JP2000173606A - Sintered-type nickel hydroxide positive electrode, alkaline storage battery using the positive electrode, and manufacture of sintered type nickel hydroxide positive electrode - Google Patents
Sintered-type nickel hydroxide positive electrode, alkaline storage battery using the positive electrode, and manufacture of sintered type nickel hydroxide positive electrodeInfo
- Publication number
- JP2000173606A JP2000173606A JP10340325A JP34032598A JP2000173606A JP 2000173606 A JP2000173606 A JP 2000173606A JP 10340325 A JP10340325 A JP 10340325A JP 34032598 A JP34032598 A JP 34032598A JP 2000173606 A JP2000173606 A JP 2000173606A
- Authority
- JP
- Japan
- Prior art keywords
- coating layer
- positive electrode
- sintered
- nickel hydroxide
- active material
- 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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、焼結式水酸化ニッ
ケル正極、この正極を用いたニッケル−水素蓄電池、ニ
ッケル−カドミウム蓄電池及びニッケル−亜鉛蓄電池な
どのアルカリ蓄電池、及び焼結式水酸化ニッケル正極の
製造方法に関する。The present invention relates to a sintered nickel hydroxide positive electrode, an alkaline storage battery such as a nickel-hydrogen battery, a nickel-cadmium battery and a nickel-zinc battery using the positive electrode, and a sintered nickel hydroxide. The present invention relates to a method for manufacturing a positive electrode.
【０００２】[0002]
【従来の技術】上記アルカリ蓄電池の正極としては、焼
結式ニッケル正極或いは非焼結式ニッケル正極が用いら
れているが、後者は活物質ペーストを発泡ニッケル等の
導電性多孔体に直接充填するものであって製造は簡便で
あるが、ハイレート特性に劣るという課題を有してい
る。一方、前者は多孔性ニッケル焼結基板を導電基体と
して、これに活物質塩を用いて化学含浸法により活物質
を充填するものであり、活物質が導電基体に密着してい
るということから、ハイレート特性等の高電流密度の用
途に適している。2. Description of the Related Art A sintered nickel positive electrode or a non-sintered nickel positive electrode is used as a positive electrode of the above-mentioned alkaline storage battery. In the latter, an active material paste is directly filled into a conductive porous material such as foamed nickel. Although it is simple and easy to manufacture, it has a problem of inferior high-rate characteristics. On the other hand, in the former, a porous nickel sintered substrate is used as a conductive substrate, and the active material is filled with an active material salt by a chemical impregnation method, and since the active material is in close contact with the conductive substrate, Suitable for high current density applications such as high rate characteristics.
【０００３】しかしながら、焼結式ニッケル正極は非焼
結式ニッケル正極に比べて、相対的に活物質の充填密度
が小さく、活物質の利用率を高める必要があった。そこ
で、特開平１−２００５５５号公報に示されるように、
活物質の表面に水酸化コバルト層を形成させ、且つ酸素
雰囲気中のアルカリ水溶液存在下で加熱して高次のコバ
ルト酸化物を形成させることにより、活物質の利用率を
改善するような方法が提案されている。However, the sintered nickel positive electrode has a relatively low active material packing density as compared with the non-sintered nickel positive electrode, and it is necessary to increase the utilization rate of the active material. Then, as shown in Japanese Patent Application Laid-Open No. 1-255555,
A method of improving the utilization rate of the active material by forming a cobalt hydroxide layer on the surface of the active material and heating it in the presence of an alkaline aqueous solution in an oxygen atmosphere to form a higher-order cobalt oxide. Proposed.
【０００４】ところが、上記従来の焼結式水酸化ニッケ
ル正極を用いたアルカリ蓄電池では、電池を充電した状
態で５０℃程度の高温で長期間保存すると、充電された
ニッケル活物質と焼結基板とが接する部分から酸素が発
生して自己放電し、保存後の電池容量が低下するという
課題を有していた。However, in the alkaline storage battery using the conventional sintered nickel hydroxide positive electrode, when the battery is charged and stored at a high temperature of about 50 ° C. for a long period of time, the charged nickel active material and the sintered substrate become However, there is a problem that oxygen is generated from a portion where the battery contacts, self-discharges, and the battery capacity after storage is reduced.
【０００５】そこで、本願発明者らが先に提案したよう
に、多孔性ニッケル焼結式基板に水酸化ニッケルを主体
とする活物質が充填されたアルカリ蓄電池用水酸化ニッ
ケル正極において、活物質の表面にカルシウム、ストロ
ンチウム等から成る金属の水酸化物層を形成する技術が
ある。[0005] Therefore, as proposed by the inventors of the present application, in a nickel hydroxide positive electrode for an alkaline storage battery in which a porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide, the surface of the active material is reduced. There is a technique for forming a metal hydroxide layer made of calcium, strontium, or the like.
【０００６】しかしながら、上記のニッケル正極におい
ては、通常の充放電時における電池容量は、金属の水酸
化物層の形成を行っていないものと同等であり、電池容
量に関しては改良の余地がある。However, in the above-mentioned nickel positive electrode, the battery capacity at the time of normal charge / discharge is equivalent to that without forming a metal hydroxide layer, and there is room for improvement in battery capacity.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、以上の事情
に鑑みなされたものであって、高温保存後の電池容量の
低下を十分に抑制することができ、しかも、通常の充放
電時における電池容量の向上を図ることができる焼結式
水酸化ニッケル正極及びこの正極を用いたアルカリ蓄電
池及び焼結式水酸化ニッケル正極の製造方法の提供を目
的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and can sufficiently suppress a decrease in battery capacity after high-temperature storage. It is an object of the present invention to provide a sintered nickel hydroxide positive electrode capable of improving battery capacity, an alkaline storage battery using the positive electrode, and a method for producing a sintered nickel hydroxide positive electrode.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
に、本発明のうちで請求項１記載の発明は、多孔性ニッ
ケル焼結基板に水酸化ニッケルを主体とする活物質が充
填された焼結式水酸化ニッケル正極において、前記活物
質の表面にコバルト化合物から成る第１被膜層が形成さ
れ、この第１被膜層の表面に、ニッケル、マグネシウ
ム、カルシウム、バリウム、ストロンチウム、スカンジ
ウム、イットリウム、ランタノイド及びビスマスから成
る群から選択される少なくとも一種の水酸化物或いは酸
化物から成る第２被膜層が形成されていることを特徴と
する。Means for Solving the Problems In order to achieve the above object, according to the present invention, a porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide. In the sintered nickel hydroxide positive electrode, a first coating layer made of a cobalt compound is formed on the surface of the active material, and nickel, magnesium, calcium, barium, strontium, scandium, yttrium, A second coating layer made of at least one hydroxide or oxide selected from the group consisting of lanthanoids and bismuth is formed.
