】１）正極２ この正極２は、活物質であるニッケル化合物を含有す
る。1) Cathode 2 This cathode 2 contains a nickel compound as an active material.
【００２８】前記ニッケル化合物としては、例えば水酸
化ニッケル、亜鉛およびコバルトが共沈された水酸化ニ
ッケルまたはニッケル酸化物等を挙げることができる。
特に、亜鉛およびコバルトが共沈された水酸化ニッケル
が好ましい。Examples of the nickel compound include nickel hydroxide and nickel oxide in which nickel hydroxide, zinc and cobalt are coprecipitated.
Particularly, nickel hydroxide in which zinc and cobalt are coprecipitated is preferable.
【００２９】前記正極（ペースト式正極）は、例えば活
物質であるニッケル化合物と導電材と結着剤を水と共に
混練してペーストを調製し、このペーストを導電性芯体
に充填し、乾燥し、必要に応じて加圧成形を施すことに
より作製される。For the positive electrode (paste type positive electrode), for example, a paste is prepared by kneading a nickel compound as an active material, a conductive material and a binder together with water, filling the paste into a conductive core, and drying the paste. It is produced by performing pressure molding as required.
【００３０】前記導電材料としては、例えばコバルト化
合物および金属コバルトから選ばれる少なくとも１種以
上のものが用いられる。前記コバルト化合物としては、
例えば水酸化コバルト［Ｃｏ（ＯＨ）2 ］、一酸化コバ
ルト（ＣｏＯ）等を挙げることができる。特に、水酸化
コバルト、一酸化コバルトもしくはこれらの混合物を導
電材料として用いることが好ましい。As the conductive material, for example, at least one selected from a cobalt compound and metallic cobalt is used. As the cobalt compound,
For example, cobalt hydroxide [Co (OH) 2 ], cobalt monoxide (CoO), and the like can be given. In particular, it is preferable to use cobalt hydroxide, cobalt monoxide, or a mixture thereof as the conductive material.
【００３１】前記結着剤としては、例えばポリテトラフ
ルオロエチレン、ポリエチレン、ポリプロピレン等の疎
水性ポリマ；カルボキシメチルセルロース、メチルセル
ロース、ヒドロキシプロピルメチルセルロース等のセル
ロース系材料；ポリアクリル酸ナトリウム等のアクリル
酸エステル；ポリビニルアルコール、ポリエチレンオキ
シド等の親水性ポリマ；ラテックス等のゴム系ポリマを
を挙げることができる。Examples of the binder include hydrophobic polymers such as polytetrafluoroethylene, polyethylene and polypropylene; cellulosic materials such as carboxymethylcellulose, methylcellulose and hydroxypropylmethylcellulose; acrylates such as sodium polyacrylate; Examples include hydrophilic polymers such as alcohol and polyethylene oxide; and rubber-based polymers such as latex.
【００３２】前記導電性芯体としては、例えばニッケ
ル、ステンレスまたはニッケルメッキが施された金属か
ら形成された網状、スポンジ状、繊維状、もしくはフェ
ルト状の金属多孔体等を挙げることができる。Examples of the conductive core include a mesh-like, sponge-like, fibrous, or felt-like porous metal body made of nickel, stainless steel, or nickel-plated metal.
【００３３】２）負極４ この負極４は、前述した一般式 Ｌｎ1-xＭｇx（Ｎｉ
1-yＴy）z（ただし、式中のＬｎはランタノイド元素，
Ｃａ，Ｓｒ，Ｓｃ，Ｙ，Ｔｉ，ＺｒおよびＨｆから選ば
れる少なくとも１つの元素で、かつＬｎに占めるＬａ量
が１０〜５０原子％であり、ＴはＬｉ，Ｖ，Ｎｂ，Ｔ
ａ，Ｃｒ，Ｍｏ，Ｍｎ，Ｆｅ，Ａｌ，Ｃｏ，Ｇａ，Ｚ
ｎ，Ｓｎ，Ｉｎ，Ｃｕ，Ｓｉ，ＰおよびＢから選ばれる
少なくとも１つの元素、ｘ，ｙ，ｚはそれぞれ０．０５
≦ｘ＜０．２０，０≦ｙ≦０．５，２．８≦ｚ≦３．９
を示す）にて表わされる水素吸蔵合金を含有する。2) Negative electrode 4 This negative electrode 4 is made of the above-mentioned general formula Ln 1-x Mg x (Ni
1-y T y ) z (where Ln is a lanthanoid element,
At least one element selected from Ca, Sr, Sc, Y, Ti, Zr and Hf, and the La content in Ln is 10 to 50 atomic%, and T is Li, V, Nb, T
a, Cr, Mo, Mn, Fe, Al, Co, Ga, Z
at least one element selected from n, Sn, In, Cu, Si, P and B, x, y and z are each 0.05
≦ x <0.20, 0 ≦ y ≦ 0.5, 2.8 ≦ z ≦ 3.9
Is shown)).
