JPH11176437A - Positive electrode active material for alkaline storage battery - Google Patents
Positive electrode active material for alkaline storage batteryInfo
- Publication number
- JPH11176437A JPH11176437A JP10246787A JP24678798A JPH11176437A JP H11176437 A JPH11176437 A JP H11176437A JP 10246787 A JP10246787 A JP 10246787A JP 24678798 A JP24678798 A JP 24678798A JP H11176437 A JPH11176437 A JP H11176437A
- Authority
- JP
- Japan
- Prior art keywords
- solid solution
- positive electrode
- active material
- layer
- powder
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルカリ蓄電池用
正極活物質の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a positive electrode active material for an alkaline storage battery.
【０００２】[0002]
【従来の技術】アルカリ蓄電池、特にその小型密閉式電
池は、他の電池系と比べて充放電特性、サイクル寿命お
よび安全性・信頼性にバランス良く優れることから、移
動体通信機器、パーソナルコンピューターなどに代表さ
れる各種ポータブル機器用主電源として普及が著しい。
また、大型電源としても充放電特性や信頼性にきわめて
優れることから、電気自動車などの移動用主電源として
も注目されている。アルカリ蓄電池を代表する電池系
は、長い歴史を持つニッケル・カドミウム蓄電池であっ
たが、カドミウム負極の代わりに水素吸蔵合金負極を用
いたニッケル・水素蓄電池が工業化され、高エネルギー
密度化が図られた。また、電極支持体においても焼結式
電極に代わり、高多孔度（９５％以上）の３次元発泡ニ
ッケル多孔体にニッケル酸化物を高密度充填した電極
（Ｓｐｏｎｇｅ Ｍｅｔａｌ Ｎｉｃｋｅｌ Ｅｌｅｃ
ｔｒｏｄｅ：ＳＭＥ）が工業化され、高エネルギー密度
化が図られた。このように、これまでアルカリ蓄電池で
は、特に電池の小型化・軽量化・高エネルギー密度化に
注力されてきた。2. Description of the Related Art Alkaline storage batteries, especially small sealed batteries, have better balance of charge / discharge characteristics, cycle life and safety / reliability than other battery systems. The main power supply for various portable devices represented by the above is widely spread.
Also, since it is extremely excellent in charge / discharge characteristics and reliability even as a large power supply, it is attracting attention as a main power supply for electric vehicles and the like. The battery system that represents alkaline storage batteries was a nickel-cadmium storage battery with a long history.However, nickel-hydrogen storage batteries using hydrogen storage alloy anodes instead of cadmium anodes were industrialized, and higher energy density was achieved. . Also in the electrode support, instead of the sintered electrode, an electrode (Sponge Metal Nickel Elec) in which a three-dimensional foamed nickel porous body having a high porosity (95% or more) is densely filled with nickel oxide.
trade: SME) has been industrialized to achieve high energy density. As described above, the alkaline storage battery has been focused on the miniaturization, weight reduction, and high energy density of the battery.
【０００３】一方、アルカリ蓄電池の電気自動車・電動
工具等への利用を考えた場合、電池の高出力化、つまり
高率放電時における作動電圧の向上が重要な課題とな
る。また、各種ポータブル機器も定電力放電で作動する
ものが多く、放電電圧が低下する放電末期には高率放電
状態となり、一層の放電電圧の低下が生じる。したがっ
て、小型密閉アルカリ蓄電池においても作動電圧の向上
が重要な課題である。On the other hand, when considering the use of an alkaline storage battery in an electric vehicle, a power tool, or the like, it is important to increase the output of the battery, that is, to improve the operating voltage during high-rate discharge. In addition, many portable devices also operate with constant power discharge. At the end of discharge when the discharge voltage decreases, a high-rate discharge state occurs, and the discharge voltage further decreases. Therefore, it is an important issue to improve the operating voltage even in a small sealed alkaline storage battery.
【０００４】この課題の解決策として、例えば特開平５
−１７４８６７号公報では、アルカリ電解液中に水酸化
ルビジウムおよび水酸化セシウムのうち少なくとも１種
の水酸化物を０．３規定〜３．５規定添加することによ
って、電解液の導電性が向上し、かつルビジウムイオン
およびセシウムイオンが触媒として作用するため、高率
放電時において作動電圧を高めることができることが記
載されている。しかし、ルビジウムおよびセシウムとい
った高価な材料を実際の電池へ使用することは困難であ
り、実用化されていない。As a solution to this problem, for example, Japanese Unexamined Patent Application Publication No.
In JP-A-174867, the conductivity of the electrolytic solution is improved by adding at least one hydroxide of rubidium hydroxide and cesium hydroxide to the alkaline electrolyte in a range of 0.3N to 3.5N. Further, it is described that since the rubidium ion and the cesium ion act as catalysts, the operating voltage can be increased during high-rate discharge. However, it is difficult to use expensive materials such as rubidium and cesium for actual batteries, and they have not been put to practical use.
【０００５】一方、米国特許５５６７５４９号（１９９
６）には、Ｎｉ（ＯＨ）2へＡｌを固溶させたアルカリ
蓄電池用正極活物質について記載されている。その内溶
は、Ｎｉ（ＯＨ）2へＡｌを固溶させることによりα−
Ｎｉ（ＯＨ）2相が安定化され、このα相を含有する多
相Ａｌ固溶Ｎｉ（ＯＨ）2は高次反応を行なうため、電
池の高容量化が実現できるというものである。On the other hand, US Pat. No. 5,567,549 (199)
6) describes a positive electrode active material for alkaline storage batteries in which Al is dissolved in Ni (OH) 2 . The internal solution is formed by dissolving Al in Ni (OH) 2 to form α-
The Ni (OH) 2 phase is stabilized, and the multi-phase Al solid solution Ni (OH) 2 containing the α-phase performs a higher-order reaction, so that a higher capacity of the battery can be realized.
【０００６】我々も、Ｎｉ（ＯＨ）2へのＡｌ添加の効
果について研究を行なったところ、Ａｌを共晶状態およ
び／または固溶状態でＮｉ（ＯＨ）2に添加する（以
下、Ａｌ固溶Ｎｉ（ＯＨ）2と略する）ことにより、前
記米国特許５５６７５４９号記載の効果の他にも、放電
電圧向上、高率放電特性向上の効果が得られることが分
かった。特に、Ｘ線回折パターンにおいてα−Ｎｉ（Ｏ
Ｈ）2に帰属する回折線を示すＡｌ固溶Ｎｉ（ＯＨ）
2（以下、α類似型Ａｌ固溶Ｎｉ（ＯＨ）2と略する）に
おいて顕著な効果が得られることが分かった。[0006] We also, was carried out a study on the effect of Al addition to the Ni (OH) 2, Al is added to the Ni (OH) 2 in a eutectic state and / or solid-solution state (hereinafter, Al solid solution Ni (OH) 2 ) has the effect of improving the discharge voltage and improving the high-rate discharge characteristics in addition to the effects described in US Pat. No. 5,567,549. In particular, in the X-ray diffraction pattern, α-Ni (O
H) Al solid solution Ni (OH) showing diffraction lines belonging to 2 )
2 (hereinafter abbreviated as α-similar type Al solid solution Ni (OH) 2 ) was found to have a remarkable effect.
【０００７】ところでα類似型Ｎｉ（ＯＨ）2について
は、Ｎｉ（ＯＨ）2のＮｉの一部を酸化数の高い金属原
子（例えばＣｏ（III）、Ｍｎ（III）、Ｆｅ（III）な
ど）で置換することで得られることが報告されており
（Ｓｏｌｉｄ Ｓｔａｔｅ Ｉｏｎｉｃｓ ３２／３
３， ｐ．１０４ （１９８９）、Ｊ． Ｐｏｗｅｒ
Ｓｏｕｒｃｅｓ， ３５， ｐ．２４９ （１９９１）
など）、酸化数の高い金属原子が固溶したために結晶構
造中のニッケルプレート層が正に帯電し、電荷補償とし
て層間にアニオン種（例えばＰＯ4 3-、ＳＯ4 2-、ＣＯ3
2-、ＮＯ3 -など）が入り込み、層間が広がった構造を持
つと考えられている（Ｊ． Ｐｏｗｅｒ Ｓｏｕｒｃｅ
ｓ， ３６， ｐ．１１３ （１９９１）、Ｍａｔｅｒ
ｉａｌｓ Ｓｃｉｅｎｃｅ Ｆｏｒｕｍ， １５２−１
５３， ｐ．２０１ （１９９４）など）。したがっ
て、α類似型Ｎｉ（ＯＨ）2は嵩高く、高密度充填が困
難であると考えられるが、我々が検討を行なったα類似
型Ａｌ固溶Ｎｉ（ＯＨ）2に関しても、放電電圧、高率
放電特性、利用率は顕著に向上するものの、充填密度が
きわめて低く、アルカリ蓄電池用正極活物質として使用
できるものではなかった。[0007] The way α similar type Ni (OH) 2 is, Ni (OH) 2 in part a high oxidation number metal atoms of Ni (e.g., Co (III), Mn (III ), Fe (III) , etc.) (Solid State Ionics 32/3).
