JP2001035524A - Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery - Google Patents

Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery

Info

Publication number
JP2001035524A
JP2001035524A JP11210978A JP21097899A JP2001035524A JP 2001035524 A JP2001035524 A JP 2001035524A JP 11210978 A JP11210978 A JP 11210978A JP 21097899 A JP21097899 A JP 21097899A JP 2001035524 A JP2001035524 A JP 2001035524A
Authority
JP
Japan
Prior art keywords
rare earth
alkaline
alkaline battery
solution
chlorine
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.)
Pending
Application number
JP11210978A
Other languages
Japanese (ja)
Inventor
Junji Ikegawa
淳史 池川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Santoku Corp
Original Assignee
Santoku Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Santoku Corp filed Critical Santoku Corp
Priority to JP11210978A priority Critical patent/JP2001035524A/en
Publication of JP2001035524A publication Critical patent/JP2001035524A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

PROBLEM TO BE SOLVED: To provide an addition agent for an alkaline battery, manufacture of the same, and an electrolyte for the battery which show a large apparent amount of dissolution to alkaline electrolyte, which are expected to improve the cycle life and the like, and are able to be added to an electrolyte for alkaline battery or an electrode material. SOLUTION: A rare earth addition agent for an alkaline battery and electrolyte, in which the agent is added are made of rare earth oxide, rare earth hydroxide, rare earth carbonate, each of which includes a rare earth element and chlorine and/or nitrate radicals, and mixture of these materials. The addition agent includes chlorine and/or nitrate radical of 0.01 to 200 atomic percent to the rare earth element. The addition agent is manufactured, in such a manner that rare earth oxide, rare earth hydroxide, rare earth carbonate, or mixture of these is dipped in acid solution not more than pH 5 or alkaline solution not less than 10-2 mol/l, both of the solutions including 0.01 wt.% or more chlorine and/or nitrate radicals and kept at a temperature of 40 deg.C or higher.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、アルカリ電池のサ
イクル寿命等の改善を期待して、アルカリ電池用電解
液、アルカリ電池の電極材料に添加できるアルカリ電池
用希土類添加剤、その製造方法及びアルカリ電池用電解
液に関する。The present invention relates to a rare earth additive for an alkaline battery which can be added to an electrolyte for an alkaline battery, an electrode material for an alkaline battery, a method for producing the same, and an alkali, with the expectation of improving the cycle life and the like of the alkaline battery. The present invention relates to a battery electrolyte.

【０００２】[0002]

【従来の技術】近年、ニッケル−カドミウム２次電池に
代わる高容量の電池として、希土類金属−ニッケル合金
をはじめとする、水素吸蔵合金を負極活物質とする金属
水素化物２次電池(以下、ＭＨ電池という)が注目されて
いる。このＭＨ電池においては、充放電サイクルの繰り
返しにより、負極を構成する水素吸蔵合金又は水素化物
が酸化され、性能が劣化するという問題がある。この問
題は、電極材料中の活物質が、充放電サイクルの繰り返
しによりアルカリ電解液中に溶出等して、電極材料中の
活物質の量が減少するためと考えられている。そこで、
電極材料中の活物質がアルカリ電解液中に溶出等するこ
とを抑制するために種々の提案がなされている。例え
ば、イットリウムを含む希土類の金属、希土類酸化物又
は希土類水酸化物を負極等の電池内部に添加するか、若
しくは希土類酸化物又は希土類水酸化物をアルカリ電解
液に実質的に溶解させ、アルカリ電解液中への活物質の
溶解度等を予め低くすることによって、前記性能の劣化
を抑制する試みがなされている(特開平６−２１５７６
５号公報、特開平８−２２２２１０号公報、特開平８−
３２９９３４号公報、特開平１０−１０６５５０号公報
等)。しかし、上記提案における希土類金属、希土類酸
化物又は希土類水酸化物を用いた場合には、アルカリ電
解液への溶解度等が非常に微量であって、通常１ｍｇ／
ｌ程度が見かけ上溶解するに過ぎない。従って、希土類
化合物添加の効果が十分に発揮されるとは言い難い。ま
た、限られた電池の容積中に活物質として働くことので
きない希土類化合物を添加することは、電池の容量低下
につながる。2. Description of the Related Art In recent years, as a high-capacity battery replacing a nickel-cadmium secondary battery, a metal hydride secondary battery (hereinafter referred to as MH) using a hydrogen storage alloy such as a rare earth metal-nickel alloy as a negative electrode active material. Battery). In this MH battery, there is a problem that the repetition of the charge / discharge cycle oxidizes the hydrogen storage alloy or hydride constituting the negative electrode, and deteriorates the performance. This problem is considered to be due to the fact that the active material in the electrode material is eluted into the alkaline electrolyte by repeated charge / discharge cycles, and the amount of the active material in the electrode material is reduced. Therefore,
Various proposals have been made to prevent the active material in the electrode material from being eluted into the alkaline electrolyte. For example, a rare earth metal containing yttrium, a rare earth oxide or a rare earth hydroxide is added to the inside of a battery such as a negative electrode, or a rare earth oxide or a rare earth hydroxide is substantially dissolved in an alkaline electrolyte to form an alkaline electrolyte. Attempts have been made to suppress the deterioration of the performance by reducing the solubility of the active material in the liquid in advance (Japanese Patent Application Laid-Open No. Hei 6-21576).
No. 5, JP-A-8-222210, JP-A-8-222210
329934, JP-A-10-106550, etc.). However, when the rare earth metal, rare earth oxide or rare earth hydroxide in the above proposal is used, the solubility and the like in an alkaline electrolyte are very small, and usually 1 mg /
Only about 1 dissolves apparently. Therefore, it is difficult to say that the effect of the rare earth compound addition is sufficiently exhibited. Also, adding a rare earth compound that cannot work as an active material to a limited battery volume leads to a reduction in battery capacity.