【０００９】上記構成の如く、活物質の表面にコバルト
化合物から成る第１被膜層が形成されていれば、これら
は水酸化ニッケルに比べて導電性が良いということに起
因して、放電容量が大きくなる。また、第１被膜層の表
面に、ニッケル等の水酸化物或いは酸化物から成る第２
被膜層が形成されていれば、高温保存時における酸素発
生が抑えられるので、自己放電が抑制され、その結果高
温保存特性が向上する。When the first coating layer made of a cobalt compound is formed on the surface of the active material as described above, these have a higher discharge capacity due to their better conductivity than nickel hydroxide. growing. Further, a second layer made of a hydroxide or oxide such as nickel is formed on the surface of the first coating layer.
When the coating layer is formed, the generation of oxygen during high-temperature storage is suppressed, so that self-discharge is suppressed, and as a result, high-temperature storage characteristics are improved.
【００１０】また、請求項２記載の発明は、請求項１記
載の発明において、前記活物質と、前記第１被膜層と、
前記第２被膜層との総量に対する、前記第２被膜層を構
成する水酸化物或いは酸化物中の金属量が、０．０５〜
５重量％に規制されることを特徴とする。[0010] The invention according to claim 2 is the invention according to claim 1, wherein the active material, the first coating layer,
The amount of metal in the hydroxide or oxide constituting the second coating layer with respect to the total amount of the second coating layer is 0.05 to
It is characterized by being regulated to 5% by weight.
【００１１】このように規制するのは、第２被膜層を構
成する水酸化物或いは酸化物中の金属量が０．０５重量
％未満であると、添加量が不十分となるため、高温保存
特性を十分に向上させることができない一方、第２被膜
層を構成する水酸化物或いは酸化物中の金属量が５重量
％を超えると、相対的な活物質量が減少するため、放電
容量が減少するという理由による。The reason for this restriction is that when the amount of metal in the hydroxide or oxide constituting the second coating layer is less than 0.05% by weight, the amount of addition is insufficient, so that high-temperature storage is required. While the characteristics cannot be sufficiently improved, when the amount of metal in the hydroxide or oxide constituting the second coating layer exceeds 5% by weight, the relative amount of the active material decreases, and the discharge capacity decreases. Because of the decrease.
【００１２】また、上記目的を達成するために、本発明
のうちで請求項３記載の発明は、多孔性ニッケル焼結基
板に水酸化ニッケルを主体とする活物質が充填された焼
結式水酸化ニッケル正極において、前記活物質の表面に
コバルト化合物から成る第１被膜層が形成され、この第
１被膜層の表面に、ニッケル、マグネシウム、カルシウ
ム、バリウム、ストロンチウム、スカンジウム、イット
リウム、ランタノイド及びビスマスから成る群から選択
される少なくとも一種とコバルトとの複合水酸化物或い
は複合酸化物から成る第２被膜層が形成されていること
を特徴とする。According to another aspect of the present invention, there is provided a sintering water in which a porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide. In the nickel oxide positive electrode, a first coating layer made of a cobalt compound is formed on the surface of the active material, and nickel, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanoid, and bismuth are formed on the surface of the first coating layer. A second coating layer made of a composite hydroxide or a composite oxide of at least one selected from the group consisting of cobalt and cobalt is formed.
【００１３】このような構成であれば、上記請求項１で
記載した理由と同様の理由により放電容量が大きくなる
と共に高温保存特性とが向上する。With this configuration, the discharge capacity is increased and the high-temperature storage characteristics are improved for the same reason as described in the first aspect.
【００１４】また、請求項４記載の発明は、請求項３記
載の発明において、前記活物質と、前記第１被膜層と、
前記第２被膜層との総量に対する、前記第２被膜層を構
成する複合水酸化物或いは複合酸化物中の金属量が、
０．０５〜５重量％に規制されることを特徴とする。こ
のように規制するのは、上記請求項２で記載した理由と
同様の理由による。The invention according to claim 4 is the invention according to claim 3, wherein the active material, the first coating layer,
The amount of metal in the composite hydroxide or composite oxide constituting the second coating layer with respect to the total amount of the second coating layer,
It is characterized by being restricted to 0.05 to 5% by weight. The restriction is made for the same reason as described in the second aspect.
【００１５】また、請求項５記載の発明は、請求項１、
２、３又は４記載の発明において、前記ランタノイドと
して、ランタン、セリウム、プラセオジウム、ネオジ
ム、サマリウム、ユーロピウム及びイッテルビウムから
成る群から選択される少なくとも一種が用いられる、請
求項１、２、３又は４記載の焼結式水酸化ニッケル正極
を用いることを特徴とする。[0015] Further, the invention described in claim 5 provides the invention according to claim 1,
5. The invention according to claim 2, 3 or 4, wherein the lanthanoid is at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium and ytterbium. Characterized in that a sintered nickel hydroxide positive electrode is used.
【００１６】また、請求項６記載の発明は、請求項１、
２、３、４又は５記載の発明において、前記活物質と、
前記第１被膜層と、前記第２被膜層との総量に対する、
前記第１被膜層を構成するコバルト化合物中のコバルト
量が、０．０５〜５重量％に規制されることを特徴とす
る。[0016] The invention according to claim 6 is based on claim 1,
The invention according to 2, 3, 4, or 5, wherein the active material is
With respect to the total amount of the first coating layer and the second coating layer,
The amount of cobalt in the cobalt compound constituting the first coating layer is regulated to 0.05 to 5% by weight.