3, p. 104 (1989); Power
Sources, 35, p. 249 (1991)
), And the nickel plate layer in the crystal structure is positively charged due to solid solution of metal atoms having a high oxidation number, and anion species (for example, PO 4 3− , SO 4 2− , CO 3
2-, NO 3 -, etc.) enters, it is believed to have the interlayer is widened structure (J. Power Source
s, 36, p. 113 (1991), Mater
ials Science Forum, 152-1
53, p. 201 (1994)). Therefore, it is considered that α-like Ni (OH) 2 is bulky and difficult to fill at high density. However, with regard to α-like Al solid solution Ni (OH) 2 which we studied, the discharge voltage and high Although the rate-discharge characteristics and the utilization factor were remarkably improved, the packing density was extremely low and could not be used as a positive electrode active material for an alkaline storage battery.
【０００８】また、正極活物質の傾斜機能化による特性
改善についても、これまでに多数報告されている。例え
ば特開平９−１７４２８号公報では、Ｎｉ（ＯＨ）2ま
たはＮｉ（ＯＨ）2を主成分とする粒子表面をＣｏおよ
び／もしくはＮｉ添加物で被覆することによって、利用
率を向上させ、放電容量を増大できることが報告されて
いる。また、特開平８−２８７９０７号公報では、Ｎｉ
（ＯＨ）2またはＮｉ（ＯＨ）2を主成分とする粒子表面
をＩＩ族元素の化合物を主成分とする第１化合物で被覆
し、さらにその表面をＣｏ化合物を主成分とする第２化
合物層で被覆した正極活物質を用いることによって、高
容量、かつ長寿命のアルカリ蓄電池を提供できることが
報告されている。さらに特開平８−３２９９４３号公報
では、ＣａをＮｉ（ＯＨ）2粒子に固溶させると同時
に、含有Ｃａの少なくとも一部を、Ｃａ（ＯＨ）2とし
てＮｉ（ＯＨ）2粒子の表面および細孔内部に被覆、含
浸させた正極活物質を用いることによって、利用率、特
に高温における利用率を高めたアルカリ蓄電池を提供で
きることが報告されている。しかしながら、正極活物質
の傾斜機能化による放電電圧、高率放電特性の改善に関
しては、これまでに何等報告されていない。[0008] Also, many reports have been made on the improvement of the characteristics of the positive electrode active material by functionalizing the positive electrode. For example, in Japanese Patent Application Laid-Open No. Hei 9-17428, the utilization rate is improved by coating the surface of particles containing Ni (OH) 2 or Ni (OH) 2 as a main component with a Co and / or Ni additive to improve the discharge capacity. Can be increased. In Japanese Patent Application Laid-Open No. 8-287907, Ni
A particle surface mainly composed of (OH) 2 or Ni (OH) 2 is coated with a first compound mainly composed of a compound of a group II element, and the surface is further coated with a second compound layer mainly composed of a Co compound. It has been reported that the use of a positive electrode active material coated with an alkaline storage battery can provide a high-capacity and long-life alkaline storage battery. Further, in Japanese Patent Application Laid-Open No. 8-329943, at the same time that Ca is dissolved in Ni (OH) 2 particles, at least a part of the contained Ca is converted into Ca (OH) 2 and the surface and pores of the Ni (OH) 2 particles are reduced. It is reported that by using a positive electrode active material coated and impregnated in the inside, an alkaline storage battery having an increased utilization factor, particularly a utilization factor at a high temperature, can be provided. However, there is no report on the improvement of the discharge voltage and the high-rate discharge characteristics by making the positive electrode active material have a gradient function.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、高容量密度
かつ放電電圧、高率放電特性に優れたアルカリ蓄電池用
正極活物質を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electrode active material for an alkaline storage battery having a high capacity density, excellent discharge voltage and high rate discharge characteristics.
【００１０】[0010]
【課題を解決するための手段】Ｎｉを主たる金属元素と
する複数金属元素の酸化物（または水酸化物）を主材料
とするアルカリ蓄電池用正極に使用する活物質粉末にお
いて、前記複数金属元素の酸化物（または水酸化物）粉
末の表面層付近に、Ａｌが共晶状態および／または固溶
状態で存在するα類似型Ｎｉ（ＯＨ）2層を配する。こ
のα類似型Ａｌ固溶Ｎｉ（ＯＨ）2層は放電電圧、高率
放電特性を向上させる作用を有する。本来、α類似型Ａ
ｌ固溶Ｎｉ（ＯＨ）2は嵩高く、高密度充填が困難であ
るが、表面層付近にのみ配するため充填密度の低下は抑
止でき、高容量密度を維持できる。さらに、上記α類似
型Ａｌ固溶Ｎｉ（ＯＨ）2被覆層にＣａ，Ｃｒ，Ｙ，Ｔ
ｉ，Ｃｏから選ばれる少なくとも一種の元素を共晶状態
および／または固溶状態で添加することにより、放電電
圧、高率放電特性、高密度充填に優れ、かつ高温充電効
率および／または充放電特性にも優れたアルカリ蓄電池
用正極活物質が得られる。また、上記α類似型Ａｌ固溶
Ｎｉ（ＯＨ）2被覆正極活物質粉末の表面をさらにＣｏ
酸化物層で被覆することにより、放電電圧、高率放電特
性、高密度充填に優れ、かつ充放電特性にも優れたアル
カリ蓄電池用正極活物質が得られる。According to the present invention, there is provided an active material powder for use in a positive electrode for an alkaline storage battery mainly comprising an oxide (or hydroxide) of a plurality of metal elements mainly composed of Ni. An α-like Ni (OH) 2 layer in which Al exists in a eutectic state and / or a solid solution state is disposed near the surface layer of the oxide (or hydroxide) powder. The α-like Al solid solution Ni (OH) 2 layer has the function of improving the discharge voltage and the high-rate discharge characteristics. Originally, α-similar type A
Although l-dissolved Ni (OH) 2 is bulky and difficult to pack at high density, since it is arranged only near the surface layer, a decrease in packing density can be suppressed and high capacity density can be maintained. Further, Ca, Cr, Y, T is added to the α-similar Al solid solution Ni (OH) 2 coating layer.
By adding at least one element selected from i and Co in a eutectic state and / or a solid solution state, it is excellent in discharge voltage, high-rate discharge characteristics, high-density filling, and high-temperature charge efficiency and / or charge-discharge characteristics. Thus, an excellent positive electrode active material for an alkaline storage battery can be obtained. Further, the surface of the α-similar Al solid solution Ni (OH) 2 -coated positive electrode active material powder is further coated with Co.
By coating with an oxide layer, a positive electrode active material for an alkaline storage battery having excellent discharge voltage, high-rate discharge characteristics, high-density filling, and excellent charge-discharge characteristics can be obtained.
【００１１】ここで本発明は、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2が正極活物質粒子内部に存在する（米国特許
５５６７５４９号（１９９６））のではなく、正極活物
質粒子表面に配されていることに特徴を有する。このよ
うな構成とすることにより、正極活物質の高密度充填が
可能となる。また、正極活物質粒子への異種金属元素固
溶に関しても、正極活物質粒子内部および／または正極
活物質粒子表面に配する（特開平９−１７４２８号公
報、特開平８−３２９９４３号公報など）のではなく、
正極活物質粒子表面に配されたα類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層に添加することに特徴を有する。この
ような構成とすることにより、放電電圧、高率放電特性
を向上させ、かつその他の特性が改善された正極活物質
が可能となる。さらに、正極活物質粒子とその表面のＣ
ｏ酸化物被覆層との間にα類似型Ａｌ固溶Ｎｉ（ＯＨ）
2層を配することに特徴を有する。このような構成とす
ることにより、放電電圧、高率放電特性を向上させ、か
つ充放電特性が改善された正極活物質が可能となる。Here, the present invention relates to an α-like Al solid solution Ni
It is characterized in that (OH) 2 is not present inside the positive electrode active material particles (US Pat. No. 5,567,549 (1996)) but is disposed on the surface of the positive electrode active material particles. With such a configuration, high-density filling of the positive electrode active material is possible. Further, regarding the dissolution of a different metal element in the positive electrode active material particles, the dissolution is disposed inside the positive electrode active material particles and / or on the surface of the positive electrode active material particles (JP-A-9-17428, JP-A-8-329943, etc.). rather than,
Α-like Al solid solution Ni on the surface of positive electrode active material particles
It is characterized in that it is added to the (OH) 2 coating layer. With such a configuration, a positive electrode active material having improved discharge voltage and high-rate discharge characteristics and improved other characteristics can be obtained. Further, the positive electrode active material particles and the C
αAl-type solid solution Ni (OH) between oxide coating layer
It is characterized by two layers. With such a configuration, a positive electrode active material having improved discharge voltage, high-rate discharge characteristics, and improved charge / discharge characteristics can be obtained.