【０００３】[0003]

【発明が解決しようとする課題】本発明の目的は、アル
カリ電解液に対する見かけ上の溶解量が大きく、アルカ
リ電池におけるサイクル寿命等の改善が期待でき、アル
カリ電池用電解液又は電極材料へ添加することができ
る、アルカリ電池用添加剤及びその製造方法を提供する
ことにある。本発明の別の目的は、アルカリ電池におけ
る充放電サイクルによって生じる電極材料中の活物質の
アルカリ電解液への溶出等を抑制し、サイクル寿命等の
改善が期待できるアルカリ電池用電解液を提供すること
にある。SUMMARY OF THE INVENTION An object of the present invention is to increase the apparent amount of dissolution in an alkaline electrolyte and to expect an improvement in cycle life and the like in an alkaline battery. To provide an additive for an alkaline battery and a method for producing the same. Another object of the present invention is to provide an electrolytic solution for an alkaline battery which can suppress elution of an active material in an electrode material caused by a charge / discharge cycle in an alkaline battery into an alkaline electrolytic solution and can be expected to improve cycle life and the like. It is in.

【０００４】[0004]

【課題を解決するための手段】本発明によれば、希土類
元素と、塩素及び／又は硝酸根とを含む希土類酸化物、
希土類水酸化物、希土類炭酸塩又はこれらの混合物から
なり、塩素及び／又は硝酸根を希土類元素に対して０．
０１〜２００原子％含むことを特徴とするアルカリ電池
用希土類添加剤が提供される。また本発明によれば、塩
素及び／又は硝酸根を０．０１重量％以上含有する、ｐ
Ｈ５以下の酸溶液、若しくは１０-2ｍｏｌ／ｌ以上のア
ルカリ溶液中に、希土類酸化物、希土類水酸化物、希土
類炭酸塩又はこれらの混合物を浸漬し、４０℃以上に保
持することを特徴とする上記アルカリ電池用希土類添加
剤の製造方法が提供される。更に本発明によれば、希土
類元素イオンと、塩素及び／又は硝酸根とを含有する水
溶液に、尿素を混合し、得られる混合溶液のｐＨを５以
下に調整した後、１気圧以上、１００℃以上の条件で水
熱処理することを特徴とする上記アルカリ電池用希土類
添加剤の製造方法が提供される。更にまた本発明によれ
ば、水酸化カリウムを含むアルカリ溶液に、上記アルカ
リ電池用希土類添加剤を実質的に溶解させた電解液であ
って、希土類元素が金属換算で５ｍｇ／ｌ以上見かけ上
溶解していることを特徴とするアルカリ電池用電解液が
提供される。According to the present invention, there is provided a rare earth oxide containing a rare earth element and chlorine and / or nitrate,
It is composed of a rare earth hydroxide, a rare earth carbonate or a mixture thereof.
There is provided a rare earth additive for an alkaline battery, characterized in that the rare earth additive contains from 0.01 to 200 atomic%. Further, according to the present invention, p containing at least 0.01% by weight of chlorine and / or nitrate,
A rare earth oxide, a rare earth hydroxide, a rare earth carbonate or a mixture thereof is immersed in an acid solution of H5 or less or an alkali solution of 10 -2 mol / l or more, and is maintained at 40 ° C or more. A method for producing the above-mentioned rare earth additive for an alkaline battery is provided. Further, according to the present invention, urea is mixed with an aqueous solution containing a rare earth element ion and chlorine and / or nitrate, and the pH of the resulting mixed solution is adjusted to 5 or less, and then 1 atm or more and 100 ° C. A method for producing the rare earth additive for an alkaline battery is provided, wherein the method is subjected to hydrothermal treatment under the above conditions. Furthermore, according to the present invention, there is provided an electrolytic solution obtained by substantially dissolving the rare earth additive for an alkaline battery in an alkaline solution containing potassium hydroxide, wherein the rare earth element is apparently dissolved in an amount of 5 mg / l or more in terms of metal. An electrolytic solution for an alkaline battery is provided.