【００１７】このように規制するのは、第１被膜層を構
成するコバルト化合物中のコバルト量が０．０５重量％
未満であると、添加量が不十分となるため、放電容量が
減少する一方、第１被膜層を構成するコバルト化合物中
のコバルト量が５重量％を超えると、相対的な活物質量
が減少するため、やはり放電容量が低下するという理由
による。The reason for this restriction is that the amount of cobalt in the cobalt compound constituting the first coating layer is 0.05% by weight.
When the amount is less than 10%, the amount of addition becomes insufficient, so that the discharge capacity decreases. On the other hand, when the amount of cobalt in the cobalt compound constituting the first coating layer exceeds 5% by weight, the relative amount of the active material decreases. Therefore, the discharge capacity is also lowered.
【００１８】また、請求項７記載の発明は、請求項１、
２、３、４、５又は６記載の発明において、焼結式水酸
化ニッケル正極と、負極と、アルカリ電解液が含浸され
たセパレータとを備えたアルカリ蓄電池において、上記
焼結式水酸化ニッケル正極として、請求項１、２、３、
４、５又は６記載の焼結式水酸化ニッケル正極を用いる
ことを特徴とする。The invention according to claim 7 is based on claim 1,
The invention according to 2, 3, 4, 5 or 6, wherein in the alkaline storage battery comprising a sintered nickel hydroxide positive electrode, a negative electrode, and a separator impregnated with an alkaline electrolyte, the sintered nickel hydroxide positive electrode Claims 1, 2, 3,
A sintered nickel hydroxide positive electrode described in 4, 5, or 6 is used.
【００１９】また、上記目的を達成するために、本発明
のうちで請求項８記載の発明は、水酸化ニッケルを主体
とする活物質が充填された焼結基板をコバルト塩の含浸
液に浸漬した後、当該焼結基板をアルカリ水溶液に浸漬
することにより、活物質の表面にコバルト化合物から成
る第１被膜層を形成する第１ステップと、上記焼結基板
をコバルト塩の含浸液に浸漬した後、ニッケル、マグネ
シウム、カルシウム、バリウム、ストロンチウム、スカ
ンジウム、イットリウム、ランタノイド及びビスマスか
ら成る群から選択される少なくとも一種の金属を含む塩
の含浸液に浸漬した後、当該焼結基板をアルカリ水溶液
に浸漬することにより、第１被膜層の表面に、上記金属
の水酸化物或いは酸化物から成る第２被膜層を形成第２
ステップとを有することを特徴とする。このような製造
方法により、請求項１記載の焼結式水酸化ニッケル正極
を作製することができる。According to another aspect of the present invention, a sintered substrate filled with an active material mainly composed of nickel hydroxide is immersed in a cobalt salt impregnation liquid. Then, a first step of forming a first coating layer made of a cobalt compound on the surface of the active material by immersing the sintered substrate in an alkaline aqueous solution, and immersing the sintered substrate in an impregnation liquid of a cobalt salt Then, after immersing in a salt impregnation liquid containing at least one metal selected from the group consisting of nickel, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanoid and bismuth, the sintered substrate is immersed in an aqueous alkaline solution To form a second coating layer made of the hydroxide or oxide of the metal on the surface of the first coating layer.
And a step. According to such a manufacturing method, the sintered nickel hydroxide positive electrode according to claim 1 can be manufactured.
【００２０】また、上記目的を達成するために、本発明
のうちで請求項９記載の発明は、水酸化ニッケルを主体
とする活物質が充填された焼結基板をコバルト塩の含浸
液に浸漬した後、当該焼結基板をアルカリ水溶液に浸漬
することにより、活物質の表面にコバルト化合物から成
る第１被膜層を形成する第１ステップと、上記焼結基板
をコバルト塩の含浸液に浸漬した後、ニッケル、マグネ
シウム、カルシウム、バリウム、ストロンチウム、スカ
ンジウム、イットリウム、ランタノイド及びビスマスか
ら成る群から選択される少なくとも一種の金属と、コバ
ルトとを含む塩の含浸液に浸漬した後、当該焼結基板を
アルカリ水溶液に浸漬することにより、第１被膜層の表
面に、上記金属の水酸化物或いは酸化物から成る第２被
膜層を形成第２ステップとを有することを特徴とする。
このような製造方法により、請求項３記載の焼結式水酸
化ニッケル正極を作製することができる。In order to achieve the above object, a ninth aspect of the present invention is to immerse a sintered substrate filled with an active material mainly composed of nickel hydroxide in an impregnation liquid of a cobalt salt. Then, a first step of forming a first coating layer made of a cobalt compound on the surface of the active material by immersing the sintered substrate in an alkaline aqueous solution, and immersing the sintered substrate in an impregnation liquid of a cobalt salt Thereafter, nickel, magnesium, calcium, barium, strontium, scandium, yttrium, at least one metal selected from the group consisting of lanthanoid and bismuth, and after immersion in a salt impregnation liquid containing cobalt, the sintered substrate By dipping in an aqueous alkaline solution, a second coating layer made of the above-mentioned metal hydroxide or oxide is formed on the surface of the first coating layer. And characterized in that it has a and-up.
According to such a manufacturing method, the sintered nickel hydroxide positive electrode according to claim 3 can be manufactured.
【００２１】また、請求項１０記載の発明は、請求項８
又は９記載の発明において、前記ランタノイドとして、
ランタン、セリウム、プラセオジウム、ネオジム、サマ
リウム、ユーロピウム及びイッテルビウムから成る群か
ら選択される少なくとも一種が用いられることを特徴と
する。Further, the invention according to claim 10 is the same as claim 8.
Or in the invention according to 9, wherein the lanthanoid is:
At least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium and ytterbium is used.
【００２２】[0022]
【発明の実施の形態】以下、本発明の実施の形態を詳細
に説明するが，本発明は下記形態に何ら限定されるもの
ではなく，その要旨を変更しない範囲において適宜変更
して実施が可能である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in detail. However, the present invention is not limited to the following embodiments, and can be implemented by appropriately changing the scope of the present invention. It is.
