JP2001325957A - Alkaline secondary cell - Google Patents
Alkaline secondary cellInfo
- Publication number
- JP2001325957A JP2001325957A JP2000143440A JP2000143440A JP2001325957A JP 2001325957 A JP2001325957 A JP 2001325957A JP 2000143440 A JP2000143440 A JP 2000143440A JP 2000143440 A JP2000143440 A JP 2000143440A JP 2001325957 A JP2001325957 A JP 2001325957A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- rare earth
- negative electrode
- hydrogen storage
- mass
- 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 an alkaline secondary battery having an improved negative electrode containing a hydrogen storage alloy for electrochemically storing and releasing hydrogen.
【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重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 weight are higher than the widely used MmNi 5 alloy, the activation is faster than the TiMn 2 alloy, and the high rate charge / discharge characteristics are excellent. 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
含む水素吸蔵合金前記水素吸蔵合金はアルカリ電解液中
での耐食性がＭｍＮｉ5系合金に比べて劣るため、この
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
はサイクル寿命が低下するという問題があった。[SUMMARY OF THE INVENTION However, since magnesium hydrogen storage alloy hydrogen absorbing alloy containing nickel and rare earth elements as a main constituent element has the resistance to corrosion in alkaline electrolyte inferior to MmNi 5 alloys, this Alkaline secondary batteries provided with a negative electrode containing a hydrogen storage alloy have a problem that the cycle life is reduced.
【０００９】本発明は、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
素吸蔵合金とイットリウムを含む希土類元素の化合物を
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。The present invention relates to a hydrogen-absorbing alloy having a high hydrogen-absorbing property at low and high temperatures, maintaining a sufficient hydrogen-absorbing amount during repeated storage and desorption, and a high hydrogen-absorbing rate, and a rare earth element containing yttrium. An object of the present invention is to provide an alkaline secondary battery having a negative electrode containing a compound of an element, achieving high capacity, and having a long charge-discharge cycle life.
【００１０】[0010]
【課題を解決するための手段】本発明に係るアルカリ二
次電池は、正極と、負極と、セパレータと、アルカリ電
解液とを備えたアルカリ二次電池において、前記負極
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，Ｓｃ，
Ｙ，Ｔｉ，ＺｒおよびＨｆから選ばれる少なくとも１つ
の元素、ＴはＬｉ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，Ｍｏ，Ｍ
ｎ，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＜ｘ＜１，０≦ｙ≦０．
５，２．５≦ｚ≦４．５を示す）にて表わされる水素吸
蔵合金と、この合金１００質量部に対して元素換算で
０．０１〜２０質量部のイットリウムを含む希土類の化
合物とを含有することを特徴とするものである。According to the present invention, there is provided an alkaline secondary battery comprising a positive electrode, a negative electrode, a separator, and an alkaline electrolyte, wherein the negative electrode has a general formula of Ln 1- x Mg x (Ni 1-y T y ) z (however,
Ln in the formula is a lanthanoid element, Ca, Sr, Sc,
At least one element selected from Y, Ti, Zr and Hf, T is Li, V, Nb, Ta, Cr, Mo, M
n, Fe, Co, Al, Ga, Zn, Sn, In, C
at least one element selected from u, Si, P and B, x, y, and z are each 0 <x <1, 0 ≦ y ≦ 0.
5,2.5 ≦ z ≦ 4.5) and a rare earth compound containing 0.01 to 20 parts by mass of yttrium in elemental conversion with respect to 100 parts by mass of the alloy. It is characterized by containing.
【００１１】[0011]
【発明の実施の形態】以下、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。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an alkaline secondary battery (for example, a cylindrical alkaline secondary battery) according to the present invention will be described with reference to FIG.
【００１２】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 a positive electrode 2, a separator 3, and a negative electrode 4 and winding them in a spiral shape is accommodated in a 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.
【００１３】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.
【００１４】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.
【００１５】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.
【００１６】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) Positive electrode 2 This positive electrode 2 contains a nickel compound as an active material.
【００１７】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, nickel oxide and nickel oxide in which nickel hydroxide, zinc and cobalt are co-precipitated.
Particularly, nickel hydroxide in which zinc and cobalt are coprecipitated is preferable.