【０００５】[0005]

【発明の実施の形態】以下本発明を更に詳細に説明す
る。本発明のアルカリ電池用希土類添加剤(以下、「本
発明の添加剤」ということがある)は、希土類元素と、
塩素及び／又は硝酸根とを含む希土類酸化物、希土類水
酸化物、希土類炭酸塩又はこれらの混合物からなり、塩
素及び／又は硝酸根を特定量含有する。好ましくは、１
Ｎ以上のアルカリ溶液に溶解させた際に、常温におい
て、希土類元素が金属換算で５ｍｇ以上、好ましくは１
０ｍｇ以上、特に好ましくは２０ｍｇ以上見かけ上溶解
させたり、負極材料や正極材料に添加して使用すること
ができる。ここで、本発明の添加剤が、アルカリ溶液に
見かけ上溶解するとは、完全な溶解は当然含むが、必ず
しも完全な溶解である必要はなく、アルカリ電池用電極
中の活物質がアルカリ電解液に溶出等することを抑制し
得るように、その一部又は全部が微細分散等の状態で存
在していても良いことを意味する。具体的には、アルカ
リ溶液に本発明の添加剤を溶解させたアルカリ電解液
を、Ｎｏ．５Ｃの定量ろ紙(アドバンテック社製等)で濾
過した際に、通過する程度に見かけ上溶解している状態
であれば良い。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Rare earth additives for alkaline batteries of the present invention (hereinafter, sometimes referred to as `` additive of the present invention ''), a rare earth element,
It is made of a rare earth oxide, a rare earth hydroxide, a rare earth carbonate or a mixture thereof containing chlorine and / or nitrate, and contains a specific amount of chlorine and / or nitrate. Preferably, 1
When dissolved in an alkali solution of N or more, at room temperature, the rare earth element is 5 mg or more, preferably 1
0 mg or more, particularly preferably 20 mg or more, can be apparently dissolved or used by being added to a negative electrode material or a positive electrode material. Here, the apparent dissolution of the additive of the present invention in an alkaline solution includes, of course, complete dissolution, but not necessarily complete dissolution, and the active material in the electrode for an alkaline battery is dissolved in the alkaline electrolyte. This means that a part or the whole thereof may be present in a state of fine dispersion or the like so that elution or the like can be suppressed. Specifically, an alkaline electrolyte obtained by dissolving the additive of the present invention in an alkaline solution was designated as It only has to be in a state where it is apparently dissolved to the extent that it passes when it is filtered through a 5C quantitative filter paper (manufactured by Advantech).

【０００６】本発明の添加剤において、希土類元素は、
イットリウム、スカンジウムを含むランタンからルテチ
ウムまでのランタノイド元素を意味する。本発明の添加
剤において、希土類酸化物、希土類水酸化物及び希土類
炭酸塩としては、例えば、Ｒ2Ｏ3、Ｒ(ＯＨ)3、Ｒ2(Ｃ
Ｏ3)3、ＲＯＯＨ、Ｒ2Ｏ(ＣＯ3)2、Ｒ2Ｏ2ＣＯ3等が挙
げられる。ここで、Ｒは、希土類元素を示す。使用に際
しては、単独でも、２種以上の混合物であっても良い。In the additive of the present invention, the rare earth element is
It means lanthanoid elements from lanthanum including yttrium and scandium to lutetium. In the additive of the present invention, as the rare earth oxide, rare earth hydroxide and rare earth carbonate, for example, R 2 O 3 , R (OH) 3 , R 2 (C
O 3 ) 3 , ROOH, R 2 O (CO 3 ) 2 , R 2 O 2 CO 3 and the like. Here, R represents a rare earth element. When used, they may be used alone or as a mixture of two or more.

【０００７】本発明の添加剤に含有される、塩素及び硝
酸根は、単独で含まれていても、両方が含まれていても
良い。本発明の添加剤中における含有割合は、総量で希
土類元素に対して、０．０１〜２００原子％、好ましく
は０．０１〜１００原子％、特に好ましくは０．０１〜
６０原子％である。塩素及び／又は硝酸根の含有割合
が、希土類元素に対して０．０１原子％未満の場合に
は、アルカリ電解液に溶解させた際の希土類元素の見か
け上の溶解度が極端に低下し、２００原子％を超える場
合には、アルカリ電解液に溶解させた際の、希土類元素
の見かけ上の溶解度の向上が見られない。[0007] The chlorine and nitrate groups contained in the additive of the present invention may be contained alone or both. The content ratio in the additive of the present invention is 0.01 to 200 atomic%, preferably 0.01 to 100 atomic%, particularly preferably 0.01 to 200 atomic% with respect to the rare earth element in total amount.
60 atomic%. When the content ratio of chlorine and / or nitrate is less than 0.01 atomic% with respect to the rare earth element, the apparent solubility of the rare earth element when dissolved in the alkaline electrolyte is extremely reduced, and If it exceeds atomic%, no apparent improvement in the solubility of the rare earth element when dissolved in an alkaline electrolyte is observed.

【０００８】本発明の添加剤には、本発明の目的が損な
われない範囲において、他の元素を含んでいても良い。
例えば、アルカリ金属元素、アルカリ土類金属元素又は
これらの混合物等が挙げられる。アルカリ金属元素及び
／又はアルカリ土類金属元素を含有させる場合の含有割
合は、希土類元素に対して、０．０１〜１６原子％が好
ましく、特に、０．０１〜２．５原子％が望ましい。ア
ルカリ金属元素及び／又はアルカリ土類金属元素の希土
類元素に対する含有割合が１６原子％を超える場合に
は、アルカリ電解液に溶解させた際の、希土類元素の見
かけ上の溶解度の向上が見られないので好ましくない。The additive of the present invention may contain other elements as long as the object of the present invention is not impaired.
For example, an alkali metal element, an alkaline earth metal element, a mixture thereof, or the like can be given. When the alkali metal element and / or the alkaline earth metal element is contained, the content ratio is preferably 0.01 to 16 atomic%, and particularly preferably 0.01 to 2.5 atomic%, based on the rare earth element. When the content ratio of the alkali metal element and / or the alkaline earth metal element to the rare earth element exceeds 16 atomic%, no apparent improvement in the solubility of the rare earth element when dissolved in the alkaline electrolyte is observed. It is not preferable.