【００１２】[0012]
【発明の実施の形態】本発明はＮｉを主たる金属元素と
する複数金属元素の酸化物または水酸化物を主材料とす
るアルカリ蓄電池用正極活物質粉末において、前記複数
金属元素の酸化物または水酸化物粉末の表面層付近に、
Ａｌが共晶状態および／または固溶状態で存在するα類
似型Ｎｉ（ＯＨ）2層を配したことを特徴とする。ここ
で、α類似型Ｎｉ（ＯＨ）2被覆層中に共晶状態および
／または固溶状態で存在するＡｌ量は、α類似型Ｎｉ
（ＯＨ）2被覆層中の金属原子比をＮｉ：Ａｌ＝１−
ｘ：ｘと表した場合、０．１０≦ｘ≦０．４０であるこ
とを特徴とする。これにより、高容量密度かつ放電電
圧、高率放電特性に優れたアルカリ蓄電池用正極活物質
が提供できる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a positive electrode active material powder for an alkaline storage battery mainly composed of an oxide or hydroxide of a plurality of metal elements containing Ni as a main metal element. Near the surface layer of the oxide powder,
An alpha-like Ni (OH) 2 layer in which Al exists in a eutectic state and / or a solid solution state is provided. Here, the amount of Al existing in the eutectic state and / or in the solid solution state in the α-like Ni (OH) 2 coating layer is the α-like Ni
The metal atomic ratio in the (OH) 2 coating layer was Ni: Al = 1−
x: when expressed as x, 0.10 ≦ x ≦ 0.40. This can provide a positive electrode active material for an alkaline storage battery having a high capacity density and excellent discharge voltage and high rate discharge characteristics.
【００１３】さらに本発明は、前記複数金属元素の酸化
物または水酸化物粉末の表面層付近に配された前記α類
似型Ｎｉ（ＯＨ）2層中に、Ｎｉ，Ａｌの他に、Ｃａ，
Ｃｒ，Ｙ，Ｔｉ，Ｃｏから選ばれる少なくとも一種の元
素が共晶状態および／または固溶状態で存在することを
特徴とする。ここで、Ｃａ，Ｃｒ，Ｙ，Ｔｉ，Ｃｏから
選ばれる少なくとも一種の元素をＭｅと表した時、α類
似型Ｎｉ（ＯＨ）2層中に共晶状態および／または固溶
状態で存在するＭｅ量は、α類似型Ｎｉ（ＯＨ）2被覆
層中の金属原子比をＮｉ＋Ａｌ：Ｍｅ＝１−ｙ：ｙと表
した場合、０．０１≦ｙ≦０．２０であることを特徴と
する。これにより、容量密度、放電電圧、高率放電特性
に優れ、かつ高温充電効率および／または充放電特性に
優れたアルカリ蓄電池用正極活物質が提供できる。Further, the present invention provides the α-like Ni (OH) 2 layer disposed near the surface layer of the oxide or hydroxide powder of a plurality of metal elements, in addition to Ni and Al, Ca,
At least one element selected from Cr, Y, Ti, and Co exists in a eutectic state and / or a solid solution state. Here, when at least one element selected from Ca, Cr, Y, Ti, and Co is represented by Me, Me present in a eutectic state and / or a solid solution state in the α-like Ni (OH) 2 layer The amount is characterized by 0.01 ≦ y ≦ 0.20 when the metal atom ratio in the α-like Ni (OH) 2 coating layer is represented by Ni + Al: Me = 1−y: y. Thereby, it is possible to provide a positive electrode active material for an alkaline storage battery having excellent capacity density, discharge voltage, high rate discharge characteristics, and high temperature charging efficiency and / or charge / discharge characteristics.
【００１４】さらに本発明は、前記α類似型Ｎｉ（Ｏ
Ｈ）2層を表面層付近に配した前記粉末の表面に、さら
にＣｏ酸化物層を配したことを特徴とする。これによ
り、容量密度、放電電圧、高率放電特性に優れ、かつ充
放電特性に優れたアルカリ蓄電池用正極活物質が提供で
きる。Further, the present invention relates to the above-mentioned α-like Ni (O
H) A Co oxide layer is further provided on the surface of the powder in which two layers are provided near the surface layer. Thereby, it is possible to provide a positive electrode active material for an alkaline storage battery having excellent capacity density, discharge voltage, high rate discharge characteristics, and excellent charge / discharge characteristics.
【００１５】[0015]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００１６】（実施例１）まず、正極活物質表面へのα
類似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆の効果について調べ
た。 （１）ＮｉＳＯ4水溶液、ＮａＯＨ水溶液、ＮＨ3水溶液
を一定流量で連続的に反応槽中に供給し、槽内温度を３
０℃、槽内溶液のｐＨ値を約１１に保った状態で撹拌・
混合を行ない、Ｎｉ（ＯＨ）2粒子を成長させた。採取
したＮｉ（ＯＨ）2粒子を水洗・乾燥し、従来Ｎｉ（Ｏ
Ｈ）2粉末Αとした。 （２）Ｎｉ（ＮＯ3）2，Ｃｏ（ＮＯ3）2およびＣｄ（Ｎ
Ｏ3）2の混合水溶液（Ｎｉ：Ｃｏ：Ｃｄ＝０．９４：
０．０３：０．０３（原子比））を用い、上記と同様の
合成・処理を行ない、従来Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）
2粉末Ｂとした。 （３）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
ＮｉＳＯ4およびＡｌ2（ＳＯ4）3の混合水溶液（Ｎｉ：
Ａｌ＝０．８０：０．２０（原子比））、ＮａＯＨ水溶
液、ＮＨ3水溶液を一定流量で連続的に反応槽中に供給
し、槽内温度を３０℃、槽内溶液のｐＨ値を約１１に保
った状態で撹拌混合を行ない、Ｎｉ（ＯＨ）2粒子表面
にＡｌ固溶Ｎｉ（ＯＨ）2を析出させ被覆を行なった。
採取した粒子を水洗・乾燥し、Ａｌ固溶Ｎｉ（ＯＨ）2
被覆Ｎｉ（ＯＨ）2粉末Ｃとした。 （４）従来Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｂについ
て上記と同様の被覆処理を行ない、Ａｌ固溶Ｎｉ（Ｏ
Ｈ）2被覆Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｄとした。Example 1 First, α was applied to the surface of the positive electrode active material.
The effect of similar type Al solid solution Ni (OH) 2 coating was investigated. (1) A NiSO 4 aqueous solution, a NaOH aqueous solution, and an NH 3 aqueous solution are continuously supplied at a constant flow rate into the reaction tank, and the temperature in the tank is set to 3
Stir at 0 ° C with the pH value of the solution in the tank kept at about 11.
Mixing was performed to grow Ni (OH) 2 particles. The collected Ni (OH) 2 particles are washed with water and dried to obtain a Ni (O) 2 particle.
H) 2 powderΑ. (2) Ni (NO 3 ) 2 , Co (NO 3 ) 2 and Cd (N
O 3 ) 2 mixed aqueous solution (Ni: Co: Cd = 0.94:
0.03: 0.03 (atomic ratio), the same synthesis and processing as described above were performed, and the conventional Co, Cd solid solution Ni (OH)
2 Powder B was obtained. (3) Conventional Ni (OH) 2 powder Α is charged into the reaction vessel,
A mixed aqueous solution of NiSO 4 and Al 2 (SO 4 ) 3 (Ni:
Al = 0.80: 0.20 (atomic ratio), an aqueous solution of NaOH and an aqueous solution of NH 3 are continuously supplied into the reaction vessel at a constant flow rate, the temperature in the vessel is 30 ° C., and the pH value of the solution in the vessel is about While keeping the temperature at 11, stirring and mixing were carried out to deposit Al-dissolved Ni (OH) 2 on the surface of the Ni (OH) 2 particles, and coating was performed.