【００１８】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。The positive electrode (paste type positive electrode) is prepared, for example, by kneading a nickel compound as an active material, 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 required.
【００１９】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.
【００２０】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; polyvinyl; Examples include hydrophilic polymers such as alcohol and polyethylene oxide; and rubber-based polymers such as latex.
【００２１】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, fiber-like, or felt-like porous metal body made of nickel, stainless steel, or nickel-plated metal.
【００２２】２）負極４ この負極４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，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、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＜ｘ＜１，０≦ｙ≦
０．５，２．５≦ｚ≦４．５を示す）にて表わされる水
素吸蔵合金と、この合金１００質量部に対して元素換算
で０．０１〜２０質量部のイットリウムを含む希土類の
化合物とを含有する。2) Negative electrode 4 This negative electrode 4 has 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, and T represents 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 0 <x <1, 0 ≦ y ≦
0.5, 2.5 ≦ z ≦ 4.5) and a rare earth compound containing 0.01 to 20 parts by mass of yttrium in elemental conversion with respect to 100 parts by mass of the alloy. And
【００２３】前記一般式のＬｎは、特にランタノイド元
素が好ましい。Ln in the above general formula is particularly preferably a lanthanoid element.
【００２４】前記一般式のｘの規定により高い水素吸蔵
量を有する水素吸蔵合金を得ることができる。特に、一
般式のｘは０．０５≦ｘ＜０．２、より好ましくは０．
１０≦ｘ＜０．１５にすることが望ましい。A hydrogen storage alloy having a high hydrogen storage amount can be obtained by the definition of x in the general formula. In particular, x in the general formula is 0.05 ≦ x <0.2, more preferably 0.
It is preferable that 10 ≦ x <0.15.
【００２５】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, the hydrogen storage capacity at high temperatures may be significantly reduced. More preferable y is 0 ≦ y ≦ 0.2.
【００２６】前記一般式中のｚを規定したのは、ｚを
２．５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
４．５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ｚは、２．８≦ｚ≦３．９、さ
らに好ましい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 2.5, 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 4.5, the hydrogen storage amount at high temperatures may be significantly reduced. More preferable z is 2.8 ≦ z ≦ 3.9, and further preferable z is 3.0 ≦ z ≦ 3.6.
【００２７】前記イットリウムを含む希土類の化合物と
しては、硝酸塩化合物、ハロゲン化合物、硫酸塩化合
物、リン酸塩化合物、炭酸塩化合物、シュウ酸塩化合物
および酢酸化合物が挙げられ、これは単独または２種以
上の混合物の形態で用いることができる。また、前記イ
ットリウムを含む希土類の化合物としては、酸化物また
は２種以上の酸化物からなる複合酸化物を用いることが
できる。この酸化物は、単独または２種以上の混合物の
形態で用いることができる。さらに、前記イットリウム
を含む希土類の化合物としては水酸化物を用いることが
できる。The rare earth compound containing yttrium includes a nitrate compound, a halogen compound, a sulfate compound, a phosphate compound, a carbonate compound, an oxalate compound, and an acetic acid compound. Can be used in the form of a mixture. Further, as the rare earth compound containing yttrium, an oxide or a composite oxide composed of two or more oxides can be used. This oxide can be used alone or in the form of a mixture of two or more. Further, as the rare earth compound containing yttrium, a hydroxide can be used.
【００２８】前記イットリウムを含む希土類の化合物の
配合量を水素吸蔵合金１００質量部に対して元素換算で
０．０１〜２０質量部に規定したのは次のような理由に
よるものである。この化合物の量を水素吸蔵合金１００
質量部に対して元素換算で０．０１質量部未満にする
と、水素吸蔵合金表面の酸化を抑制することが困難にな
る。一方、この化合物の量が水素吸蔵合金１００質量部
に対して元素換算で２０質量部を超えると、負極中に占
める前記化合物量が増大して負極容量が低下する虞があ
る。より好ましい前記化合物の量は、水素吸蔵合金１０
０質量部に対して元素換算で０．１〜５質量部である。The reason why the compounding amount of the rare earth compound containing yttrium is specified to be 0.01 to 20 parts by mass in terms of element relative to 100 parts by mass of the hydrogen storage alloy is as follows. The amount of this compound is determined by
If the amount is less than 0.01 parts by mass in terms of element relative to parts by mass, it becomes difficult to suppress oxidation of the surface of the hydrogen storage alloy. On the other hand, if the amount of this compound exceeds 20 parts by mass in terms of element with respect to 100 parts by mass of the hydrogen storage alloy, the amount of the compound in the negative electrode may increase and the capacity of the negative electrode may decrease. More preferred amount of the compound is hydrogen storage alloy 10
It is 0.1 to 5 parts by mass based on 0 parts by mass in terms of element.