【０００９】本発明の添加剤において、含有される塩素
及び／又は硝酸根、必要により含有される他の元素は、
本発明の目的が達成される範囲において、希土類酸化
物、希土類水酸化物、希土類炭酸塩又はこれらの混合物
と、化学的に結合した状態であっても、物理的に結合し
た状態であっても良い。好ましくは、後述する本発明の
添加剤の製造方法にしたがって得られる状態が好まし
い。In the additive of the present invention, the chlorine and / or nitrate groups contained, and other elements contained as necessary,
Within the range in which the object of the present invention is achieved, rare earth oxides, rare earth hydroxides, rare earth carbonates or mixtures thereof, even in a chemically bonded state or a physically bonded state good. Preferably, the state obtained according to the additive manufacturing method of the present invention described below is preferable.

【００１０】本発明の添加剤の形態は、特に限定され
ず、粒状、粉状等が挙げられる。例えば、アルカリ電池
用電解液に見かけ上溶解させる場合には、通常、平均粒
径０．１〜１０μｍ程度で使用することが望ましい。一
方、アルカリ電池の正極材料又は負極材料に添加する場
合には、通常、平均粒径０．１〜５μｍ程度の大きさと
することが望ましい。[0010] The form of the additive of the present invention is not particularly limited, and examples thereof include a granular form and a powder form. For example, when apparently dissolved in an electrolytic solution for an alkaline battery, it is usually desirable to use it with an average particle size of about 0.1 to 10 μm. On the other hand, when it is added to a positive electrode material or a negative electrode material of an alkaline battery, it is usually desirable that the average particle size is about 0.1 to 5 μm.

【００１１】本発明の添加剤を製造するには、塩素及び
／又は硝酸根を特定量以上含有する、特定の酸溶液、若
しくは特定のアルカリ溶液中に、希土類酸化物、希土類
水酸化物、希土類炭酸塩又はこれらの混合物を浸漬し、
特定温度以上に保持する方法(以下、「本発明の第１の
方法」という)、希土類元素イオンと、塩素及び／又は
硝酸根とを含有する水溶液に、尿素を混合し、得られる
混合溶液のｐＨを特定値以下に調整した後、特定の条件
で水熱処理する方法(以下、「本発明の第２の方法」とい
う)等が好ましく挙げられる。In order to produce the additive of the present invention, a rare earth oxide, a rare earth hydroxide, a rare earth hydroxide or a rare earth element is added to a specific acid solution or a specific alkali solution containing a specific amount of chlorine and / or nitrate. Dipping carbonates or mixtures thereof,
A method of maintaining the temperature at a specific temperature or higher (hereinafter, referred to as "first method of the present invention"), mixing urea with an aqueous solution containing rare earth element ions and chlorine and / or nitrate, and obtaining the resulting mixed solution. A method in which the pH is adjusted to a specific value or less and then subjected to hydrothermal treatment under specific conditions (hereinafter, referred to as “the second method of the present invention”) is preferably used.

【００１２】本発明の第１の方法に用いる特定の酸溶液
は、塩素及び／又は硝酸根を０．０１重量％以上、好ま
しくは０．０１〜１５重量％含む、ｐＨ５以下、好まし
くはｐＨ−０．３〜５の溶液である。一方、特定のアル
カリ溶液は、塩素及び／又は硝酸根を０．０１重量％以
上、好ましくは０．０１〜１５重量％含む、１０-2ｍｏ
ｌ／ｌ以上溶液である。即ち、本発明においては、ｐＨ
５を超え、ｐＨ１２未満(１０-2ｍｏｌ／ｌの溶液はｐ
Ｈ１２に相当)の溶液を除く酸溶液若しくはアルカリ溶
液が使用できる。上記酸溶液及びアルカリ溶液におい
て、塩素及び／又は硝酸根の含有割合が、０．０１重量
％未満の場合には、塩素及び／又は硝酸根を希土類元素
に対して０．０１〜２００原子％含む本発明の添加剤が
得られ難い。また、溶液のｐＨが、５を超え、１２未満
の場合にも、塩素及び／又は硝酸根を希土類元素に対し
て０．０１〜２００原子％含む本発明の添加剤が得られ
難い。The specific acid solution used in the first method of the present invention contains chlorine and / or nitrate in an amount of 0.01% by weight or more, preferably 0.01 to 15% by weight, and has a pH of 5 or less, preferably a pH of not more than 5%. 0.3 to 5 solution. On the other hand, certain alkaline solution, chlorine and / or nitrate and 0.01 wt% or more, preferably from 0.01 to 15 wt%, 10 -2 mo
1 / l or more solution. That is, in the present invention, pH
Over 5 and below pH 12 (a solution of 10 -2 mol / l
An acid solution or an alkali solution except for the solution of H12) can be used. When the content of chlorine and / or nitrate in the acid solution and alkali solution is less than 0.01% by weight, the content of chlorine and / or nitrate is 0.01 to 200 atomic% based on the rare earth element. It is difficult to obtain the additive of the present invention. Also, when the pH of the solution is more than 5 and less than 12, it is difficult to obtain the additive of the present invention containing 0.01 to 200 atomic% of chlorine and / or nitrate relative to the rare earth element.