【００２３】先ず、水酸化ニッケルを主体とする活物質
が充填された焼結基板を、３重量％の硝酸コバルト水溶
液に浸漬した後、２５％のＮａＯＨ水溶液（８０℃）中
に浸漬することによって、活物質の表面を水酸化コバル
トで被覆して第１被膜層を形成した。次に、上記第１被
膜層が形成された焼結基板を、３重量％のニッケル（Ｎ
ｉ）の硝酸塩水溶液に浸漬した後、２５％のＮａＯＨ水
溶液中（８０℃）に浸漬して、上記第１被膜層の表面に
ニッケルの水酸化物から成る第２被膜層を形成した。First, a sintered substrate filled with an active material mainly composed of nickel hydroxide is immersed in a 3% by weight aqueous solution of cobalt nitrate and then immersed in a 25% aqueous solution of NaOH (80 ° C.). Then, the surface of the active material was coated with cobalt hydroxide to form a first coating layer. Next, the sintered substrate on which the first coating layer was formed was coated with 3% by weight of nickel (N
After immersion in the nitrate aqueous solution of i), it was immersed in a 25% aqueous NaOH solution (80 ° C.) to form a second coating layer made of nickel hydroxide on the surface of the first coating layer.
【００２４】ここで、上記のようにして作製した活物質
についてＸ線回折を行ったところ、水酸化ニッケルのピ
ーク以外に第１被膜層及び第２被膜層を構成する各水酸
化物層のピークが観察され、これらの水酸化物が形成さ
れていることを確認した。Here, when the X-ray diffraction was performed on the active material prepared as described above, the peaks of the hydroxide layers constituting the first coating layer and the second coating layer were observed in addition to the peak of nickel hydroxide. Was observed, and it was confirmed that these hydroxides were formed.
【００２５】この後、上記焼結式水酸化ニッケル正極
と、組成式Ｍｍ1.0 Ｎｉ3.2 Ｃｏ1.0Ａｌ0.2 Ｍｎ0.6
で示される水素吸蔵合金負極と、ポリオレフィン不織布
から成るセパレータとを渦巻状に巻回して渦巻電極体を
作製した後、この渦巻電極体を電池缶内に収納し、更に
６Ｎの水酸化カリウム溶液を電池缶内に注入した後、電
池缶を封口することにより、密閉型ニッケル−水素蓄電
池を作製した。Thereafter, the above-mentioned sintered nickel hydroxide positive electrode and a composition formula Mm 1.0 Ni 3.2 Co 1.0 Al 0.2 Mn 0.6
And a separator made of a polyolefin non-woven fabric is spirally wound to form a spiral electrode body. The spiral electrode body is housed in a battery can, and a 6N potassium hydroxide solution is further added thereto. After pouring into the battery can, the battery can was sealed to produce a sealed nickel-hydrogen storage battery.
【００２６】ここで、第２被膜層を形成する際の硝酸塩
水溶液としては、上記ニッケル（Ｎｉ）の硝酸塩水溶液
に限定するものではなく、マグネシウム（Ｍｇ）、カル
シウム（Ｃａ）、バリウム（Ｂａ）、ストロンチウム
（Ｓｒ）、スカンジウム（Ｓｃ）、イットリウム
（Ｙ）、ランタン（Ｌａ）、セリウム（Ｃｅ）、プラセ
オジウム（Ｐｒ）、ネオジム（Ｎｄ）、サマリウム（Ｓ
ｍ）、ユーロピウム（Ｅｕ）、イッテルビウム（Ｙ
ｂ）、ビスマス（Ｂｉ）の硝酸塩水溶液を用いても良
い。Here, the aqueous nitrate solution for forming the second coating layer is not limited to the above-mentioned aqueous solution of nickel (Ni) nitrate, but may be magnesium (Mg), calcium (Ca), barium (Ba), Strontium (Sr), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (S
m), europium (Eu), ytterbium (Y
b), an aqueous solution of bismuth (Bi) nitrate may be used.
【００２７】また、コバルト化合物としては、水酸化コ
バルトに限定するものではなく、酸化コバルトであって
も良い。この場合、酸化コバルトを例えばスラリー等に
し、表面に塗付することにより形成することができる。The cobalt compound is not limited to cobalt hydroxide but may be cobalt oxide. In this case, it can be formed by applying cobalt oxide to a slurry or the like, for example, and applying it to the surface.
【００２８】更に、本発明は上記ニッケル−水素蓄電池
に限定するものではなく、ニッケル−カドミウム蓄電
池、ニッケル−亜鉛蓄電池などの他のアルカリ蓄電池に
も適用しうることは勿論である。Further, the present invention is not limited to the above-mentioned nickel-hydrogen storage battery, but can be applied to other alkaline storage batteries such as a nickel-cadmium storage battery and a nickel-zinc storage battery.
【００２９】[0029]
【実施例】〔実施例１〕実施例１としては、前記発明の
実施の形態で示す方法により作製したニッケル−水素蓄
電池を用いた。このようにして作製した電池を、以下、
本発明電池Ａ１と称する。EXAMPLES Example 1 In Example 1, a nickel-hydrogen storage battery manufactured by the method described in the embodiment of the present invention was used. The battery fabricated in this manner is hereinafter described.
The battery is referred to as “invention battery A1”.
【００３０】〔実施例２〜１５〕第２被膜層を形成する
際の硝酸塩水溶液として、上記ニッケルの硝酸塩水溶液
に代えて、マグネシウム、カルシウム、バリウム、スト
ロンチウム、スカンジウム、イットリウム、ランタン、
セリウム、プラセオジウム、ネオジム、サマリウム、ユ
ーロピウム、イッテルビウム及びビスマスの硝酸塩水溶
液を用いた他は、上記実施例１と同様にしてニッケル−
水素蓄電池を作製した。このようにして作製した電池
を、以下、それぞれ本発明電池Ａ２〜Ａ１５と称する。Examples 2 to 15 As the aqueous nitrate solution for forming the second coating layer, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanum, and the like were used instead of the above-mentioned aqueous solution of nickel nitrate.