【００２９】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.
【００３０】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 in 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.
【００３１】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.
【００３２】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.
【００３３】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 This 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.
【００３４】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.
【００３５】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、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＜ｘ＜１，０≦ｙ≦０．
５，２．５≦ｚ≦４．５を示す）にて表わされる水素吸
蔵合金と、この合金１００質量部に対して元素換算で
０．０１〜２０質量部のイットリウムを含む希土類の化
合物とを含有する負極を備える。The alkaline secondary battery according to the present invention described above has the 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, 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 each 0 <x <1, 0 ≦ y ≦ 0.
5,2.5 ≦ z ≦ 4.5) and a rare earth compound containing 0.01 to 20 parts by mass of yttrium in elemental conversion with respect to 100 parts by mass of the alloy. A negative electrode is included.
【００３６】前記負極中の水素吸蔵合金は、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。一方、イットリウムを含む希土類の
化合物は、アルカリ電解液中で溶解し、クラックにより
新たに発生した前記水素吸蔵合金の活性面に析出し、こ
の活性面を被覆するため、前記水素吸蔵合金表面の酸化
を抑制してその水素吸蔵能力の低下を防止する。The hydrogen storage alloy in the negative electrode 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. On the other hand, the rare earth compound containing yttrium dissolves in the alkaline electrolyte, precipitates on the active surface of the hydrogen storage alloy newly generated by cracks, and covers the active surface, thereby oxidizing the surface of the hydrogen storage alloy. To prevent a decrease in its hydrogen storage capacity.
【００３７】したがって、前記水素吸蔵合金による高容
量化と前記イットリウムを含む希土類の化合物による水
素吸蔵合金への耐食性の付与によって、高容量で、サイ
クル寿命の長いすアルカリ二次電池を得ることができ
る。Therefore, by increasing the capacity by the hydrogen storage alloy and imparting corrosion resistance to the hydrogen storage alloy by the rare earth compound containing yttrium, an alkaline secondary battery having a high capacity and a long cycle life can be obtained. .
【００３８】[0038]
【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.
【００３９】（実施例１〜３）各純金属をＬａ0.33Ｃｅ
0.03Ｐｒ0.09Ｎｄ0.26Ｙｂ0.01Ｍｇ0.28Ｎｉ2.70Ｃｏ
0.45Ｃｒ0.05Ｍｎ0.07Ａｌ0.03の組成になるように混合
したものを高周波溶解炉を用いてアルゴン雰囲気中で溶
解・冷却した。このインゴットをアルゴン雰囲気中、９
００℃で１０時間熱処理して均質化を行ない、不活性雰
囲気中で粉砕後、７５μｍ以下になるように篩を通し、
水素吸蔵合金粉末を得た。(Examples 1 to 3) Each pure metal was La0.33Ce
0.03Pr0.09Nd0.26Yb0.01Mg0.28Ni2.70Co
0.45Cr0.05Mn0.07Al0.03Mixed so that the composition becomes
Was melted in an argon atmosphere using a high-frequency melting furnace.
Dissolved and cooled. This ingot was placed in an argon atmosphere at 9
Heat treatment at 00 ° C for 10 hours to homogenize,
After pulverizing in an atmosphere, pass through a sieve to 75 μm or less,
A hydrogen storage alloy powder was obtained.