【００１３】本発明の第１の方法に用いる希土類酸化
物、希土類水酸化物、希土類炭酸塩又はこれらの混合物
は、上述の例示のものを好ましく挙げることができる。
上記希土類酸化物、希土類水酸化物、希土類炭酸塩又は
これらの混合物を、上記酸溶液又はアルカリ溶液に浸漬
させた際には、処理時間を短縮するために撹拌等を行な
っても良い。希土類酸化物、希土類水酸化物、希土類炭
酸塩又はこれらの混合物を浸漬させる量は、特に限定さ
れないが、酸溶液又はアルカリ溶液中に、１０〜３５容
量％が好ましい。As the rare earth oxide, rare earth hydroxide, rare earth carbonate or mixture thereof used in the first method of the present invention, those exemplified above can be preferably mentioned.
When the above-mentioned rare earth oxide, rare earth hydroxide, rare earth carbonate or a mixture thereof is immersed in the above acid solution or alkali solution, stirring or the like may be performed in order to shorten the treatment time. The amount of the rare earth oxide, the rare earth hydroxide, the rare earth carbonate or the mixture thereof is not particularly limited, but is preferably 10 to 35% by volume in the acid solution or the alkali solution.

【００１４】本発明の第１の方法において、上記希土類
酸化物、希土類水酸化物、希土類炭酸塩又はこれらの混
合物を浸漬させた上記酸溶液又はアルカリ溶液は、４０
℃以上、好ましくは６０℃以上、特に好ましくは８０〜
１００℃に保持することにより、本発明の添加剤を得る
ことができる。保持時間は、温度や濃度等によって異な
り、適宜選択することができるが、通常、１〜５時間と
なるように各条件を設定することが望ましい。保持温度
が４０℃未満の場合であっても本発明の添加剤を得るこ
とができるが、長時間を要するので４０℃以上とする必
要がある。得られた本発明の添加剤は、公知の精製法に
より精製、洗浄、乾燥等を行なうことによって得ること
ができる。In the first method of the present invention, the acid solution or the alkali solution impregnated with the rare earth oxide, the rare earth hydroxide, the rare earth carbonate or a mixture thereof is 40% or less.
° C or higher, preferably 60 ° C or higher, particularly preferably 80 to
By maintaining at 100 ° C., the additive of the present invention can be obtained. The holding time varies depending on the temperature, the concentration, and the like, and can be appropriately selected. However, it is usually desirable to set each condition so as to be 1 to 5 hours. Even when the holding temperature is lower than 40 ° C., the additive of the present invention can be obtained. The obtained additive of the present invention can be obtained by performing purification, washing, drying and the like by a known purification method.

【００１５】本発明の第２の方法に用いる、希土類元素
イオンと、塩素及び／又は硝酸根とを含有する水溶液に
おいて、希土類元素イオン濃度は、通常１ｍｏｌ／ｌ以
下、好ましくは０．８ｍｏｌ／ｌ以下、特に好ましくは
０．１〜０．５ｍｏｌ／ｌが望ましい。希土類元素イオ
ン濃度が１ｍｏｌ／ｌを超える場合には、希土類元素の
溶解が困難であるので好ましくない。一方、塩素及び／
又は硝酸根の含有割合は、上記水溶液中に通常０．０１
重量％以上、好ましくは０．０１〜１０重量％が望まし
い。In the aqueous solution containing rare earth element ions and chlorine and / or nitrate used in the second method of the present invention, the rare earth element ion concentration is usually 1 mol / l or less, preferably 0.8 mol / l. Hereinafter, particularly preferably 0.1 to 0.5 mol / l is desirable. If the rare earth element ion concentration exceeds 1 mol / l, it is difficult to dissolve the rare earth element, which is not preferable. On the other hand, chlorine and / or
Or the content of nitrate is usually 0.01% in the above aqueous solution.
% Or more, preferably 0.01 to 10% by weight.

【００１６】本発明の第２の方法において、希土類元素
イオンと、塩素及び／又は硝酸根とを含有する水溶液に
混合する尿素の混合割合は、希土類元素イオンとの反応
に必要な当量以上であれば良い。好ましくは、反応性を
良好にするために、希土類元素イオンとの反応に必要な
当量の２〜３倍量が望ましい。In the second method of the present invention, the mixing ratio of urea to be mixed with the aqueous solution containing rare earth ions and chlorine and / or nitrate is not less than the equivalent required for the reaction with the rare earth ions. Good. Preferably, in order to improve the reactivity, the amount is preferably 2 to 3 times the equivalent required for the reaction with the rare earth element ion.