The collected particles are washed with water and dried to obtain a solid solution of Ni (OH) 2
A coated Ni (OH) 2 powder C was obtained. (4) The same coating treatment as described above was performed on the conventional Co, Cd solid solution Ni (OH) 2 powder B to obtain the Al solid solution Ni (O
H) 2 coated Co, Cd solid solution Ni (OH) 2 powder D.
【００１７】以上の粉末の被覆層は粉末断面のＡｌ特性
Ｘ線像にてＡｌの存在を確認した。また、粉末Ａ，Ｂの
Ｘ線回折パターンにはβ−Ｎｉ（ＯＨ）2に帰属する回
折線のみが現れるのに対し、被覆処理粉末Ｃ，ＤのＸ線
回折パターンには新たにα−Ｎｉ（ＯＨ）2に帰属する
回折線が現れることより、被覆層がα類似型Ａｌ固溶Ｎ
ｉ（ＯＨ）2相を含むことを確認した。被覆粉末のタッ
プ密度は１．９ｇ／ｃｃ〜２．０ｇ／ｃｃと良好であっ
た。The presence of Al in the powder coating layer was confirmed by an Al characteristic X-ray image of the powder cross section. Further, while only the diffraction lines belonging to β-Ni (OH) 2 appear in the X-ray diffraction patterns of powders A and B, the α-Ni Since the diffraction line belonging to (OH) 2 appears, the coating layer is made of α-like Al solid solution N
It was confirmed to contain i (OH) 2 phase. The tap density of the coated powder was as good as 1.9 g / cc to 2.0 g / cc.
【００１８】合成粉末１００ｇに１０ｇのＣｏ（ＯＨ）
2粉末、０．５ｇのポリテトラフルオロエチレン（ＰＴ
ＦＥ）粉末、４２ｇの水を加え混練しペースト状にし
た。これを多孔度９５％の発泡ニッケル基板に充填し、
乾燥後加圧成形し、厚さ０．７ｍｍ、容量密度約６３０
ｍＡｈ／ｃｃのニッケル正極板を得た。このようにして
得られた正極板を３９×７５ｍｍに切断し、基板中にあ
らかじめ設けたリード接続部に電極リードをスポット溶
接し、理論容量１３００ｍＡｈのニッケル正極とした。
ここで理論容量はＮｉのみが充放電に寄与すると仮定
し、かつＮｉに対し１電子反応をするとして算定したも
のである。10 g of Co (OH) is added to 100 g of the synthetic powder.
2 powder, 0.5 g of polytetrafluoroethylene (PT
FE) Powder and 42 g of water were added and kneaded to form a paste. This is filled into a 95% porosity nickel foam substrate,
After drying, press molding, thickness 0.7mm, capacity density about 630
A mAh / cc nickel positive electrode plate was obtained. The positive electrode plate thus obtained was cut into a size of 39 × 75 mm, and an electrode lead was spot-welded to a lead connection portion provided in advance on the substrate to obtain a nickel positive electrode having a theoretical capacity of 1300 mAh.
Here, the theoretical capacity is calculated by assuming that only Ni contributes to charge and discharge and assuming a one-electron reaction with Ni.
【００１９】一方負極には正極に対しその容量が十分大
きい水素吸蔵合金負極（ＭｍＮｉ3. 8Ｃｏ0.5Ｍｎ0.4Ａ
ｌ0.3）を用いた。使用した水素吸蔵合金は所望の割合
で混合したＭｍ，Ｎｉ，Ｃｏ，Ｍｎ，Ａｌをアーク溶解
炉にて溶解することによって得た。この合金塊を不活性
雰囲気中でボールミルにて粉砕し、平均粒径３０μｍの
粉末とした。これに結着剤としてカルボキシメチルセル
ロース（ＣＭＣ）を加えた後混練し、電極支持体に加圧
充填し、厚さ０．４５ｍｍ、容量密度１３５０ｍＡｈ／
ｃｃの水素吸蔵負極板を得た。この負極板を３９×１０
０ｍｍに切断し理論容量２４００ｍＡｈの負極とした。Meanwhile its capacity to the positive electrode to the negative electrode is sufficiently large hydrogen storage alloy negative electrode (MmNi 3. 8 Co 0.5 Mn 0.4 A
l 0.3 ) was used. The used hydrogen storage alloy was obtained by melting Mm, Ni, Co, Mn, and Al mixed in a desired ratio in an arc melting furnace. This alloy lump was pulverized by a ball mill in an inert atmosphere to obtain a powder having an average particle diameter of 30 μm. After adding carboxymethylcellulose (CMC) as a binder to the mixture and kneading the mixture, the mixture was pressure-filled into an electrode support, and had a thickness of 0.45 mm and a capacity density of 1350 mAh /
cc of the hydrogen storage negative electrode plate was obtained. 39 × 10
It was cut into 0 mm to obtain a negative electrode having a theoretical capacity of 2400 mAh.
【００２０】この正極と負極を厚さ０．１５ｍｍのスル
フォン化ポリプロピレン不織布からなるセパレーターを
間に介して渦巻状の電極群に構成し、この電極群を外装
缶内に挿入した。電解液として７．２ｍｏｌ／ｌＫＯＨ
＋１．０ｍｏｌ／ｌＬｉＯＨ混合アルカリ水溶液を前記
電極群を挿入した外装缶内に注入後、作動弁圧が２０kg
f／cm2の安全弁を持つ封口体により密閉し、公称容量が
１３００ｍＡｈであるＡＡサイズの円筒密閉形ニッケル
・水素蓄電池を作製した。The positive and negative electrodes were formed into a spiral electrode group with a separator made of a sulfonated polypropylene nonwoven fabric having a thickness of 0.15 mm therebetween, and this electrode group was inserted into an outer can. 7.2 mol / l KOH as electrolyte
After injecting +1.0 mol / l LiOH mixed alkaline aqueous solution into the outer can into which the electrode group was inserted, the operating valve pressure was reduced to 20 kg.
The container was sealed with a sealing member having a safety valve of f / cm 2 to produce an AA-size cylindrical sealed nickel-metal hydride storage battery having a nominal capacity of 1300 mAh.
【００２１】この電池を充放電試験によって評価した。
充電を０．１Ｃで１５時間、放電は１．０Ｃで終止電圧
１．０Ｖまで、雰囲気温度は２０℃とした。なお、電池
の活性化が終了するまで数サイクル要するため、１０サ
イクルめの平均放電電圧、利用率を比較値とした。ここ
で利用率は、上記正極の理論容量に対する１．０Ｃの測
定容量の比率を％で表したものである。その結果を表１
に示す。This battery was evaluated by a charge / discharge test.
The charging was performed at 0.1 C for 15 hours, the discharging was performed at 1.0 C to a final voltage of 1.0 V, and the ambient temperature was set at 20 ° C. Since several cycles are required until the activation of the battery is completed, the average discharge voltage and utilization rate at the tenth cycle were used as comparative values. Here, the utilization rate represents a ratio of the measured capacity of 1.0 C to the theoretical capacity of the positive electrode in%. Table 1 shows the results.
Shown in
【００２２】[0022]
【表１】 [Table 1]
【００２３】α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆処理
を施したＮｉ（ＯＨ）2粉末Ｃにおいて、処理前の従来
Ｎｉ（ＯＨ）2粉末Αに比べ、４０ｍＶの放電電圧の向
上が確認された。また、α類似型Ａｌ固溶Ｎｉ（ＯＨ）
2被覆処理を施したＣｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｄ
においても、処理前の従来Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）
2粉末Ｂに比べ、４０ｍＶの放電電圧の向上が確認され
た。以上の結果から、α類似型Ａｌ固溶Ｎｉ（ＯＨ）2
被覆処理により、放電電圧向上が可能であることが明ら
かである。It has been confirmed that the Ni (OH) 2 powder C coated with α-similar type Al solid solution Ni (OH) 2 has an improved discharge voltage of 40 mV compared to the conventional Ni (OH) 2 powder before the treatment. Was done. Also, α-similar type Al solid solution Ni (OH)
2 Co, Cd solid solution Ni (OH) 2 powder D
Also, the conventional Co, Cd solid solution Ni (OH)
(2 ) An improvement in discharge voltage of 40 mV as compared with Powder B was confirmed. From the above results, α-similar type Al solid solution Ni (OH) 2
It is clear that the coating treatment can improve the discharge voltage.