【００３４】前記負極（ペースト式負極）は、例えば前
記水素吸蔵合金粉末と導電材料と結着剤を水と共に混練
してペーストを調製し、このペーストを導電性芯体に充
填し、乾燥し、必要に応じて加圧成形を施すことにより
作製される。The negative electrode (paste type negative electrode) is prepared, for example, by kneading the hydrogen storage alloy powder, a conductive material and a binder together with water to prepare a paste, filling the paste into a conductive core, and drying the paste. It is produced by performing pressure molding as necessary.
【００３５】前記結着剤としては、前記正極２で用いた
のと同様なものを挙げることができる。この結着剤は、
前記水素吸蔵合金粉末１００質量部に対して０．５〜６
質量部配合することが好ましい。Examples of the binder include those similar to those used for the positive electrode 2. This binder is
0.5 to 6 with respect to 100 parts by mass of the hydrogen storage alloy powder
It is preferable to mix parts by mass.
【００３６】前記導電性材料としては、例えばアセチレ
ンブラック、ケッチェンブラック（ライオンアグゾ社製
商品名）、ファーネスブラックのようなカーボンブラッ
ク、または黒鉛等を用いることができる。この導電材
料は、前記水素吸蔵合金粉末１００質量部に対して５質
量部以下配合することが好ましい。As the conductive material, for example, carbon black such as acetylene black, Ketjen black (trade name, manufactured by Lion Aguso), furnace black, or graphite can be used. This conductive material is preferably blended in an amount of 5 parts by mass or less with respect to 100 parts by mass of the hydrogen storage alloy powder.
【００３７】前記導電性芯体としては、パンチドメタ
ル、エキスパンデッドメタル、穿孔鋼板、金網などの二
次元構造や、発泡メタル、網状焼結金属繊維などの三次
元構造のものを挙げることができる。Examples of the conductive core include those having a two-dimensional structure such as punched metal, expanded metal, perforated steel sheet, and wire mesh, and a three-dimensional structure such as foamed metal and reticulated sintered metal fiber. it can.
【００３８】３）セパレータ３ このセパレータ３は、例えばポリエチレン繊維製不織
布、エチレン−ビニルアルコール共重合体繊維製不織
布、ポリプロピレン繊維製不織布などのオレフィン系繊
維製不織布、またはポリプロピレン繊維製不織布のよう
なオレフィン系繊維製不織布に親水性官能基を付与した
もの、ナイロン６，６のようなポリアミド繊維製不織布
を挙げることができる。前記オレフィン系繊維製不織布
に親水性官能基を付与するには、例えばコロナ放電処
理、スルホン化処理、グラフト共重合、または界面活性
剤や親水性樹脂の塗布等を採用することができる。3) Separator 3 The separator 3 is made of, for example, an olefin-based nonwoven fabric such as a nonwoven fabric made of polyethylene fiber, a nonwoven fabric made of ethylene-vinyl alcohol copolymer fiber, or a nonwoven fabric made of polypropylene fiber, or an olefin such as a nonwoven fabric made of polypropylene fiber. Examples thereof include nonwoven fabrics made of a nonwoven fabric made of a base fiber and hydrophilic functional groups, and nonwoven fabrics made of polyamide fibers such as nylon 6,6. In order to impart a hydrophilic functional group to the olefin fiber nonwoven fabric, for example, corona discharge treatment, sulfonation treatment, graft copolymerization, or application of a surfactant or a hydrophilic resin can be employed.
【００３９】４）アルカリ電解液 このアルカリ電解液としては、例えば水酸化ナトリウム
（ＮａＯＨ）と水酸化リチウム（ＬｉＯＨ）の混合液、
水酸化カリウム（ＫＯＨ）とＬｉＯＨの混合液、ＫＯＨ
とＬｉＯＨとＮａＯＨの混合液等を用いることができ
る。4) Alkaline Electrolyte As the alkaline electrolyte, for example, a mixed solution of sodium hydroxide (NaOH) and lithium hydroxide (LiOH),
A mixture of potassium hydroxide (KOH) and LiOH, KOH
And a mixed solution of LiOH and NaOH.