【００１７】希土類元素イオンと、塩素及び／又は硝酸
根とを含有する水溶液には、後述する水熱処理により得
られる本発明の添加剤の凝集等を防止するために、高分
子分散剤等を添加することもできる。高分子分散剤とし
ては、例えば、平均分子量５００以上、特に５０００〜
１００００のポリアクリル酸、ポリエチレンオキサイ
ド、ゼラチン等が挙げられる。高分子分散剤の添加量は
適宜選択することができる。To the aqueous solution containing rare earth element ions and chlorine and / or nitrate, a polymer dispersant or the like is added in order to prevent aggregation of the additive of the present invention obtained by the hydrothermal treatment described below. You can also. As the polymer dispersant, for example, an average molecular weight of 500 or more, especially 5000 to
10,000 polyacrylic acid, polyethylene oxide, gelatin and the like. The amount of the polymer dispersant added can be appropriately selected.

【００１８】本発明の第２の方法において、希土類元素
イオンと、塩素及び／又は硝酸根とを含有する水溶液に
尿素等を混合した混合溶液のｐＨは、５以下、好ましく
はｐＨ１〜５に調整する必要がある。このｐＨの調整
は、塩酸、硝酸等の酸を添加することにより調整でき
る。ｐＨが５を超える場合には、塩素及び／又は硝酸根
を希土類元素に対して０．０１〜２００原子％含む本発
明の添加剤が得られ難い。In the second method of the present invention, the pH of a mixed solution obtained by mixing urea or the like with an aqueous solution containing a rare earth ion and chlorine and / or nitrate is adjusted to 5 or less, preferably pH 1 to 5. There is a need to. The pH can be adjusted by adding an acid such as hydrochloric acid or nitric acid. When the pH exceeds 5, it is difficult to obtain the additive of the present invention containing 0.01 to 200 atomic% of chlorine and / or nitrate relative to the rare earth element.

【００１９】本発明の第２の方法において、水熱処理の
条件は、圧力が１気圧以上、好ましくは１〜３気圧、温
度が１００℃以上、好ましくは１００〜１４０℃の範囲
である。圧力が１気圧未満、温度が１００℃未満の場合
には、いずれも塩素及び／又は硝酸根を希土類元素に対
して０．０１〜２００原子％含む本発明の添加剤が得ら
れ難い。水熱処理の時間は適宜選択することができる
が、通常１〜４時間が望ましい。上記水熱処理のスラリ
ーを濾別、洗浄、乾燥等することにより、本発明の添加
剤を得ることができるが、更に酸化物とするために、得
られた添加剤を焼成することもできる。焼成は、７００
℃以下の温度で行なうことが好ましい。７００℃を超え
る温度で焼成する場合には、添加剤中の塩素及び／又は
硝酸根の量が必要以上に減少する恐れがあるので好まし
くない。In the second method of the present invention, the conditions of the hydrothermal treatment are a pressure of 1 atm or more, preferably 1 to 3 atm, and a temperature of 100 ° C or more, preferably 100 to 140 ° C. When the pressure is less than 1 atm and the temperature is less than 100 ° C., it is difficult to obtain the additive of the present invention containing 0.01 to 200 atomic% of chlorine and / or nitrate relative to the rare earth element. Although the time of the hydrothermal treatment can be appropriately selected, usually 1 to 4 hours is desirable. The additive of the present invention can be obtained by filtering, washing, and drying the slurry of the hydrothermal treatment, but the obtained additive can be calcined to further form an oxide. Firing is 700
It is preferable to carry out at a temperature of not more than ℃. Firing at a temperature exceeding 700 ° C. is not preferable because the amount of chlorine and / or nitrate in the additive may be reduced more than necessary.

【００２０】本発明のアルカリ電池用電解液は、水酸化
カリウムを含むアルカリ溶液に、本発明の添加剤を溶解
させた電解液であって、希土類元素が金属換算で５ｍｇ
／ｌ以上、好ましくは１０ｍｇ／ｌ以上、特に好ましく
は２０ｍｇ／ｌ以上見かけ上溶解している電解液であ
る。上記水酸化カリウムを含むアルカリ溶液には、本発
明の添加剤の他に、通常アルカリ電池用電解液に含有さ
れる他の化合物等を含んでいても良い。また、水酸化カ
リウムの濃度も、使用するアルカリ電池の種類や容量等
に応じて適宜選択することができる。The electrolyte for an alkaline battery of the present invention is an electrolyte obtained by dissolving the additive of the present invention in an alkaline solution containing potassium hydroxide, wherein the rare earth element is 5 mg in terms of metal.
/ L or more, preferably 10 mg / l or more, particularly preferably 20 mg / l or more. The alkaline solution containing potassium hydroxide may contain, in addition to the additive of the present invention, other compounds that are usually contained in an electrolytic solution for alkaline batteries. Also, the concentration of potassium hydroxide can be appropriately selected according to the type and capacity of the alkaline battery used.