Except for using a nitrate aqueous solution of cerium, praseodymium, neodymium, samarium, europium, ytterbium and bismuth, nickel was used in the same manner as in Example 1 above.
A hydrogen storage battery was manufactured. The batteries fabricated in this manner are hereinafter referred to as Batteries A2 to A15 of the invention, respectively.
【００３１】尚、上記本発明電池Ａ１〜Ａ１５における
第１被膜層及び第２被膜層は、使用する元素に係わらず
５〜６ｍｇ／ｃｍ2 とほぼ−定値であり、含浸充填させ
た活物質、第１被膜層及び第２被膜層の総重量に対し、
それぞれ２．９、３重量％に相当する。これを金属の量
に換算すると、第１被膜層のコバルトでは１．８重量％
となり、第２被膜層中の金属は１．３〜２．４重量％と
なる。Incidentally, the first coating layer and the second coating layer in the batteries A1 to A15 of the present invention have a substantially constant value of 5 to 6 mg / cm 2 irrespective of the element used. With respect to the total weight of the first coating layer and the second coating layer,
These correspond to 2.9 and 3% by weight, respectively. When this is converted into the amount of metal, the weight of cobalt in the first coating layer is 1.8% by weight.
And the metal content in the second coating layer is 1.3 to 2.4% by weight.
【００３２】〔実施例１６〜３０〕第２被膜層を形成す
る際の硝酸塩水溶液として、上記ニッケルの硝酸塩水溶
液に代えて、ニッケル、マグネシウム、カルシウム、バ
リウム、ストロンチウム、スカンジウム、イットリウ
ム、ランタン、セリウム、プラセオジウム、ネオジム、
サマリウム、ユーロピウム、イッテルビウム及びビスマ
スとコバルトとを１：１の重量比で混合させた硝酸塩水
溶液を用いることにより、第２被膜層を複合水酸化物層
とした他は、上記実施例１と同様にしてニッケル−水素
蓄電池を作製した。このようにして作製した電池を、以
下、それぞれ本発明電池Ａ１６〜Ａ３０と称する。Examples 16 to 30 As the aqueous nitrate solution for forming the second coating layer, nickel, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanum, cerium, Praseodymium, neodymium,
A samarium, europium, ytterbium, and nitric acid aqueous solution in which bismuth and cobalt were mixed at a weight ratio of 1: 1 was used in the same manner as in Example 1 except that the second coating layer was a composite hydroxide layer. To produce a nickel-hydrogen storage battery. The batteries fabricated in this manner are hereinafter referred to as Batteries A16 to A30 of the invention, respectively.
【００３３】尚、上記本発明電池Ａ１６〜Ａ３０におけ
る第２被膜層は、使用する元素に係わらず５〜６ｍｇ／
ｃｍ2 とほぼ−定値であり、含浸充填させた活物質、第
１被膜層及び第２被膜層の総重量に対し、３重量％に相
当する。これを金属の量に換算すると、第２被膜層中の
金属は１．６〜２．２重量％となる。The second coating layer in each of the batteries A16 to A30 of the present invention has a content of 5 to 6 mg / regardless of the element used.
cm 2, which is approximately −constant value, and corresponds to 3% by weight based on the total weight of the impregnated active material, the first coating layer and the second coating layer. When this is converted into the amount of metal, the metal in the second coating layer is 1.6 to 2.2% by weight.
【００３４】〔比較例１〜１５〕第１被膜層を形成しな
い他は、上記実施例１〜１５と同様にしてニッケル−水
素蓄電池を作製した。このようにして作製した電池を、
以下、それぞれ比較電池Ｘ１〜Ｘ１５と称する。Comparative Examples 1 to 15 Nickel-hydrogen batteries were produced in the same manner as in Examples 1 to 15 except that the first coating layer was not formed. The battery fabricated in this way is
Hereinafter, they are referred to as comparative batteries X1 to X15, respectively.
【００３５】〔比較例１６〜３０〕第１被膜層を形成し
ない他は、上記実施例１６〜３０と同様にしてニッケル
−水素蓄電池を作製した。このようにして作製した電池
を、以下、それぞれ比較電池Ｘ１６〜Ｘ３０と称する。Comparative Examples 16 to 30 Nickel-hydrogen batteries were produced in the same manner as in Examples 16 to 30 except that the first coating layer was not formed. The batteries fabricated in this manner are hereinafter referred to as comparative batteries X16 to X30, respectively.
【００３６】〔比較例３１〕第１被膜層及び第２被膜層
を形成しない他は、上記実施例１と同様にしてニッケル
−水素蓄電池を作製した。このようにして作製した電池
を、以下、比較電池Ｘ３１と称する。Comparative Example 31 A nickel-hydrogen storage battery was manufactured in the same manner as in Example 1 except that the first coating layer and the second coating layer were not formed. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X31.
【００３７】〔比較例３２〕第２被膜層を形成しない他
は、上記実施例１と同様にしてニッケル−水素蓄電池を
作製した。尚、この電池は、特公昭５７−５０１８号公
報に開示された技術思想に近いものである。このように
して作製した電池を、以下、比較電池Ｘ３２と称する。Comparative Example 32 A nickel-hydrogen storage battery was manufactured in the same manner as in Example 1 except that the second coating layer was not formed. This battery is similar to the technical idea disclosed in Japanese Patent Publication No. 57-5018. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X32.
【００３８】（実験１）上記本発明電池Ａ１〜Ａ３０及
び比較電池Ｘ１〜Ｘ３２における１０サイクル目の放電
容量（活性化後の放電容量）と高温保存特性とを調べた
ので、それらの結果を表１〜表４に示す。尚実験条件は
下記に示す通りである。 実験条件 充電条件：各電池を充電電流１００ｍＡで１６時間充電 放電条件：各電池を放電電流１００ｍＡで電池電圧が
１．０Ｖに達するまで放電(Experiment 1) The discharge capacity at 10th cycle (discharge capacity after activation) and the high-temperature storage characteristics of the batteries A1 to A30 of the present invention and the comparative batteries X1 to X32 were examined. 1 to Table 4. The experimental conditions are as shown below. Experimental conditions Charging condition: Each battery was charged at a charging current of 100 mA for 16 hours. Discharging condition: Each battery was discharged at a discharging current of 100 mA until the battery voltage reached 1.0 V.