【００４０】次いで、前記水素吸蔵合金粉末１００質量
部と下記表１に示すＹｂ2Ｏ3、ＹｂとＥｒの複合酸化物
（Ｙｂ2Ｏ3：Ｅｒ2Ｏ3＝１：１）およびＥｒとＤｙの複
合酸化物（Ｅｒ2Ｏ3：Ｄｙ2Ｏ3＝１：１）５質量部（希
土類元素換算）と結着剤としてカルボキシメチルセルロ
ース（ＣＭＣ）０．２質量部とを水５０質量部と共に添
加した後、混練することによりペーストを調製した。つ
づいて、前記ペーストを多孔度９５％の発泡ニッケルに
充填した後、１２５℃で乾燥し、厚さ０．３４ｍｍにプ
レス成形し、さらに幅６１ｍｍ、長さ１６３ｍｍに裁断
することにより３種のペースト式の負極を作製した。Next, 100 parts by mass of the hydrogen storage alloy powder and Yb 2 O 3 , a composite oxide of Yb and Er (Yb 2 O 3 : Er 2 O 3 = 1: 1) and Er and Dy shown in Table 1 below Of a composite oxide (Er 2 O 3 : Dy 2 O 3 = 1: 1) (in terms of rare earth element) and 0.2 parts by mass of carboxymethyl cellulose (CMC) as a binder were added together with 50 parts by mass of water After that, a paste was prepared by kneading. Subsequently, after filling the paste into foamed nickel having a porosity of 95%, the paste was dried at 125 ° C., press-molded to a thickness of 0.34 mm, and further cut into a width of 61 mm and a length of 163 mm to obtain three kinds of pastes. A negative electrode of the formula was prepared.
【００４１】＜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.
【００４２】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３種の４／３
Ａサイズの円筒形ニッケル水素二次電池（容量４２００
ｍＡｈ）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. Three types of 4/3 with structure
A-size cylindrical nickel-metal hydride rechargeable battery (capacity 4200
mAh).
【００４３】（比較例１）実施例１と同様な組成の水素
吸蔵合金粉末１００質量部と結着剤としてカルボキシメ
チルセルロース（ＣＭＣ）０．２質量部とを水５０質量
部と共に添加した後、混練することによりペーストを調
製し、前記ペーストを多孔度９５％の発泡ニッケルに充
填した後、１２５℃で乾燥し、厚さ０．３４ｍｍにプレ
ス成形し、さらに幅６１ｍｍ、長さ１６３ｍｍに裁断す
ることにより得たペースト式の負極を用いた以外、実施
例１と同様な円筒形ニッケル水素二次電池（容量４２０
０ｍＡｈ）を組み立てた。Comparative Example 1 100 parts by mass of a hydrogen storage alloy powder having the same composition as in Example 1 and 0.2 parts by mass of carboxymethylcellulose (CMC) as a binder were added together with 50 parts by mass of water, followed by kneading. A paste is prepared by filling the paste into nickel foam having a porosity of 95%, dried at 125 ° C., pressed into a thickness of 0.34 mm, and further cut into a width of 61 mm and a length of 163 mm. Cylindrical nickel-metal hydride secondary battery (capacity 420) except that the paste type negative electrode obtained by
0 mAh).
【００４４】得られた実施例１〜３および比較例１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
条件で充放電を繰り返すサイクル試験を行なってサイク
ル寿命を調べた。なお、サイクル寿命は、二次電池の容
量が初期容量の８０％に達するまでのサイクル数の平均
値として求めた。The obtained secondary batteries of Examples 1 to 3 and Comparative Example 1 were charged at 25 ° C. for 13 hours at a rate of 10 hours, and discharged at 25 ° C. to a final voltage of 1.0 V at a rate of 5 hours. The cycle life was examined by performing a cycle test in which charge and discharge were repeated. The cycle life was determined as an average value of the number of cycles until the capacity of the secondary battery reached 80% of the initial capacity.
【００４５】これらの結果を下記表１に併記する。The results are shown in Table 1 below.
【００４６】[0046]
【表１】 [Table 1]
【００４７】前記表１から明らかなように希土類酸化物
または希土類複合酸化物を含有する負極を備えた実施例
１〜３の二次電池は、前記希土類酸化物を含有しない負
極を備えた比較例１に比べて優れたサイクル寿命を有す
ることがわかる。As is clear from Table 1, the secondary batteries of Examples 1 to 3 provided with the negative electrode containing the rare earth oxide or the rare earth composite oxide were the comparative examples provided with the negative electrode not containing the rare earth oxide. It can be seen that it has an excellent cycle life as compared with No. 1.