【００２１】本発明のアルカリ電池用電解液において、
希土類元素が金属換算で見かけ上溶解している量は、ア
ルカリ電池用電解液を６０℃まで昇温した後、常温まで
冷却し、定量ろ紙Ｎｏ．５Ｃ(アドバンテック社製等)を
用いて濾過した濾液をＩＣＰ発光分光分析装置(セイコ
ーインスツルメンツ(株)製、ＳＰＳ−１７００ＨＶＲ)
を用いて測定することができる。In the electrolyte for an alkaline battery of the present invention,
The amount in which the rare earth element is apparently dissolved in terms of metal is determined by raising the temperature of the electrolyte for an alkaline battery to 60 ° C., cooling the same to room temperature, and removing the amount of the quantitative filter paper no. The filtrate filtered using 5C (manufactured by Advantech Co., Ltd.) was subjected to ICP emission spectroscopy (manufactured by Seiko Instruments Inc., SPS-1700HVR).
Can be measured.

【００２２】本発明のアルカリ電池用電解液を調製する
には、例えば、所望量の水酸化カリウムを含む水溶液
を、好ましくは４０℃以上、特に好ましくは６０℃以上
に加温した後、本発明の添加剤をやや過剰に添加し、溶
解させ、常温まで冷却し、次いで、定量ろ紙Ｎｏ．５Ｃ
(アドバンテック社製)等を用いて濾過する方法等により
製造することができる。In order to prepare the electrolytic solution for an alkaline battery of the present invention, for example, an aqueous solution containing a desired amount of potassium hydroxide is preferably heated to 40 ° C. or more, particularly preferably 60 ° C. or more. Is slightly added, dissolved and cooled to room temperature. 5C
(Manufactured by Advantech Co., Ltd.) and the like.

【００２３】[0023]

【発明の効果】本発明のアルカリ電池用添加剤は、特定
量の塩素及び／又は硝酸根を含む希土類酸化物、希土類
水酸化物、希土類炭酸塩又はこれらの混合物からなるの
で、アルカリ電解液に溶解した際に、見かけ上の溶解量
を大きくすることができ、アルカリ電池におけるサイク
ル寿命等を改善することができ、アルカリ電池用電解液
又は電極材料へ添加して用いることができる。また、本
発明の製造方法は、このようなアルカリ電池用添加剤を
容易に得ることができる。更に本発明のアルカリ電池用
電解液は、希土類元素が特定量以上見かけ上溶解してい
るので、アルカリ電池における充放電サイクルによって
生じる電極材料中の活物質のアルカリ電解液への溶出等
を抑制することができ、アルカリ電池のサイクル寿命等
を改善することができる。The additive for an alkaline battery of the present invention comprises a rare earth oxide, a rare earth hydroxide, a rare earth carbonate or a mixture thereof containing a specific amount of chlorine and / or nitrate. When dissolved, the apparent amount of dissolution can be increased, the cycle life and the like in an alkaline battery can be improved, and it can be used by being added to an electrolyte or an electrode material for an alkaline battery. Moreover, the production method of the present invention can easily obtain such an additive for an alkaline battery. Furthermore, since the rare earth element is apparently dissolved in a specific amount or more in the alkaline battery electrolyte solution of the present invention, elution of the active material in the electrode material to the alkaline electrolyte solution caused by the charge / discharge cycle in the alkaline battery is suppressed. Thus, the cycle life and the like of the alkaline battery can be improved.

【００２４】[0024]

【実施例】以下本発明を実施例及び比較例により更に詳
細に説明するが、本発明はこれらに限定されるものでは
ない。なお、例中の平均粒径は、二次粒子の平均粒径を
示す。実施例１ 酸化イットリウム１００ｇを、１ｍｏｌ／ｌの塩酸溶液
(ｐＨ０)５００ｍｌに投入し、撹拌しながら１００℃で
４時間処理した。次いで、得られた溶液を２０℃に冷却
した後、Ｎｏ．５Ｃの定量ろ紙(アドバンテック社製)で
濾過、洗浄を行なった。得られた濾過物を１１０℃の乾
燥器中で乾燥して、アルカリ電池用添加剤粉末(平均粒
径３．８９μｍ)を製造した。得られた粉末について組
成分析及び６Ｎ水酸化カリウム溶液に溶解した際の見か
け上の溶解量を測定した。結果を表１に示す。表１にお
けるカリウム量、塩素量及び硝酸根量は、得られた化合
物中の希土類元素に対する量として示す。尚、見かけ上
の溶解量の測定は、得られたアルカリ電池用添加剤粉末
１ｇを６Ｎ水酸化カリウム溶液５０ｍｌに添加し、撹拌
しながら６０℃まで昇温した後、常温まで冷却し、定量
ろ紙Ｎｏ．５Ｃ(アドバンテック社製)を用いて濾過した
濾液を、ＩＣＰ発光分光分析装置(セイコーインスツル
メンツ(株)製、ＳＰＳ−１７００ＨＶＲ)により測定し
た。The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the average particle diameter in an example shows the average particle diameter of a secondary particle. Example 1 100 g of yttrium oxide was added to a 1 mol / l hydrochloric acid solution
(pH 0), and the mixture was treated at 100 ° C. for 4 hours with stirring. Then, after cooling the obtained solution to 20 ° C., Filtration and washing were performed with a 5C quantitative filter paper (manufactured by Advantech). The obtained filtrate was dried in a dryer at 110 ° C. to produce an additive powder for an alkaline battery (average particle size: 3.89 μm). The resulting powder was analyzed for composition and the apparent amount dissolved when dissolved in a 6N potassium hydroxide solution. Table 1 shows the results. The amount of potassium, the amount of chlorine, and the amount of nitrate in Table 1 are shown as amounts relative to the rare earth element in the obtained compound. The apparent dissolution amount was measured by adding 1 g of the obtained additive powder for an alkaline battery to 50 ml of a 6N potassium hydroxide solution, heating the mixture to 60 ° C. while stirring, cooling the mixture to room temperature, and measuring the amount of the quantitative filter paper. No. The filtrate filtered using 5C (manufactured by Advantech) was measured by an ICP emission spectrometer (SPS-1700HVR, manufactured by Seiko Instruments Inc.).