【００２４】また、粉末Ａ，Ｂを比較した場合、Ｃｏ，
Ｃｄを固溶させた粉末Ｂの利用率が高く、充放電特性が
優れている。Ｎｉ（ＯＨ）2へのＣｏ，Ｃｄ固溶による
充放電特性向上については日本国特許１８２７６３９号
（１９８４）および特開平３−５０３８４号公報に記載
されている。α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆処理
を施した粉末Ｃ，Ｄを比較した場合にも同様の効果が認
められることから、α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被
覆処理は、内部粒子の特性を損なうことなく、放電電圧
向上が可能であることが明らかである。When powders A and B were compared, Co,
The utilization rate of the powder B in which Cd is dissolved is high, and the charge and discharge characteristics are excellent. Improvement of charge / discharge characteristics by dissolving Co and Cd in Ni (OH) 2 is described in Japanese Patent No. 1827639 (1984) and Japanese Patent Application Laid-Open No. H3-50384. alpha similar type Al solid solution Ni (OH) powder C was subjected to 2 coated processing, since the observed similar effects when compared to D, alpha similar type Al solid solution Ni (OH) 2 coating process, It is clear that the discharge voltage can be improved without impairing the characteristics of the internal particles.
【００２５】（実施例２）次に、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層中のＡｌ固溶量の適切値を求めるため
に、実施例１で用いた従来Ｎｉ（ＯＨ）2粉末Αを反応
槽中に投入し、種々のＮｉＳＯ4およびＡｌ2（ＳＯ4）3
の混合水溶液（Ｎｉ：Ａｌ＝１−ｘ：ｘ，ｘ＝０．０
５，０．１０，０．３０，０．４０，０．４５（原子
比））を用い、実施例１と同様の被覆処理を行ない、Ａ
ｌ固溶Ｎｉ（ＯＨ）2被覆Ｎｉ（ＯＨ）2粉末Ε〜Ｉとし
た。被覆粉末のタップ密度は１．８ｇ／ｃｃ〜２．０ｇ
／ｃｃと良好であった。得られた粉末Ε〜Ｉを用い、実
施例１と同様の製法で電池を作製し、同様の方法で充放
電試験により評価した。得られた結果を表２に示す。(Example 2) Next, α-like Al solid solution Ni
To obtain an appropriate value of the amount of solid solution of Al in the (OH) 2 coating layer, the conventional Ni (OH) 2 powder used in Example 1 was charged into a reaction vessel, and various NiSO 4 and Al 2 ( SO 4 ) 3
(Ni: Al = 1-x: x, x = 0.0
5, 0.10, 0.30, 0.40, 0.45 (atomic ratio)), and the same coating treatment as in Example 1 was performed.
1 Solid solution Ni (OH) 2 coated Ni (OH) 2 powder Tap density of coated powder is 1.8g / cc-2.0g
/ Cc, which was good. Using the obtained powders I to I, a battery was produced in the same manner as in Example 1, and evaluated by a charge / discharge test in the same manner. Table 2 shows the obtained results.
【００２６】[0026]
【表２】 [Table 2]
【００２７】放電電圧向上の効果は、被覆層のＡｌ固溶
比が０．１０〜０．４５の場合に確認されたが、０．０
５の場合には確認されなかった。被覆粉末Ｃ，Ｆ〜Ｉの
Ｘ線回折パターンにはα−Ｎｉ（ＯＨ）2に帰属する回
折線が現れるのに対し、被覆粉末ＥのＸ線回折パターン
にはα−Ｎｉ（ＯＨ）2に帰属する回折線が現れなかっ
た。すなわち、被覆粉末Ｃ，Ｆ〜Ｉの被覆層はα類似型
Ａｌ固溶Ｎｉ（ＯＨ） 2相を含むため放電電圧が向上す
るが、被覆粉末Ｅの被覆層はα類似型Ａｌ固溶Ｎｉ（Ｏ
Ｈ）2相を含まないため放電電圧向上の効果が現れない
と推察される。しかし、Ａｌ固溶比が０．４５の被覆粉
末Ｉでは利用率の低下が確認され、容量密度の点で問題
である。The effect of improving the discharge voltage is as follows.
It was confirmed when the ratio was 0.10 to 0.45, but 0.0
In the case of 5, it was not confirmed. Of coated powders C, FI
Α-Ni (OH) for X-ray diffraction patternTwoTimes belonging to
X-ray diffraction pattern of the coated powder E
Contains α-Ni (OH)TwoNo diffraction line attributed to
Was. That is, the coating layers of the coating powders C and F to I are α-similar types.
Al solid solution Ni (OH) TwoIncludes phases to improve discharge voltage
However, the coating layer of the coating powder E is α-like Al solid solution Ni (O
H)TwoNo effect of improving discharge voltage because no phase is included
It is inferred. However, a coating powder having an Al solid solution ratio of 0.45
At the end I, a decrease in the utilization rate was confirmed, and there was a problem with the
It is.
【００２８】以上より、放電電圧向上の効果はα類似型
Ａｌ固溶Ｎｉ（ＯＨ）2被覆処理で得られ、その場合の
Ａｌ固溶比は被覆層中のＮｉとＡｌの総原子数に対し
０．１０〜０．４０である。From the above, the effect of improving the discharge voltage can be obtained by the α-like Al solid solution Ni (OH) 2 coating treatment. In this case, the Al solid solution ratio is based on the total number of atoms of Ni and Al in the coating layer. 0.10 to 0.40.
【００２９】（実施例３）次に、α類似型Ａｌ固溶Ｎｉ
2（ＯＨ）2被覆層中への異種金属固溶効果について調べ
た。 （１）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3およびＣａ（ＮＯ3）2
の混合水溶液（Ｎｉ：Ａｌ：Ｃａ＝０．７５：０．２
０：０．０５（原子比））を用い、実施例１と同様の被
覆処理を行ない、Ａｌ，Ｃａ固溶Ｎｉ（ＯＨ）2被覆Ｎ
ｉ（ＯＨ）2粉末Ｊとした。 （２）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3およびＣｒ（ＮＯ3）3
の混合水溶液（Ｎｉ：Ａｌ：Ｃｒ＝０．７５：０．２
０：０．０５（原子比））を用い、実施例１と同様の被
覆処理を行ない、Ａｌ，Ｃｒ固溶Ｎｉ（ＯＨ）2被覆Ｎ
ｉ（ＯＨ）2粉末Ｋとした。 （３）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3およびＹ（ＮＯ3）3の
混合水溶液（Ｎｉ：Ａｌ：Ｙ＝０．７５：０．２０：
０．０５（原子比））を用い、実施例１と同様の被覆処
理を行ない、Ａｌ，Ｙ固溶Ｎｉ（ＯＨ）2被覆Ｎｉ（Ｏ
Ｈ）2粉末Ｌとした。 （４）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
ＮｉＣｌ2，ＡｌＣｌ3およびＴｉＣｌ3の混合水溶液
（Ｎｉ：Ａｌ：Ｔｉ＝０．７５：０．２０：０．０５
（原子比））を用い、実施例１と同様の被覆処理を行な
い、Ａｌ，Ｔｉ固溶Ｎｉ（ＯＨ）2被覆Ｎｉ（ＯＨ）2粉
末Ｍとした。 （５）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
ＮｉＳＯ4，Ａｌ2（ＳＯ4）3およびＣｏＳＯ4の混合水
溶液（Ｎｉ：Ａｌ：Ｃｏ＝０．７５：０．２０：０．０
５（原子比））を用い、実施例１と同様の被覆処理を行
ない、Ａｌ，Ｃｏ固溶Ｎｉ（ＯＨ）2被覆Ｎｉ（ＯＨ）2
粉末Ｎとした。 （６）従来Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｂを反応
槽中に投入し、Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3および
Ｃａ（ＮＯ3）3の混合水溶液（Ｎｉ：Ａｌ：Ｃａ＝０．
７５：０．２０：０．０５（原子比））を用い、実施例
１と同様の被覆処理を行ない、Ａｌ，Ｃａ固溶Ｎｉ（Ｏ
Ｈ）2被覆Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｏとした。 （７）従来Ｎｉ（ＯＨ）2粉末Αを反応槽中に投入し、
Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3，Ｃａ（ＮＯ3）2およ
びＣｏ（ＮＯ3）2の混合水溶液（Ｎｉ：Ａｌ：Ｃａ：Ｃ
ｏ＝０．７４：０．２０：０．０３：０．０３（原子
比））を用い、実施例１と同様の被覆処理を行ない、Ａ
ｌ，Ｃａ，Ｃｏ固溶Ｎｉ（ＯＨ）2被覆Ｎｉ（ＯＨ）2粉
末Ｐとした。 （８）従来Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｂを反応
槽中に投入し、Ｎｉ（ＮＯ3）2，Ａｌ（ＮＯ3）3，Ｃｒ
（ＮＯ3）3およびＣｏ（ＮＯ3）2の混合水溶液（Ｎｉ：
Ａｌ：Ｃｒ：Ｃｏ＝０．７４：０．２０：０．０３：
０．０３（原子比））を用い、実施例１と同様の被覆処