【００３９】上記充放電サイクルを、室温にて１０回繰
り返し１０回目の放電容量を測定する（これが、活性化
後の放電容量である）。その後、１１サイクル目の充電
を行い、更に５０℃で２週間保存した後、これら電池を
室温に戻して電池電圧１．０Ｖに達するまで放電させ
て、残存容量を求めた。そして、当該残存容量と上記１
０サイクル目の放電容量と比較してその比率を算出する
ことによりことにより、下記（１）式に示す５０℃での
高温保存特性を調べた。 高温保存特性（％）＝（１１サイクル目の放電容量／１
０サイクル目の放電容量）×１００The above charge / discharge cycle is repeated 10 times at room temperature, and the 10th discharge capacity is measured (this is the discharge capacity after activation). Thereafter, the battery was charged at the eleventh cycle, and after further storing at 50 ° C. for 2 weeks, the batteries were returned to room temperature and discharged until the battery voltage reached 1.0 V, and the remaining capacity was determined. Then, the remaining capacity and the above 1
By calculating the ratio in comparison with the discharge capacity at the 0th cycle, the high-temperature storage characteristics at 50 ° C. shown in the following equation (1) were examined. High temperature storage characteristics (%) = (discharge capacity at eleventh cycle / 1)
(0th cycle discharge capacity) x 100
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【表４】 [Table 4]
【００４４】上記表１〜表４から明らかなように、本発
明電池Ａ１〜Ａ３０は比較電池Ｘ１〜Ｘ３２に比べて、
１０サイクル目の放電容量（活性化後の放電容量）と高
温保存特性とに優れていることが認められる。As is clear from Tables 1 to 4, the batteries A1 to A30 of the present invention are more in comparison with the comparative batteries X1 to X32.
It is recognized that the discharge capacity at the 10th cycle (discharge capacity after activation) and the high-temperature storage characteristics are excellent.
【００４５】（実験２）水酸化コバルトから成る第１被
膜層のコバルト量を変化させる他は、前記実施例７と同
様の電池を作製し、１０サイクル目の放電容量と高温保
存特性とを調べたので、その結果を表５に示す。尚、コ
バルト量は硝酸コバルトの量を変化させることにより変
え、また、１０サイクル目の放電容量と高温保存特性と
は上記実験１と同様にして求めた。(Experiment 2) A battery was manufactured in the same manner as in Example 7 except that the amount of cobalt in the first coating layer made of cobalt hydroxide was changed, and the discharge capacity at the 10th cycle and the high-temperature storage characteristics were examined. Table 5 shows the results. The amount of cobalt was changed by changing the amount of cobalt nitrate, and the discharge capacity at the tenth cycle and the high-temperature storage characteristics were obtained in the same manner as in Experiment 1.
【００４６】[0046]
【表５】 [Table 5]
【００４７】上記表５から明らかなように、活物質と、
第１被膜層と、第２被膜層との総量に対するコバルト量
が、０．０５重量％未満或いは５重量％を超えると、１
０サイクル目の放電容量が低下していることが認められ
る。したがって、活物質と、第１被膜層と、第２被膜層
との総量に対するコバルト量は、０．０５〜５重量％で
あることが望ましい。As apparent from Table 5 above, the active material and
If the amount of cobalt relative to the total amount of the first coating layer and the second coating layer is less than 0.05% by weight or more than 5% by weight, 1
It can be seen that the discharge capacity at the 0th cycle has decreased. Therefore, the amount of cobalt with respect to the total amount of the active material, the first coating layer, and the second coating layer is desirably 0.05 to 5% by weight.
【００４８】（実験３）水酸化イットリウムから成る第
２被膜層のイットリウム量を変化させる他は、前記実施
例７と同様の電池を作製し、１０サイクル目の放電容量
と高温保存特性とを調べたので、その結果を表６に示
す。尚、イットリウム量は硝酸イットリウムの量を変化
させることにより変え、また、１０サイクル目の放電容
量と高温保存特性とは上記実験１と同様にして求めた。(Experiment 3) A battery was manufactured in the same manner as in Example 7 except that the amount of yttrium in the second coating layer made of yttrium hydroxide was changed, and the discharge capacity at the 10th cycle and high-temperature storage characteristics were examined. Table 6 shows the results. The amount of yttrium was changed by changing the amount of yttrium nitrate, and the discharge capacity at 10th cycle and the high-temperature storage characteristics were determined in the same manner as in Experiment 1.
【００４９】[0049]
【表６】 [Table 6]
【００５０】上記表６から明らかなように、活物質と、
第１被膜層と、第２被膜層との総量に対するイットリウ
ム量が、０．０５重量％未満であると高温保存特性が悪
くなる一方、イットリウム量が５重量％を超えると、１
０サイクル目の放電容量が低下していることが認められ
る。したがって、活物質と、第１被膜層と、第２被膜層
との総量に対するイットリウム量は、０．０５〜５重量
％であることが望ましい。As apparent from Table 6 above, the active material and
When the amount of yttrium with respect to the total amount of the first coating layer and the second coating layer is less than 0.05% by weight, the high-temperature storage characteristics are deteriorated. On the other hand, when the amount of yttrium exceeds 5% by weight, 1%.
It can be seen that the discharge capacity at the 0th cycle has decreased. Therefore, the amount of yttrium relative to the total amount of the active material, the first coating layer, and the second coating layer is preferably 0.05 to 5% by weight.
【００５１】[0051]
【発明の効果】以上説明したように、本発明によれば、
高温保存後の電池容量の低下を十分に抑制することがで
き、しかも、通常の充放電時における電池容量の向上を
図ることができるといった優れた効果を奏する。As described above, according to the present invention,
An excellent effect is obtained in that the reduction in battery capacity after high-temperature storage can be sufficiently suppressed, and the battery capacity during normal charge and discharge can be improved.