【００４０】以上説明した本発明に係わるアルカリ二次
電池は、一般式 Ｌｎ1-xＭｇx（Ｎｉ1-yＴy）z（ただ
し、式中のＬｎはランタノイド元素，Ｃａ，Ｓｒ，Ｓ
ｃ，Ｙ，Ｔｉ，ＺｒおよびＨｆから選ばれる少なくとも
１つの元素で、かつＬｎに占めるＬａ量が１０〜５０原
子％であり、ＴはＬｉ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，Ｍｏ，
Ｍｎ，Ｆｅ，Ｃｏ，Ａｌ，Ｇａ，Ｚｎ，Ｓｎ，Ｉｎ，Ｃ
ｕ，Ｓｉ，ＰおよびＢから選ばれる少なくとも１つの元
素、ｘ，ｙ，ｚはそれぞれ０．０５≦ｘ＜０．２０，０
≦ｙ≦０．５，２．８≦ｚ≦３．９を示す）にて表わさ
れる水素吸蔵合金を含有する負極を備える。この負極
は、前記水素吸蔵合金により高容量化と高耐食性を有す
るため、高容量で、高率充放電性および長寿命を同時に
満たすアルカリ二次電池を得ることができる。The alkaline secondary battery according to the present invention described above has a general formula Ln 1-x Mg x (Ni 1-y T y ) z (where Ln is a lanthanoid element, Ca, Sr, S
at least one element selected from c, Y, Ti, Zr and Hf, wherein the La content in Ln is 10 to 50 atomic%, and T is Li, V, Nb, Ta, Cr, Mo,
Mn, Fe, Co, Al, Ga, Zn, Sn, In, C
at least one element selected from u, Si, P, and B, x, y, and z are respectively 0.05 ≦ x <0.20, 0
≤ y ≤ 0.5, 2.8 ≤ z ≤ 3.9). Since this negative electrode has a high capacity and a high corrosion resistance due to the hydrogen storage alloy, it is possible to obtain an alkaline secondary battery having a high capacity and simultaneously satisfying a high rate charge / discharge property and a long life.
【００４１】[0041]
【実施例】以下、本発明の好ましい実施例を図面を参照
して詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail with reference to the drawings.
【００４２】（実施例１〜８および比較例１〜７）Ｌ
ａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｍｇ，Ｎｉ，Ｃｏ，Ｃｒ，Ｍｎ
およびＡｌの各元素を混合し、高周波溶解炉を用いてア
ルゴン雰囲気中で溶解・冷却することにより下記表１に
示す組成を有する１５種の水素吸蔵合金を製造した。(Examples 1 to 8 and Comparative Examples 1 to 7) L
a, Ce, Pr, Nd, Mg, Ni, Co, Cr, Mn
And Al were mixed and melted and cooled in an argon atmosphere using a high-frequency melting furnace to produce 15 types of hydrogen storage alloys having the compositions shown in Table 1 below.
【００４３】[0043]
【表１】 [Table 1]
【００４４】得られた各水素吸蔵合金を所定の容器内に
それぞれ収納し、水素を８０℃の温度下で各容器内に１
時間供給した後の水素吸蔵速度（Ｈ／Ｍ・ｈ-1）を測定
した。その結果、実施例１〜８の水素吸蔵合金は０．９
Ｈ／Ｍ・ｈ-1以上であったのに対し、比較例１〜７の水
素吸蔵合金は０．６〜０．９Ｈ／Ｍ・ｈ-1以上であっ
た。Each of the obtained hydrogen storage alloys is stored in a predetermined container, and hydrogen is stored in each container at a temperature of 80 ° C.
The hydrogen storage rate (H / M · h −1 ) after supply for a time was measured. As a result, the hydrogen storage alloys of Examples 1 to 8
H / M · h −1 or more, whereas the hydrogen storage alloys of Comparative Examples 1 to 7 were 0.6 to 0.9 H / M · h −1 or more.
【００４５】次に、前記水素吸蔵合金を含む負極を備え
たニッケル水素二次電池について説明する。Next, a nickel hydride secondary battery provided with a negative electrode containing the above-mentioned hydrogen storage alloy will be described.