理を行ない、Ａｌ，Ｃｒ，Ｃｏ固溶Ｎｉ（ＯＨ）2被覆
Ｃｏ，Ｃｄ固溶Ｎｉ（ＯＨ）2粉末Ｑとした。Example 3 Next, α-like Al solid solution Ni
The effect of dissolving dissimilar metals in the 2 (OH) 2 coating layer was investigated. (1) Conventional Ni (OH) 2 powder Α is charged into a reaction vessel,
Ni (NO 3 ) 2 , Al (NO 3 ) 3 and Ca (NO 3 ) 2
(Ni: Al: Ca = 0.75: 0.2)
0: 0.05 with (atomic ratio)) performs the same coating treatment as in Example 1, Al, Ca solid solution Ni (OH) 2-coated N
i (OH) 2 powder J. (2) Conventional Ni (OH) 2 powder Α is charged into a reaction vessel,
Ni (NO 3 ) 2 , Al (NO 3 ) 3 and Cr (NO 3 ) 3
(Ni: Al: Cr = 0.75: 0.2)
0: 0.05 (atomic ratio), and the same coating treatment as in Example 1 was performed to form a Ni (OH) 2 coated N
i (OH) 2 powder K was used. (3) Conventional Ni (OH) 2 powder Α is charged into the reaction vessel,
A mixed aqueous solution of Ni (NO 3 ) 2 , Al (NO 3 ) 3 and Y (NO 3 ) 3 (Ni: Al: Y = 0.75: 0.20:
0.05 (atomic ratio), the same coating treatment as in Example 1 was performed, and the Al, Y solid solution Ni (OH) 2 coated Ni (O
H) 2 powder L. (4) Conventional Ni (OH) 2 powder Α is charged into a reaction vessel,
A mixed aqueous solution of NiCl 2 , AlCl 3 and TiCl 3 (Ni: Al: Ti = 0.75: 0.20: 0.05
(Atomic ratio)) was used, performs the same coating treatment as in Example 1 was Al, and Ti solid solution Ni (OH) 2-coated Ni (OH) 2 powder M. (5) Conventional Ni (OH) 2 powder Α is charged into the reaction vessel,
A mixed aqueous solution of NiSO 4 , Al 2 (SO 4 ) 3 and CoSO 4 (Ni: Al: Co = 0.75: 0.20: 0.0)
5 (atomic ratio)), and the same coating treatment as in Example 1 was performed to form a Ni (OH) 2 coated Ni (OH) 2 solid solution of Al and Co.
Powder N was obtained. (6) Conventionally, Co and Cd solid solution Ni (OH) 2 powder B is charged into a reaction tank, and a mixed aqueous solution of Ni (NO 3 ) 2 , Al (NO 3 ) 3 and Ca (NO 3 ) 3 (Ni: Al: Ca = 0.
75: 0.20: 0.05 (atomic ratio), and the same coating treatment as in Example 1 was performed.
H) 2 coated Co, Cd solid solution Ni (OH) 2 powder O. (7) Conventional Ni (OH) 2 powder Α is charged into a reaction vessel,
A mixed aqueous solution of Ni (NO 3 ) 2 , Al (NO 3 ) 3 , Ca (NO 3 ) 2 and Co (NO 3 ) 2 (Ni: Al: Ca: C
o = 0.74: 0.20: 0.03: 0.03 (atomic ratio), and the same coating treatment as in Example 1 was performed.
The Ni (OH) 2 powder P coated with 1, Ca, Co solid solution Ni (OH) 2 was obtained. (8) Conventionally, a Co, Cd solid solution Ni (OH) 2 powder B is charged into a reaction tank, and Ni (NO 3 ) 2 , Al (NO 3 ) 3 , Cr
(NO 3 ) 3 and Co (NO 3 ) 2 mixed aqueous solution (Ni:
Al: Cr: Co = 0.74: 0.20: 0.03:
0.03 (atomic ratio), and the same coating treatment as in Example 1 was performed to obtain Al, Cr, Co solid solution Ni (OH) 2 coated Co, Cd solid solution Ni (OH) 2 powder Q.
【００３０】これらすべての被覆粉末のＸ線回折パター
ンにα−Ｎｉ（ＯＨ）2に帰属する回折線が現れること
より、被覆層がα類似型Ａｌ，異種金属固溶Ｎｉ（Ｏ
Ｈ）2相を含むことを確認した。被覆粉末のタップ密度
は１．９ｇ／ｃｃ〜２．０ｇ／ｃｃと良好であった。The diffraction layer belonging to α-Ni (OH) 2 appears in the X-ray diffraction patterns of all of these coating powders.
H) It was confirmed that two phases were contained. The tap density of the coated powder was as good as 1.9 g / cc to 2.0 g / cc.
【００３１】得られた粉末Ｊ〜Ｑを用い、実施例１と同
様の製法で電池を作製し、同様の方法で充放電試験によ
り評価した。さらに、雰囲気温度４５℃にて、充電を
０．１Ｃで１５時間行ない、引き続き雰囲気温度２０℃
にて、放電を１．０Ｃで終止電圧１．０Ｖまで行なうこ
とにより、高温充電効率の評価を実施した。得られた結
果を表３に示す。Using the obtained powders J to Q, a battery was produced in the same manner as in Example 1, and evaluated by a charge / discharge test in the same manner. Further, at an ambient temperature of 45 ° C., charging was performed at 0.1 C for 15 hours, and subsequently, an ambient temperature of 20 ° C.
, The high-temperature charging efficiency was evaluated by performing discharge at 1.0 C to a final voltage of 1.0 V. Table 3 shows the obtained results.
【００３２】[0032]
【表３】 [Table 3]
【００３３】これらすべての被覆粉末において放電電圧
向上の効果が確認された。また、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層にＣａ，Ｃｒ，Ｙ，Ｔｉを固溶させた
粉末Ｊ，Ｋ，Ｌ，Ｍ，Ｏにおいて、未固溶のα類似型Ａ
ｌ固溶Ｎｉ（ＯＨ）2粉末Ｃ，Ｄに比べ、高温充電効率
の向上が確認された。The effect of improving the discharge voltage was confirmed in all of these coated powders. Also, α-similar Al solid solution Ni
In powders J, K, L, M, and O in which Ca, Cr, Y, and Ti are dissolved in the (OH) 2 coating layer, α-like A
1) It was confirmed that the high-temperature charging efficiency was improved as compared with the solid solution Ni (OH) 2 powders C and D.
【００３４】さらに、α類似型Ａｌ固溶Ｎｉ（ＯＨ）2
被覆層にＣｏを固溶させた粉末Ｎにおいて、未固溶のα
類似型Ａｌ固溶Ｎｉ（ＯＨ）2粉末Ｃに比べ、利用率の
向上が確認された。Further, α-like Al solid solution Ni (OH) 2
In powder N in which Co is dissolved in the coating layer, undissolved α
The improvement of the utilization rate was confirmed as compared with the similar type Al solid solution Ni (OH) 2 powder C.
【００３５】また、α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被
覆層にＣａ，ＣｏまたはＣｒ，Ｃｏを固溶させた粉末
Ｐ，Ｑにおいて、未固溶のα類似型Ａｌ固溶Ｎｉ（Ｏ
Ｈ）2被覆粉末Ｃ，Ｄに比べ、高温充電効率と利用率の
向上が確認された。Further, in powders P and Q in which Ca, Co or Cr, Co are dissolved in the α-like Al solid solution Ni (OH) 2 coating layer, α-similar Al solid solution Ni (O
H) It was confirmed that the high-temperature charging efficiency and the utilization were improved as compared with the powders C and D coated with 2 ).