フロントページの続き (72)発明者 前田 礼造 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 米津 育郎 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H017 AA02 AS02 CC27 CC28 DD05 EE01 EE04 HH01 5H028 AA01 BB03 BB10 CC20 EE01 HH01 Continuing from the front page (72) Inventor Reizou Maeda 2-5-2-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Toshiyuki Noma 2-5-2 Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd. (72) Inventor Ikuro Yonezu 2-5-5 Keihanhondori, Moriguchi-shi, Osaka F-term in Sanyo Electric Co., Ltd. BB03 BB10 CC20 EE01 HH01
Claims (10)
ルを主体とする活物質が充填された焼結式水酸化ニッケ
ル正極において、 前記活物質の表面にコバルト化合物から成る第１被膜層
が形成され、この第１被膜層の表面に、ニッケル、マグ
ネシウム、カルシウム、バリウム、ストロンチウム、ス
カンジウム、イットリウム、ランタノイド及びビスマス
から成る群から選択される少なくとも一種の水酸化物或
いは酸化物から成る第２被膜層が形成されていることを
特徴とする焼結式水酸化ニッケル正極。1. A sintered nickel hydroxide positive electrode in which a porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide, wherein a first coating layer made of a cobalt compound is formed on the surface of the active material. And a second coating layer made of at least one hydroxide or oxide selected from the group consisting of nickel, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanoid and bismuth on the surface of the first coating layer. A sintered nickel hydroxide positive electrode, characterized in that a positive electrode is formed.
第２被膜層との総量に対する、前記第２被膜層を構成す
る水酸化物或いは酸化物中の金属量が、０．０５〜５重
量％に規制される、請求項１記載の焼結式水酸化ニッケ
ル正極。2. The method according to claim 1, wherein the amount of metal in the hydroxide or oxide constituting the second coating layer is 0.05 with respect to the total amount of the active material, the first coating layer, and the second coating layer. The sintered nickel hydroxide positive electrode according to claim 1, wherein the positive electrode is regulated to 5% by weight.
ルを主体とする活物質が充填された焼結式水酸化ニッケ
ル正極において、 前記活物質の表面にコバルト化合物から成る第１被膜層
が形成され、この第１被膜層の表面に、ニッケル、マグ
ネシウム、カルシウム、バリウム、ストロンチウム、ス
カンジウム、イットリウム、ランタノイド及びビスマス
から成る群から選択される少なくとも一種とコバルトと
の複合水酸化物或いは複合酸化物から成る第２被膜層が
形成されていることを特徴とする焼結式水酸化ニッケル
正極。3. A sintered nickel hydroxide positive electrode in which a porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide, wherein a first coating layer made of a cobalt compound is formed on a surface of the active material. The surface of this first coating layer is formed from a composite hydroxide or composite oxide of at least one selected from the group consisting of nickel, magnesium, calcium, barium, strontium, scandium, yttrium, lanthanoid and bismuth with cobalt. A sintered nickel hydroxide positive electrode having a second coating layer formed thereon.
第２被膜層との総量に対する、前記第２被膜層を構成す
る複合水酸化物或いは複合酸化物中の金属量が、０．０
５〜５重量％に規制される、請求項３記載の焼結式水酸
化ニッケル正極。4. The amount of metal in the composite hydroxide or composite oxide constituting the second coating layer with respect to the total amount of the active material, the first coating layer, and the second coating layer is 0. .0
The sintered nickel hydroxide positive electrode according to claim 3, which is regulated to 5 to 5% by weight.
リウム、プラセオジウム、ネオジム、サマリウム、ユー
ロピウム及びイッテルビウムから成る群から選択される
少なくとも一種が用いられる、請求項１、２、３又は４
記載の焼結式水酸化ニッケル正極。5. The lanthanoid used is at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium and ytterbium.
The sintered nickel hydroxide positive electrode according to the above.
第２被膜層との総量に対する、前記第１被膜層を構成す
るコバルト化合物中のコバルト量が、０．０５〜５重量
％に規制される、請求項１、２、３、４又は５記載の焼
結式水酸化ニッケル正極。6. The amount of cobalt in the cobalt compound constituting the first coating layer is 0.05 to 5% by weight based on the total amount of the active material, the first coating layer, and the second coating layer. The sintered nickel hydroxide positive electrode according to claim 1, 2, 3, 4, or 5, which is regulated as follows.
アルカリ電解液が含浸されたセパレータとを備えたアル
カリ蓄電池において、 上記焼結式水酸化ニッケル正極として、請求項１、２、
３、４、５又は６記載の焼結式水酸化ニッケル正極を用
いることを特徴とするアルカリ蓄電池。7. A sintered nickel hydroxide positive electrode, a negative electrode,
An alkaline storage battery comprising a separator impregnated with an alkaline electrolyte, wherein the sintered nickel hydroxide positive electrode is used as the positive electrode.
An alkaline storage battery using the sintered nickel hydroxide positive electrode described in 3, 4, 5, or 6.
填された焼結基板をコバルト塩の含浸液に浸漬した後、
当該焼結基板をアルカリ水溶液に浸漬することにより、
活物質の表面にコバルト化合物から成る第１被膜層を形
成する第１ステップと、 上記焼結基板をコバルト塩の含浸液に浸漬した後、ニッ
ケル、マグネシウム、カルシウム、バリウム、ストロン
チウム、スカンジウム、イットリウム、ランタノイド及
びビスマスから成る群から選択される少なくとも一種の
金属を含む塩の含浸液に浸漬した後、当該焼結基板をア
ルカリ水溶液に浸漬することにより、第１被膜層の表面
に、上記金属の水酸化物或いは酸化物から成る第２被膜
層を形成する第２ステップと、 を有することを特徴とする焼結式水酸化ニッケル正極の
製造方法。8. After immersing a sintered substrate filled with an active material mainly composed of nickel hydroxide in an impregnation liquid of a cobalt salt,
By immersing the sintered substrate in an alkaline aqueous solution,
A first step of forming a first coating layer made of a cobalt compound on the surface of the active material, and after immersing the sintered substrate in an impregnating solution of a cobalt salt, nickel, magnesium, calcium, barium, strontium, scandium, yttrium, After being immersed in an impregnating solution of a salt containing at least one metal selected from the group consisting of lanthanoids and bismuth, the sintered substrate is immersed in an alkaline aqueous solution, so that the surface of the first coating layer has the water of the metal. A second step of forming a second coating layer made of an oxide or an oxide; and a method of producing a sintered nickel hydroxide positive electrode.