【００４８】（実施例４〜１２）各純金属をＬａ0.33Ｃ
ｅ0.03Ｐｒ0.09Ｎｄ0.26Ｙｂ0.01Ｍｇ0.28Ｎｉ2.70Ｃｏ
0.45Ｃｒ0.05Ｍｎ0.07Ａｌ0.03の組成になるように混合
したものを高周波溶解炉を用いてアルゴン雰囲気中で溶
解・冷却した。このインゴットをアルゴン雰囲気中、９
００℃で１０時間熱処理して均質化を行ない、不活性雰
囲気中で粉砕後、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、前記水素吸蔵合金
粉末１００質量部と下記表２に示すイットリウムを含む
希土類の硝酸化合物１０質量部（希土類元素換算）と結
着剤としてカルボキシメチルセルロース（ＣＭＣ）０．
２質量部とを水５０質量部と共に添加した後、混練する
ことによりペーストを調製した。つづいて、前記ペース
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０．３４ｍｍにプレス成形し、さらに
幅６１ｍｍ、長さ１６３ｍｍに裁断することにより９種
のペースト式の負極を作製した。(Examples 4 to 12) Each pure metal was La0.33C
e0.03Pr0.09Nd0.26Yb0.01Mg0.28Ni2.70Co
0.45Cr0.05Mn0.07Al0.03Mixed so that the composition becomes
Was melted in an argon atmosphere using a high-frequency melting furnace.
Dissolved and cooled. This ingot was placed in an argon atmosphere at 9
Heat treatment at 00 ° C for 10 hours to homogenize,
After pulverizing in an atmosphere, pass through a sieve to 75 μm or less,
A hydrogen storage alloy powder was obtained. Subsequently, the hydrogen storage alloy
Contains 100 parts by mass of powder and yttrium shown in Table 2 below
Concluded with 10 parts by weight of rare earth nitrate compound (converted to rare earth element)
Carboxymethyl cellulose (CMC) 0.
After adding 2 parts by mass and 50 parts by mass of water, kneading is performed.
Thus, a paste was prepared. Next, the pace
After filling into 95% porosity foamed nickel.
Dried at ℃, pressed to a thickness of 0.34mm,
Nine kinds by cutting to 61mm width and 163mm length
Was prepared.
【００４９】前記各負極を用いて実施例１と同様な方法
により前述した図１に示す構造を有する９種の４／３Ａ
サイズの円筒形ニッケル水素二次電池（容量４２００ｍ
Ａｈ）を組み立てた。Nine kinds of 4 / 3A having the above-described structure shown in FIG.
Size cylindrical nickel-metal hydride rechargeable battery (capacity 4200m
Ah) was assembled.
【００５０】得られた実施例４〜１２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充放電を
繰り返すサイクル試験を行なってサイクル寿命を調べ
た。なお、サイクル寿命は二次電池の容量が初期容量の
８０％に達するまでのサイクル数の平均値として求め
た。The obtained secondary batteries of Examples 4 to 12 were charged at a rate of 10 hours at 25 ° C. for 13 hours.
A cycle test was performed in which charge and discharge were repeated under the condition of discharging to a final voltage of 1.0 V at a time rate, and the cycle life was examined. The cycle life was obtained as an average value of the number of cycles until the capacity of the secondary battery reached 80% of the initial capacity.
【００５１】これらの結果を下記表２に併記する。表２
には、前述した比較例１の結果も併記した。The results are shown in Table 2 below. Table 2
, The results of Comparative Example 1 described above are also shown.
【００５２】[0052]
【表２】 [Table 2]
【００５３】前記表２から明らかなように希土類硝酸塩
化合物を含有する負極を備えた実施例４〜１２の二次電
池は、前記希土類硝酸塩酸化物を含有しない負極を備え
た比較例１に比べて優れたサイクル寿命を有することが
わかる。As is clear from Table 2, the secondary batteries of Examples 4 to 12 provided with the negative electrode containing the rare earth nitrate compound were compared with Comparative Example 1 provided with the negative electrode not containing the rare earth nitrate oxide. It turns out that it has excellent cycle life.