【００３６】以上の結果から、上記異種金属元素を固溶
させたα類似型Ａｌ固溶Ｎｉ（ＯＨ）2をＮｉ（ＯＨ）2
粒子に被覆することにより、放電電圧が向上し、かつそ
の他の特性改善も可能であることが明らかである。From the above results, the α-like Al solid solution Ni (OH) 2 in which the above-mentioned dissimilar metal elements are dissolved is converted to Ni (OH) 2
It is clear that by coating the particles, the discharge voltage is improved, and other characteristics can be improved.
【００３７】（実施例４）次に、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層中の異種金属固溶量の適切値を求める
ために、実施例１で用いた従来Ｎｉ（ＯＨ）2粉末Αを
反応槽中に投入し、種々のＮｉ（ＮＯ3）2，Ａｌ（ＮＯ
3）3およびＣａ（ＮＯ3）2の混合水溶液（Ｎｉ：Ａｌ：
Ｃａ＝１−ｙ：０．２０：ｙ ， ｙ＝０．０１，０．
０５，０．１０，０．２０，０．２５（原子比））を用
い、実施例１と同様の被覆処理を行ない、Ａｌ，Ｃａ固
溶Ｎｉ（ＯＨ）2被覆Ｎｉ（ＯＨ）2粉末Ｒ〜Ｕとした。Example 4 Next, α-like Al solid solution Ni
In order to determine an appropriate value of the amount of dissimilar metal solid solution in the (OH) 2 coating layer, the conventional Ni (OH) 2 powder used in Example 1 was charged into the reaction tank, and various Ni (NO 3 ) 2 , Al (NO
3 ) A mixed aqueous solution of 3 and Ca (NO 3 ) 2 (Ni: Al:
Ca = 1-y: 0.20: y, y = 0.01, 0.
05, 0.10, 0.20, 0.25 (atomic ratio), and the same coating treatment as in Example 1 was performed to obtain a Ni (OH) 2 coated Ni (OH) 2 powder R To U.
【００３８】これらすべての被覆粉末のＸ線回折パター
ンにα−Ｎｉ（ＯＨ）2に帰属する回折線が現れること
より、被覆層がα類似型Ａｌ，Ｃａ固溶Ｎｉ（ＯＨ）2
相を含むことを確認した。被覆粉末のタップ密度は１．
８ｇ／ｃｃ〜１．９ｇ／ｃｃと良好であった。Since the X-ray diffraction patterns of all of these coating powders show diffraction lines belonging to α-Ni (OH) 2 , the coating layer is made of α-like Al, Ca solid solution Ni (OH) 2.
Phase. The tap density of the coated powder was 1.
It was as good as 8 g / cc to 1.9 g / cc.
【００３９】得られた粉末Ｒ〜Ｕを用い、実施例１と同
様の製法で電池を作製し、実施例３と同様の方法で充放
電試験により評価した。得られた結果を表４に示す。Using the obtained powders RU, a battery was produced in the same manner as in Example 1 and evaluated by a charge / discharge test in the same manner as in Example 3. Table 4 shows the obtained results.
【００４０】[0040]
【表４】 [Table 4]
【００４１】α類似型Ａｌ，Ｃａ固溶Ｎｉ（ＯＨ）2被
覆層のＣａ固溶比が０．０１〜０．２０の場合に高温充
電効率の向上が確認された。しかし、被覆層のＣａ固溶
比が０．２５の場合には放電電圧、高温充電効率ともに
効果が認められなかった。被覆層にα類似型Ａｌ，Ｃａ
固溶Ｎｉ（ＯＨ）2相を含むにも関わらず、放電電圧が
向上しない原因は明らかではないが、実施例３でα類似
型Ａｌ固溶Ｎｉ（ＯＨ）2層に固溶させたすべての異種
金属において同様の結果が得られ、０．０１〜０．２０
の固溶比の範囲で特性改善の効果が確認された。It was confirmed that the high-temperature charging efficiency was improved when the Ca-dissolved ratio of the α-like Al, Ca-dissolved Ni (OH) 2 coating layer was 0.01 to 0.20. However, when the Ca solid solution ratio of the coating layer was 0.25, no effect was observed in both the discharge voltage and the high-temperature charging efficiency. Α-like Al, Ca
Although it is not clear why the discharge voltage is not improved in spite of the inclusion of the solid solution Ni (OH) 2 phase, all the solid solutions in the α-like Al solid solution Ni (OH) 2 layer in Example 3 were dissolved. Similar results are obtained with dissimilar metals, from 0.01 to 0.20
The effect of improving characteristics was confirmed within the range of the solid solution ratio.
【００４２】以上の結果から、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層に異種金属元素を０．０１〜０．２０
の固溶比の範囲で固溶させた場合、放電電圧が向上し、
かつその他の特性改善が可能であることが明らかであ
る。From the above results, it can be seen that α-similar Al solid solution Ni
(OH) 2 A different metal element is added to the coating layer in an amount of 0.01 to 0.20.
When the solid solution is dissolved within the range of the solid solution ratio, the discharge voltage is improved,
It is clear that other property improvements are possible.
【００４３】（実施例５）次に、α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆正極活物質表面へのＣｏ酸化物被覆の効
果について調べた。Example 5 Next, α-similar Al solid solution Ni
The effect of Co oxide coating on the (OH) 2 -coated positive electrode active material surface was examined.
【００４４】α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆粉末
Ｃ，Ｄ，Ｊ，Ｏを反応槽中に投入し、ＣｏＳＯ4水溶
液、ＮａＯＨ水溶液、ＮＨ3水溶液を一定流量で連続的
に反応槽中に供給し、槽内温度を３０℃、槽内溶液のｐ
Ｈ値を約１１に保った状態で撹拌混合を行ない、粒子表
面にＣｏ（ＯＨ）2を析出させ被覆を行なった。採取し
た粒子を水洗・乾燥し、粉末Ｖ〜Ｙとした。The α-similar Al-dissolved Ni (OH) 2 -coated powder C, D, J, and O are charged into a reaction tank, and a CoSO 4 aqueous solution, an NaOH aqueous solution, and an NH 3 aqueous solution are continuously fed at a constant flow rate into the reaction tank. Into the tank, the temperature in the tank is 30 ° C.,
While the H value was kept at about 11, stirring and mixing were carried out, and Co (OH) 2 was deposited on the particle surface to perform coating. The collected particles were washed and dried to obtain powders V to Y.
【００４５】以上の粉末の被覆層は粉末断面のＣｏ特性
Ｘ線像にてＣｏの存在を確認した。被覆粉末のタップ密
度は１．８ｇ／ｃｃ〜２．０ｇ／ｃｃと良好であった。The presence of Co in the powder coating layer was confirmed by a Co characteristic X-ray image of the powder cross section. The tap density of the coated powder was as good as 1.8 g / cc to 2.0 g / cc.
【００４６】このようにして得られた粉末Ｖ〜Ｙを用
い、実施例１と同様の製法で電池を作製し、同様の方法
で充放電試験により評価した。得られた結果を表５に示
す。Using the powders V to Y obtained as described above, a battery was produced in the same manner as in Example 1, and evaluated by a charge / discharge test in the same manner. Table 5 shows the obtained results.
【００４７】[0047]
【表５】 [Table 5]
【００４８】Ｃｏ（ＯＨ）2被覆粉末Ｖ〜Ｙにおいて、
未処理粉末Ｃ，Ｄ，Ｊ，Ｏと比較して利用率の向上が確
認された。放電電圧はわずかに低下するが、未被覆処理
粉末Ａ，Ｂと比較すると放電電圧は向上しており、α類
似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆処理による放電電圧向
上の効果が確認された。In the Co (OH) 2 coated powders V to Y,
It was confirmed that the utilization rate was improved as compared with the untreated powders C, D, J and O. Although the discharge voltage slightly decreased, the discharge voltage was improved as compared with the uncoated powders A and B, and the effect of improving the discharge voltage by the α-like Al solid solution Ni (OH) 2 coating treatment was confirmed. .
【００４９】Ｎｉ（ＯＨ）2またはＮｉ（ＯＨ）2を主成
分とする粒子表面をＣｏ化合物で被覆することにより、
利用率を向上できることは特開昭６２−２２２５６６号
公報および特開昭６２−２３４８６７号公報に記載され
ている。By coating Ni (OH) 2 or the particle surface mainly composed of Ni (OH) 2 with a Co compound,
The ability to improve the utilization factor is described in JP-A-62-222566 and JP-A-62-234867.