填された焼結基板をコバルト塩の含浸液に浸漬した後、
当該焼結基板をアルカリ水溶液に浸漬することにより、
活物質の表面にコバルト化合物から成る第１被膜層を形
成する第１ステップと、 上記焼結基板をコバルト塩の含浸液に浸漬した後、ニッ
ケル、マグネシウム、カルシウム、バリウム、ストロン
チウム、スカンジウム、イットリウム、ランタノイド及
びビスマスから成る群から選択される少なくとも一種の
金属と、コバルトとを含む塩の含浸液に浸漬した後、当
該焼結基板をアルカリ水溶液に浸漬することにより、第
１被膜層の表面に、上記金属の水酸化物或いは酸化物か
ら成る第２被膜層を形成する第２ステップと、 を有することを特徴とする焼結式水酸化ニッケル正極の
製造方法。9. After immersing a sintered substrate filled with an active material mainly composed of nickel hydroxide in an impregnation liquid of a cobalt salt,
By immersing the sintered substrate in an alkaline aqueous solution,
A first step of forming a first coating layer made of a cobalt compound on the surface of the active material, and after immersing the sintered substrate in an impregnating solution of a cobalt salt, nickel, magnesium, calcium, barium, strontium, scandium, yttrium, After immersing in at least one metal selected from the group consisting of lanthanoids and bismuth and a salt impregnating solution containing cobalt, the sintered substrate is immersed in an alkaline aqueous solution, so that the surface of the first coating layer is A second step of forming a second coating layer made of a hydroxide or an oxide of the above-mentioned metal; and a method for producing a sintered nickel hydroxide positive electrode.
セリウム、プラセオジウム、ネオジム、サマリウム、ユ
ーロピウム及びイッテルビウムから成る群から選択され
る少なくとも一種が用いられる、請求項８又は９記載の
焼結式水酸化ニッケル正極の製造方法。10. A lanthanum as the lanthanoid,
The method for producing a sintered nickel hydroxide positive electrode according to claim 8 or 9, wherein at least one selected from the group consisting of cerium, praseodymium, neodymium, samarium, europium, and ytterbium is used.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10340325A JP2000173606A (en) | 1998-11-30 | 1998-11-30 | Sintered-type nickel hydroxide positive electrode, alkaline storage battery using the positive electrode, and manufacture of sintered type nickel hydroxide positive electrode |
| CA002290655A CA2290655A1 (en) | 1998-11-30 | 1999-11-26 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
| CA2629335A CA2629335C (en) | 1998-11-30 | 1999-11-26 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
| EP99123604A EP1006598A3 (en) | 1998-11-30 | 1999-11-26 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
| EP07022706A EP1901373A1 (en) | 1998-11-30 | 1999-11-26 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
| KR10-1999-0053386A KR100517581B1 (en) | 1998-11-30 | 1999-11-29 | Nickel pole for alkaline storage battery and alkaline storage battery |
| US09/449,552 US6548210B1 (en) | 1998-11-30 | 1999-11-29 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
| US10/369,706 US20030219651A1 (en) | 1998-11-30 | 2003-02-21 | Nickel electrodes for alkaline secondary battery and alkaline secondary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10340325A JP2000173606A (en) | 1998-11-30 | 1998-11-30 | Sintered-type nickel hydroxide positive electrode, alkaline storage battery using the positive electrode, and manufacture of sintered type nickel hydroxide positive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000173606A true JP2000173606A (en) | 2000-06-23 |
| JP2000173606A5 JP2000173606A5 (en) | 2005-09-29 |
Family
ID=18335871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10340325A Withdrawn JP2000173606A (en) | 1998-11-30 | 1998-11-30 | Sintered-type nickel hydroxide positive electrode, alkaline storage battery using the positive electrode, and manufacture of sintered type nickel hydroxide positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000173606A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075346A (en) * | 2000-08-30 | 2002-03-15 | Sanyo Electric Co Ltd | Sintered nickel electrode and its manufacturing method |
| WO2003050898A1 (en) * | 2001-12-12 | 2003-06-19 | Sanyo Electric Co., Ltd. | Nickel-hydrogen cell |
| WO2012018077A1 (en) * | 2010-08-05 | 2012-02-09 | 株式会社Ｇｓユアサ | Alkali battery and method for manufacturing positive electrode material for alkali battery |
| CN113937267A (en) * | 2021-09-30 | 2022-01-14 | 蜂巢能源科技有限公司 | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery |
-
1998
- 1998-11-30 JP JP10340325A patent/JP2000173606A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075346A (en) * | 2000-08-30 | 2002-03-15 | Sanyo Electric Co Ltd | Sintered nickel electrode and its manufacturing method |
| WO2003050898A1 (en) * | 2001-12-12 | 2003-06-19 | Sanyo Electric Co., Ltd. | Nickel-hydrogen cell |
| WO2012018077A1 (en) * | 2010-08-05 | 2012-02-09 | 株式会社Ｇｓユアサ | Alkali battery and method for manufacturing positive electrode material for alkali battery |
| US8883349B2 (en) | 2010-08-05 | 2014-11-11 | Gs Yuasa International Ltd. | Alkaline secondary battery and method for manufacturing positive electrode material for alkaline secondary battery |
| JP5783178B2 (en) * | 2010-08-05 | 2015-09-24 | 株式会社Ｇｓユアサ | Alkaline storage battery and method for producing positive electrode material for alkaline storage battery |
| CN113937267A (en) * | 2021-09-30 | 2022-01-14 | 蜂巢能源科技有限公司 | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery |
| CN113937267B (en) * | 2021-09-30 | 2023-03-10 | 蜂巢能源科技有限公司 | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery |
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