【００５４】（実施例１３〜２５）各純金属をＬａ0.33
Ｃｅ0.03Ｐｒ0.09Ｎｄ0.26Ｙｂ0.01Ｍｇ0.28Ｎｉ2.70Ｃ
ｏ 0.45Ｃｒ0.05Ｍｎ0.07Ａｌ0.03の組成になるように混
合したものを高周波溶解炉を用いてアルゴン雰囲気中で
溶解・冷却した。このインゴットをアルゴン雰囲気中、
９００℃で１０時間熱処理して均質化を行ない、不活性
雰囲気中で粉砕後、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、前記水素吸蔵
合金粉末１００質量部と下記表３に示すイットリウムを
含む希土類の化合物１０質量部（希土類元素換算）と結
着剤としてカルボキシメチルセルロース（ＣＭＣ）０．
２質量部とを水５０質量部と共に添加した後、混練する
ことによりペーストを調製した。つづいて、前記ペース
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０．３４ｍｍにプレス成形し、さらに
幅６１ｍｍ、長さ１６３ｍｍに裁断することにより１３
種のペースト式の負極を作製した。(Examples 13 to 25) Each pure metal was La0.33
Ce0.03Pr0.09Nd0.26Yb0.01Mg0.28Ni2.70C
o 0.45Cr0.05Mn0.07Al0.03Mixed so that the composition becomes
In an argon atmosphere using a high-frequency melting furnace
Dissolved and cooled. Put this ingot in an argon atmosphere,
Inert by heat treatment at 900 ° C for 10 hours to homogenize
After crushing in an atmosphere, pass through a sieve to 75 μm or less.
Thus, a hydrogen storage alloy powder was obtained. Then, the hydrogen storage
100 parts by mass of alloy powder and yttrium shown in Table 3 below
With 10 parts by weight (converted to rare earth element)
Carboxymethyl cellulose (CMC) 0.
After adding 2 parts by mass and 50 parts by mass of water, kneading is performed.
Thus, a paste was prepared. Next, the pace
After filling into 95% porosity foamed nickel.
Dried at ℃, pressed to a thickness of 0.34mm,
13 by cutting to 61mm width and 163mm length
Various paste-type negative electrodes were prepared.
【００５５】前記各負極を用いて実施例１と同様な方法
により前述した図１に示す構造を有する１３種の４／３
Ａサイズの円筒形ニッケル水素二次電池（容量４２００
ｍＡｈ）を組み立てた。Thirteen kinds of 4/3 having the structure shown in FIG.
A-size cylindrical nickel-metal hydride rechargeable battery (capacity 4200
mAh).
【００５６】得られた実施例１３〜２５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充放電
を繰り返すサイクル試験を行なってサイクル寿命を調べ
た。なお、サイクル寿命は二次電池の容量が初期容量の
８０％に達するまでのサイクル数の平均値として求め
た。The obtained secondary batteries of Examples 13 to 25 were charged at 25 ° C. at a rate of 10 hours for 13 hours.
A cycle test was repeated in which charging and discharging were repeated under conditions of discharging to a final voltage of 1.0 V at a rate of 5 hours, and the cycle life was examined. The cycle life was obtained as an average value of the number of cycles until the capacity of the secondary battery reached 80% of the initial capacity.
【００５７】これらの結果を下記表３に併記する。表３
には、前述した比較例１の結果も併記した。The results are shown in Table 3 below. Table 3
, The results of Comparative Example 1 described above are also shown.
【００５８】[0058]
【表３】 [Table 3]
【００５９】前記表３から明らかなようにフッ化ユウロ
ビウムのような希土類化合物を含有する負極を備えた実
施例１３〜２５の二次電池は、前記希土類化物を含有し
ない負極を備えた比較例１に比べて優れたサイクル寿命
を有することがわかる。As is apparent from Table 3, the secondary batteries of Examples 13 to 25 provided with the negative electrode containing a rare earth compound such as eurobium fluoride, and Comparative Example 1 provided with the negative electrode containing no rare earth compound. It can be seen that it has an excellent cycle life as compared with.
【００６０】なお、実施例１〜２５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１〜２５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 a hydrogen storage alloy represented by the above-mentioned general formula other than the hydrogen storage alloy having the composition used in Examples 1 to 25 was used, an alkali metal exhibiting the same excellent characteristics as in Examples 1 to 25 was used. The following battery can be obtained.