【００５０】本実施例の結果から、正極活物質粒子とそ
の表面のＣｏ酸化物層との間にα類似型Ａｌ固溶Ｎｉ
（ＯＨ）2層を配することによって、利用率を向上さ
せ、さらに放電電圧を向上できることが明らかである。From the results of this example, it can be seen that α-like Al solid solution Ni is present between the positive electrode active material particles and the Co oxide layer on the surface thereof.
It is clear that the use of two (OH) layers can improve the utilization factor and further increase the discharge voltage.
【００５１】なお本発明は、アルカリ蓄電池の正極活物
質の改良に関する技術であるため、実施例に記載した以
外の組成の水素吸蔵合金を用いるニッケル・水素蓄電池
においても同等の効果が得られる。さらにニッケル酸化
物をベースにした正極活物質を用いるすべてのアルカリ
蓄電池（例えば、ニッケル・カドミウム蓄電池、ニッケ
ル・鉄蓄電池、ニッケル・亜鉛蓄電池等）においても同
等の効果が得られる。また、電極支持体、活物質添加物
およびセパレータ等が異なる場合についても同等の効果
が得られる。また、ＡＡサイズの円筒密閉電池について
のみ記載したが他のサイズの円筒密閉電池、角型密閉電
池、据え置き型蓄電池、大型蓄電池、中型蓄電池あるい
は開放型電池等についても同等の効果が得られる。さら
に、焼結式正極を用いるアルカリ蓄電池においても、正
極表面に同様の被覆処理を施した場合に同等の効果が得
られる。Since the present invention relates to a technique for improving a positive electrode active material of an alkaline storage battery, the same effect can be obtained in a nickel-hydrogen storage battery using a hydrogen storage alloy having a composition other than that described in the embodiment. Further, the same effect can be obtained in all alkaline storage batteries using a positive electrode active material based on nickel oxide (for example, nickel-cadmium storage battery, nickel-iron storage battery, nickel-zinc storage battery, etc.). The same effect can be obtained when the electrode support, the active material additive, the separator, and the like are different. Although only the AA size cylindrical sealed battery is described, the same effect can be obtained for other sizes of cylindrical sealed battery, square sealed battery, stationary storage battery, large storage battery, medium storage battery, open battery, and the like. Further, even in an alkaline storage battery using a sintered positive electrode, the same effect can be obtained when the same coating treatment is performed on the positive electrode surface.
【００５２】[0052]
【発明の効果】正極活物質粉末の表面をα類似型Ａｌ固
溶Ｎｉ（ＯＨ）2で被覆することにより、容量密度、放
電電圧、高率放電特性に優れたアルカリ蓄電池用正極活
物質が提供できる。また、上記α類似型Ａｌ固溶Ｎｉ
（ＯＨ）2被覆層中にＣａ，Ｃｒ，Ｙ，Ｔｉ，Ｃｏから
選ばれる少なくとも一種の異種金属元素を固溶させるこ
とにより、容量密度、放電電圧、高率放電特性に優れ、
かつ高温充電効率および／または充放電特性に優れたア
ルカリ蓄電池用正極活物質が提供できる。さらに、上記
α類似型Ａｌ固溶Ｎｉ（ＯＨ）2被覆正極活物質粉末の
表面をＣｏ酸化物で被覆させることにより、容量密度、
放電電圧、高率放電特性に優れ、かつ充放電特性に優れ
たアルカリ蓄電池用正極活物質が提供できる。According to the present invention, a positive electrode active material for an alkaline storage battery having excellent capacity density, discharge voltage, and high rate discharge characteristics is provided by coating the surface of the positive electrode active material powder with α-like Al solid solution Ni (OH) 2. it can. In addition, the α-similar Al solid solution Ni
By dissolving at least one dissimilar metal element selected from Ca, Cr, Y, Ti, and Co in the (OH) 2 coating layer, it is excellent in capacity density, discharge voltage, and high-rate discharge characteristics,
In addition, a positive electrode active material for an alkaline storage battery having excellent high-temperature charging efficiency and / or charge / discharge characteristics can be provided. Further, by coating the surface of the α-like Al solid solution Ni (OH) 2 -coated positive electrode active material powder with a Co oxide, the capacity density,
A positive electrode active material for an alkaline storage battery having excellent discharge voltage and high-rate discharge characteristics and excellent charge / discharge characteristics can be provided.
フロントページの続き (72)発明者 和泉 陽一 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 松本 功 大阪府門真市大字門真1006番地 松下電器 産業株式会社内Continuing on the front page (72) Inventor Yoichi Izumi 1006 Kazuma Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd.
Claims (5)
素の酸化物または水酸化物を主材料とするアルカリ蓄電
池用正極に使用する活物質粉末であって、前記複数金属
元素の酸化物または水酸化物粉末の表面層付近に、Ａｌ
が共晶状態および／または固溶状態で存在するα類似型
Ｎｉ（ＯＨ）2層を配したことを特徴とするアルカリ蓄
電池用正極活物質。1. An active material powder for use in a positive electrode for an alkaline storage battery mainly composed of an oxide or hydroxide of a plurality of metal elements mainly composed of Ni, wherein the oxide or water of the plurality of metal elements is used. Al near the surface layer of the oxide powder
Characterized in that an α-like Ni (OH) 2 layer is present in a eutectic state and / or a solid solution state.
および／または固溶状態で存在するＡｌ量は、前記α類
似型Ｎｉ（ＯＨ）2層中の金属原子比をＮｉ：Ａｌ＝１
−ｘ：ｘと表したとき、０．１０≦ｘ≦０．４０である
ことを特徴とする請求項１記載のアルカリ蓄電池用正極
活物質。Wherein α similar type Ni (OH) Al content present in eutectic conditions and / or solid solution in two layers in the said α similar type Ni (OH) metal atomic ratio of 2 layer Ni: Al = 1
The positive electrode active material for an alkaline storage battery according to claim 1, wherein, when expressed as -x: x, 0.10? X? 0.40.
末の表面層付近に配されたα類似型Ｎｉ（ＯＨ）2層中
には、Ｎｉ，Ａｌの他にＣａ，Ｃｒ，Ｙ，Ｔｉ，Ｃｏか
ら選ばれた少なくとも一種の元素が共晶状態および／ま
たは固溶状態で存在することを特徴とする請求項１記載
のアルカリ蓄電池用正極活物質。3. An α-like Ni (OH) 2 layer disposed near a surface layer of an oxide or hydroxide powder of a plurality of metal elements includes Ca, Cr, Y, Ti in addition to Ni and Al. The positive electrode active material for an alkaline storage battery according to claim 1, wherein at least one element selected from the group consisting of, and Co is present in a eutectic state and / or a solid solution state.
および／または固溶状態で存在するＣａ，Ｃｒ，Ｙ，Ｔ
ｉ，Ｃｏから選ばれる少なくとも一種の元素をＭｅと表
した時、そのＭｅ量は前記α類似型Ｎｉ（ＯＨ）2層中
の金属原子比をＮｉ＋Ａｌ：Ｍｅ＝１−ｙ：ｙと表した
場合、０．０１≦ｙ≦０．２０であることを特徴とする
請求項３記載のアルカリ蓄電池用正極活物質。4. Ca, Cr, Y, T existing in a eutectic state and / or a solid solution state in an α-like Ni (OH) 2 layer
When at least one element selected from i and Co is represented by Me, the amount of Me is based on the case where the metal atomic ratio in the α-like Ni (OH) 2 layer is represented by Ni + Al: Me = 1-y: y. 4. The positive electrode active material for an alkaline storage battery according to claim 3, wherein 0.01 ≦ y ≦ 0.20.
に配した活物質粉末の表面に、さらにＣｏ酸化物層を配
したことを特徴とする請求項１から４のいずれかに記載
のアルカリ蓄電池用正極活物質。5. The method according to claim 1, wherein a Co oxide layer is further disposed on the surface of the active material powder having the α-like Ni (OH) 2 layer disposed near the surface layer. The positive electrode active material for an alkaline storage battery according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24678798A JP4366729B2 (en) | 1997-10-06 | 1998-09-01 | Cathode active material for alkaline storage battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27237197 | 1997-10-06 | ||
| JP9-272371 | 1997-10-06 | ||
| JP24678798A JP4366729B2 (en) | 1997-10-06 | 1998-09-01 | Cathode active material for alkaline storage battery |
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| Publication Number | Publication Date |
|---|---|
| JPH11176437A true JPH11176437A (en) | 1999-07-02 |
| JP4366729B2 JP4366729B2 (en) | 2009-11-18 |
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|---|---|---|---|
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