【００４６】＜ペースト式負極の作製＞前記表１に示す
組成の水素吸蔵合金（インゴット）を熱処理して均質化
を行ない、不活性雰囲気中で粉砕後、粒径が７５μｍ以
下になるように篩を通し水素吸蔵合金粉末を得た。つづ
いて、前記各水素吸蔵合金粉末１００質量部に結着剤と
してカルボキシメチルセルロース（ＣＭＣ）０．２質量
部および水５０質量部と共に添加した後、混練すること
により１５種のペーストを調製した。つづいて、前記各
ペーストを多孔度９５％の発泡ニッケルに充填した後、
１２５℃で乾燥し、厚さ０．３ｍｍにプレス成形し、さ
らに幅６０ｍｍ、長さ１６８ｍｍに裁断することにより
１５種のペースト式負極を作製した。<Preparation of Paste Negative Electrode> A hydrogen storage alloy (ingot) having the composition shown in Table 1 above was heat-treated to homogenize it, pulverized in an inert atmosphere, and then sieved to a particle size of 75 μm or less. To obtain a hydrogen storage alloy powder. Subsequently, after adding 0.2 parts by mass of carboxymethylcellulose (CMC) and 50 parts by mass of water as binders to 100 parts by mass of the respective hydrogen storage alloy powders, 15 kinds of pastes were prepared by kneading. Subsequently, after filling each paste into foamed nickel having a porosity of 95%,
The paste was dried at 125 ° C., press-molded to a thickness of 0.3 mm, and further cut to a width of 60 mm and a length of 168 mm to produce 15 types of paste-type negative electrodes.
【００４７】＜ペースト式正極の作製＞水酸化ニッケル
粉末９０質量部および一酸化コバルト粉末１０質量部か
らなる混合粉体に、ポリテトラフルオロエチレン１質量
部およびカルボキシメチルセルロース０．２質量部を添
加し、これらに純水を６０質量部添加して混練すること
によりペーストを調製した。つづいて、このペーストを
発泡ニッケルに充填し、乾燥した後、プレス成形するこ
とにより幅６０ｍｍ、長さ１３５ｍｍ、厚さ０．７５ｍ
ｍのペースト式正極を作製した。<Preparation of Paste-Type Positive Electrode> To a mixed powder consisting of 90 parts by mass of nickel hydroxide powder and 10 parts by mass of cobalt monoxide powder, 1 part by mass of polytetrafluoroethylene and 0.2 parts by mass of carboxymethyl cellulose were added. A paste was prepared by adding 60 parts by mass of pure water to these and kneading them. Subsequently, this paste was filled in foamed nickel, dried, and then press-molded to obtain a width of 60 mm, a length of 135 mm, and a thickness of 0.75 m.
m of paste-type positive electrodes were prepared.
【００４８】次いで、前記各負極と前記正極との間にポ
リプロピレン繊維製不織布を介装し、渦巻状に捲回して
電極群を作製した。このような各電極群を有底円筒状容
器に収納した後、比重１．３１の水酸化カリウム水溶液
からなる電解液を前記容器内に注入し、封口等を行うこ
とにより前述した図１に示す構造を有する１５種の４／
３Ａサイズの円筒形ニッケル水素二次電池（容量４２０
０ｍＡｈ）を組み立てた。Next, a nonwoven fabric made of polypropylene fiber was interposed between each of the negative electrode and the positive electrode, and spirally wound to form an electrode group. After each such electrode group is accommodated in a bottomed cylindrical container, an electrolytic solution comprising a potassium hydroxide aqueous solution having a specific gravity of 1.31 is injected into the container, and the container is sealed and the like, as shown in FIG. 1 described above. 15 types of 4 /
3A size cylindrical nickel-metal hydride secondary battery (capacity 420
0 mAh).