【００６１】また、前記各実施例では円筒型のニッケル
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 each of the above embodiments, an example in which the present invention is applied to a cylindrical nickel-metal hydride secondary battery has been described. However, the present invention is applied to a square nickel-metal hydride secondary battery in which a positive electrode, a separator and a negative electrode are laminated to form an electrode group. Can be similarly applied.
【００６２】[0062]
【発明の効果】以上説明したように本発明によれば、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とイットリウム
を含む希土類元素の化合物を含む負極を備え、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。As described above, according to the present invention, it has high hydrogen storage properties at low and high temperatures, maintains a sufficient amount of hydrogen storage during repeated storage and release, and achieves a higher hydrogen storage rate. It is possible to provide an alkaline secondary battery having a negative electrode containing a compound of a rare earth element including yttrium and a hydrogen storage alloy having the same and 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 AA01 AA05 CC12 EE01 HH01 5H050 BA14 CB16 CB18 DA03 DA09 EA02 EA11 EA12 EA29 FA05 HA01 HA02 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuta Takeno 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Toshiba Battery Corporation F-term (reference) 5H028 AA01 AA05 CC12 EE01 HH01 5H050 BA14 CB16 CB18 DA03 DA09 EA02 EA11 EA12 EA29 FA05 HA01 HA02
Claims (4)
リ電解液とを備えたアルカリ二次電池において、 前記負極は、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，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、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＜ｘ＜１，０≦ｙ≦
０．５，２．５≦ｚ≦４．５を示す）にて表わされる水
素吸蔵合金と、この合金１００質量部に対して元素換算
で０．０１〜２０質量部のイットリウムを含む希土類の
化合物とを含有することを特徴とするアルカリ二次電
池。1. An alkaline secondary battery comprising a positive electrode, a negative electrode, a separator, and an alkaline electrolyte, wherein the negative electrode has a 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, and T represents 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 0 <x <1, 0 ≦ y ≦
0.5, 2.5 ≦ z ≦ 4.5) and a rare earth compound containing 0.01 to 20 parts by mass of yttrium in elemental conversion with respect to 100 parts by mass of the alloy. And an alkaline secondary battery comprising:
は、イットリウムを含む希土類の硝酸塩化合物、ハロゲ
ン化合物、硫酸塩化合物、リン酸塩化合物、炭酸塩化合
物、シュウ酸塩化合物および酢酸化合物から選ばれる少
なくとも１つの化合物であることを特徴とする請求項１
記載のアルカリ二次電池。2. The rare earth compound containing yttrium is at least one selected from the group consisting of a rare earth nitrate compound, a halogen compound, a sulfate compound, a phosphate compound, a carbonate compound, an oxalate compound and an acetic acid compound containing yttrium. 2. The compound of claim 1, wherein
The alkaline secondary battery according to the above.
は、イットリウムを含む希土類の酸化物または２種以上
の酸化物からなる複合酸化物であることを特徴とする請
求項１記載のアルカリ二次電池。3. The alkaline secondary battery according to claim 1, wherein the rare earth compound containing yttrium is a rare earth oxide containing yttrium or a composite oxide composed of two or more oxides.
は、イットリウムを含む希土類の水酸化物であることを
特徴とする請求項１記載のアルカリ二次電池。4. The alkaline secondary battery according to claim 1, wherein the rare earth compound containing yttrium is a rare earth hydroxide containing yttrium.
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|---|---|---|---|
| JP2000143440A JP2001325957A (en) | 2000-05-16 | 2000-05-16 | Alkaline secondary cell |
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ID=18650259
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Cited By (8)
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|---|---|---|---|---|
| JP2006037122A (en) * | 2004-07-22 | 2006-02-09 | Yuasa Corp | Hydrogen storage alloy, hydrogen storage electrode and nickel-hydrogen storage battery |
| EP1727229A1 (en) * | 2005-05-26 | 2006-11-29 | Saft | Active material composition and alkaline electrolyte accumulator |
| EP1900834A1 (en) * | 2006-09-15 | 2008-03-19 | Saft Groupe Sa | Composition for negative electrode of accumulator with alkaline electrolyte |
| JP2010003551A (en) * | 2008-06-20 | 2010-01-07 | Sanyo Electric Co Ltd | Nickel metal hydride secondary battery |
| US7758805B2 (en) * | 2006-03-30 | 2010-07-20 | Kabushiki Kaisha Toshiba | Hydrogen occlusive alloy, hydrogen storage film and hydrogen storage tank |
| US7776258B2 (en) | 2006-09-29 | 2010-08-17 | Kabushiki Kaisha Toshiba | Hydrogen storage alloy, hydrogen separation membrane, hydrogen storage tank, and hydrogen absorption and desorption method |
| CN103236552A (en) * | 2013-03-14 | 2013-08-07 | 浙江野马电池有限公司 | high-capacity alkaline zinc-manganese battery |
| JP2016149299A (en) * | 2015-02-13 | 2016-08-18 | Fdk株式会社 | Nickel hydrogen secondary battery |
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| JP2000021439A (en) * | 1998-06-30 | 2000-01-21 | Toshiba Corp | Nickel hydrogen secondary battery |
| JP2000082491A (en) * | 1998-09-08 | 2000-03-21 | Toshiba Battery Co Ltd | Nickel-hydrogen secondary battery |
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| WO1997008353A1 (en) * | 1995-08-31 | 1997-03-06 | Santoku Metal Industry Co., Ltd. | Rare earth metal/nickel-base hydrogen absorbing alloy, process for preparing the same, and negative electrode for nickel-hydrogen secondary battery |
| JP2000021439A (en) * | 1998-06-30 | 2000-01-21 | Toshiba Corp | Nickel hydrogen secondary battery |
| JP2000082491A (en) * | 1998-09-08 | 2000-03-21 | Toshiba Battery Co Ltd | Nickel-hydrogen secondary battery |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006037122A (en) * | 2004-07-22 | 2006-02-09 | Yuasa Corp | Hydrogen storage alloy, hydrogen storage electrode and nickel-hydrogen storage battery |
| JP4540045B2 (en) * | 2004-07-22 | 2010-09-08 | 株式会社Ｇｓユアサ | Hydrogen storage alloy, hydrogen storage electrode and nickel metal hydride storage battery |
| EP1727229A1 (en) * | 2005-05-26 | 2006-11-29 | Saft | Active material composition and alkaline electrolyte accumulator |
| FR2886462A1 (en) * | 2005-05-26 | 2006-12-01 | Accumulateurs Fixes | ACTIVE MATERIAL COMPOSITION AND ALKALINE ELECTROLYTE BATTERY |
| US7820325B2 (en) | 2005-05-26 | 2010-10-26 | Saft | Alkaline electrolyte storage battery having an anode formed of an active material composition |
| US7758805B2 (en) * | 2006-03-30 | 2010-07-20 | Kabushiki Kaisha Toshiba | Hydrogen occlusive alloy, hydrogen storage film and hydrogen storage tank |
| EP1900834A1 (en) * | 2006-09-15 | 2008-03-19 | Saft Groupe Sa | Composition for negative electrode of accumulator with alkaline electrolyte |
| JP2008071759A (en) * | 2006-09-15 | 2008-03-27 | Saft Groupe Sa | Composition of anode of alkaline electrolytic solution battery, anode composed of the composition, and alkaline electrolytic solution battery composed of this anode |
| FR2906084A1 (en) * | 2006-09-15 | 2008-03-21 | Accumulateurs Fixes | COMPOSITION FOR NEGATIVE ELECTRODE OF ALKALINE ELECTROLYTE BATTERY. |
| US8652684B2 (en) | 2006-09-15 | 2014-02-18 | Saft Groupe Sa | Composition for negative electrode of alkaline electrolyte battery |
| US7776258B2 (en) | 2006-09-29 | 2010-08-17 | Kabushiki Kaisha Toshiba | Hydrogen storage alloy, hydrogen separation membrane, hydrogen storage tank, and hydrogen absorption and desorption method |
| JP2010003551A (en) * | 2008-06-20 | 2010-01-07 | Sanyo Electric Co Ltd | Nickel metal hydride secondary battery |
| CN103236552A (en) * | 2013-03-14 | 2013-08-07 | 浙江野马电池有限公司 | high-capacity alkaline zinc-manganese battery |
| JP2016149299A (en) * | 2015-02-13 | 2016-08-18 | Fdk株式会社 | Nickel hydrogen secondary battery |
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