【００４９】得られた実施例１〜８および比較例１〜７
の二次電池について、２５℃、１０時間率で１３時間充
電し、２５℃、５時間率で終止電圧１．０Ｖまで放電す
る条件で３サイクル行い、その後２５℃、０．１時間率
で６分間充電し、２５℃、０．１時間率で終止電圧１．
０Ｖ間で放電する条件で１サイクル行い、さらに５サイ
クル目以降を２５℃、１０時間率で１０時間充電し、２
５℃、１０時間率で終止電圧１．０Ｖまで放電する条件
で充放電を繰り返し、初期容量、０．１時間率容量およ
びサイクル寿命を調べた。なお、初回の放電容量を初期
容量とし、初期容量に対して０．１時間率での放電容量
を０．１時間率容量とし、初期容量に対して８０％の容
量に達した時のサイクル数をサイクル寿命とした。The obtained Examples 1 to 8 and Comparative Examples 1 to 7
The battery was charged at 25 ° C. for 13 hours at a rate of 10 hours, discharged at 25 ° C. for 5 hours at a rate of 5 hours to a final voltage of 1.0 V, and then subjected to three cycles. Charge for 25 minutes at 25 ° C. and 0.1 hour rate.
One cycle is performed under the condition of discharging between 0 V, and the fifth and subsequent cycles are further charged at 25 ° C. for 10 hours at a rate of 10 hours.
The charge and discharge were repeated under the condition of discharging at 5 ° C. and a 10-hour rate to a final voltage of 1.0 V, and the initial capacity, 0.1-hour rate capacity and cycle life were examined. The initial discharge capacity is defined as the initial capacity, the discharge capacity at a 0.1 hour rate relative to the initial capacity is defined as the 0.1 hour rate capacity, and the number of cycles when the capacity reaches 80% of the initial capacity. Was defined as the cycle life.
【００５０】これらの結果を下記表２に示す。The results are shown in Table 2 below.
【００５１】[0051]
【表２】 [Table 2]
【００５２】前記表１および表２から明らかなように一
般式Ｌｎ1-xＭｇx（Ｎｉ1-yＴy）zで表わされ、Ｌｎに
占めるＬａ量が１０〜５０原子％、ｘ（Ｍｇ量）が０．
０５≦ｘ＜０．２０，ｙ（Ｎｉに対する置換量）が０≦
ｙ≦０．５，ｚが２．８≦ｚ≦３．９である水素吸蔵合
金を含む負極を備えた実施例１〜８の二次電池はＬｎ中
のＬａ量、ｘ，ｙ，ｚが前記範囲から外れる水素吸蔵合
金を含む負極を備えた比較例１〜７に比べて優れた初期
容量、０．１時間率容量およびサイクル寿命を有するこ
とがわかる。特に、Ｌｎ中のＬａ量は２０〜４０原子
％、ｘ（Ｍｇ量）が０．１０≦ｘ＜０．１５、ｙ（Ｎｉ
に対する置換量）が０≦ｙ≦０．２、ｚが３．０≦ｚ≦
３．６である水素吸蔵合金を含む負極を備えた実施例
２，４，５，７の二次電池は初期容量、０．１時間率容
量およびサイクル寿命がいずれも比較例１〜７に比べて
優れていることがわかる。As is clear from Tables 1 and 2, the formula is represented by the general formula Ln 1-x Mg x (Ni 1-y T y ) z , where the La content in Ln is 10 to 50 atomic%, x ( Mg content).
05 ≦ x <0.20, y (substitution amount for Ni) is 0 ≦
The secondary batteries of Examples 1 to 8 each including the negative electrode containing a hydrogen storage alloy in which y ≦ 0.5 and z satisfy 2.8 ≦ z ≦ 3.9 have the La content in Ln, x, y, and z. It can be seen that it has excellent initial capacity, 0.1 hour rate capacity and cycle life as compared with Comparative Examples 1 to 7 provided with the negative electrode containing the hydrogen storage alloy out of the above range. In particular, the La content in Ln is 20 to 40 atomic%, x (Mg content) is 0.10 ≦ x <0.15, and y (Ni
0 ≦ y ≦ 0.2, and z is 3.0 ≦ z ≦
The secondary batteries of Examples 2, 4, 5, and 7 including the negative electrode containing the hydrogen storage alloy of 3.6 had an initial capacity, a 0.1 hour rate capacity, and a cycle life which were all smaller than those of Comparative Examples 1 to 7. It is understood that it is excellent.
【００５３】なお、実施例１〜８で用いた組成の水素吸
蔵合金以外の前記一般式で表わされる水素吸蔵合金を用
いた場合でも、実施例１〜８と同様な優れた特性を示す
アルカリ二次電池を得ることができる。Incidentally, even when the hydrogen storage alloy represented by the above general formula other than the hydrogen storage alloy having the composition used in Examples 1 to 8 was used, the alkaline storage alloy having the same excellent characteristics as those of Examples 1 to 8 was used. The following battery can be obtained.
【００５４】また、前記実施例では円筒形のニッケル水
素二次電池に適用した例を説明したが正極、セパレータ
および負極を積層して電極群を構成する角形の形状のニ
ッケル水素二次電池にも同様に適用することができる。In the above-described embodiment, an example in which the present invention is applied to a cylindrical nickel-metal hydride secondary battery has been described. The same can be applied.
【００５５】[0055]
【発明の効果】以上説明したように本発明によれば、優
れた耐酸化性を有し、低温および高温で高い水素吸蔵性
を有し、かつ吸蔵・放出の繰り返しにおいて十分な水素
吸蔵量を維持し、さらに高い水素吸蔵速度を有する水素
吸蔵合金を提供することができる。As described above, according to the present invention, the present invention has excellent oxidation resistance, has high hydrogen storage properties at low and high temperatures, and has a sufficient hydrogen storage amount in repeated storage and release. It is possible to provide a hydrogen storage alloy that maintains and has a higher hydrogen storage rate.
【００５６】また、本発明によれば前記優れた特性を有
する水素吸蔵合金を含む負極を備え、高容量化を実現し
つつ、充放電サイクル寿命の長いアルカリ二次電池を提
供することができる。Further, according to the present invention, it is possible to provide an alkaline secondary battery having a negative electrode containing a hydrogen storage alloy having the above-mentioned excellent characteristics, realizing high capacity, and having a long charge-discharge cycle life.
【図１】本発明に係わるアルカリ二次電池の一例である
ニッケル水素二次電池の斜視図。FIG. 1 is a perspective view of a nickel-metal hydride secondary battery which is an example of an alkaline secondary battery according to the present invention.
１…容器、 ２…正極、 ３…セパレータ、 ４…負極、 ５…電極群、 ７…封口板。 DESCRIPTION OF SYMBOLS 1 ... Container, 2 ... Positive electrode, 3 ... Separator, 4 ... Negative electrode, 5 ... Electrode group, 7 ... Sealing plate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 武野 和太 東京都品川区南品川３丁目４番10号 東芝 電池株式会社内 Ｆターム(参考） 5H028 EE01 FF04 HH00 5H050 AA07 AA08 BA14 CA03 CB16 EA03 EA12 EA23 EA24 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kazuta Takeno 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Toshiba Battery Corporation F-term (reference) 5H028 EE01 FF04 HH00 5H050 AA07 AA08 BA14 CA03 CB16 EA03 EA12 EA23 EA24
Claims (3)
（ただし、式中のＬｎはランタノイド元素，Ｃａ，Ｓ
ｒ，Ｓｃ，Ｙ，Ｔｉ，ＺｒおよびＨｆから選ばれる少な
くとも１つの元素で、かつＬｎに占めるＬａ量が１０〜
５０原子％であり、ＴはＬｉ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，
Ｍｏ，Ｍｎ，Ｆｅ，Ｃｏ，Ａｌ，Ｇａ，Ｚｎ，Ｓｎ，Ｉ
ｎ，Ｃｕ，Ｓｉ，ＰおよびＢから選ばれる少なくとも１
つの元素、ｘ，ｙ，ｚはそれぞれ０．０５≦ｘ＜０．２
０，０≦ｙ≦０．５，２．８≦ｚ≦３．９を示す）にて
表わされる水素吸蔵合金。1. The general formula Ln 1-x Mg x (Ni 1-y T y ) z
(Where Ln is a lanthanoid element, Ca, S
at least one element selected from the group consisting of r, Sc, Y, Ti, Zr and Hf;
50 atomic%, and T is Li, V, Nb, Ta, Cr,
Mo, Mn, Fe, Co, Al, Ga, Zn, Sn, I
at least one selected from n, Cu, Si, P and B
X, y, and z are respectively 0.05 ≦ x <0.2.
0, 0 ≦ y ≦ 0.5, 2.8 ≦ z ≦ 3.9).
０．１５であることを特徴とする水素吸蔵合金。2. In the general formula, x is 0.05 ≦ x <
0.15, wherein the hydrogen storage alloy is 0.15.
を備えたことを特徴とするアルカリ二次電池。3. An alkaline secondary battery comprising a negative electrode containing the hydrogen storage alloy according to claim 1.
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