【００２５】実施例２ 塩酸溶液を硝酸溶液(ｐＨ０)に代えた以外は、実施例１
と同様にアルカリ電池用添加剤粉末(平均粒径４．５０
μｍ)を製造した。得られた粉末について組成分析及び
６Ｎ水酸化カリウム溶液に対する見かけ上の溶解量を測
定した。結果を表１に示す。 Example 2 Example 1 was repeated except that the hydrochloric acid solution was replaced with a nitric acid solution (pH 0).
In the same manner as described above, the additive powder for an alkaline battery (average particle size 4.50)
μm). The resulting powder was analyzed for composition and the apparent amount dissolved in a 6N potassium hydroxide solution. Table 1 shows the results.

【００２６】実施例３ 酸化イットリウム１００ｇを、塩化カリウム５ｇが溶解
した５ｍｏｌ／ｌの水酸化カリウム溶液５００ｍｌに投
入し、撹拌しながら１００℃で４時間処理した。次い
で、得られた溶液を２０℃に冷却した後、Ｎｏ．５Ｃの
定量ろ紙(アドバンテック社製)で濾過、洗浄を行なっ
た。得られた濾過物を１１０℃の乾燥器中で乾燥して、
アルカリ電池用添加剤粉末(平均粒径４．９８μｍ)を製
造した。得られた粉末について組成分析及び６Ｎ水酸化
カリウム溶液に溶解した際の見かけ上の溶解量を実施例
１と同様に測定した。結果を表１に示す。 Example 3 100 g of yttrium oxide was put into 500 ml of a 5 mol / l potassium hydroxide solution in which 5 g of potassium chloride was dissolved, and treated at 100 ° C. for 4 hours with stirring. Then, after cooling the obtained solution to 20 ° C., Filtration and washing were performed with a 5C quantitative filter paper (manufactured by Advantech). The obtained filtrate is dried in a dryer at 110 ° C.,
An additive powder for an alkaline battery (average particle size 4.98 μm) was produced. The obtained powder was analyzed for composition and the apparent amount dissolved in a 6N potassium hydroxide solution was measured in the same manner as in Example 1. Table 1 shows the results.

【００２７】実施例４ ０．３ｍｏｌ／ｌの塩化イットリウム溶液１リットルに
１０２ｇの尿素を溶解させた後、塩酸を用いて溶液のｐ
Ｈを１に調整した。この溶液をオートクレーブ中におい
て、２ｋｇｆ／ｃｍ2の圧力下、１３５℃の温度で１時
間撹拌して水熱処理を行なった。得られたスラリーを濾
過及び水洗した。次いで、得られた沈澱物を６５０℃で
２時間焼成し、アルカリ電池用添加剤粉末(平均粒径
２．６０μｍ)を得た。得られた粉末について組成分析
及び６Ｎ水酸化カリウム溶液に対する見かけ上の溶解量
を実施例１と同様に測定した。結果を表１に示す。 Example 4 After dissolving 102 g of urea in 1 liter of a 0.3 mol / l yttrium chloride solution, the solution was added with hydrochloric acid to obtain a p-type solution.
H was adjusted to 1. This solution was stirred in an autoclave under a pressure of 2 kgf / cm 2 at a temperature of 135 ° C. for 1 hour to perform a hydrothermal treatment. The obtained slurry was filtered and washed with water. Next, the obtained precipitate was calcined at 650 ° C. for 2 hours to obtain an additive powder for an alkaline battery (average particle size: 2.60 μm). The obtained powder was subjected to composition analysis and apparent dissolution in a 6N potassium hydroxide solution in the same manner as in Example 1. Table 1 shows the results.

【００２８】実施例５ ０．３ｍｏｌ／ｌの硝酸イットリウム溶液１リットルに
１０２ｇの尿素を溶解させた後、硝酸を用いて溶液のｐ
Ｈを１に調整した。この溶液をオートクレーブ中におい
て、２ｋｇｆ／ｃｍ2の圧力下、１３５℃の温度で１時
間撹拌して水熱処理を行なった。得られたスラリーを濾
過及び水洗した。次いで、得られた沈澱物を４００℃で
２時間焼成し、アルカリ電池用添加剤粉末(平均粒径
４．７１μｍ)を得た。得られた粉末について組成分析
及び６Ｎ水酸化カリウム溶液に対する見かけ上の溶解量
を実施例１と同様に測定した。結果を表１に示す。 Example 5 After dissolving 102 g of urea in 1 liter of a 0.3 mol / l yttrium nitrate solution, the solution was dissolved in nitric acid to obtain a p-type solution.
H was adjusted to 1. This solution was stirred in an autoclave under a pressure of 2 kgf / cm 2 at a temperature of 135 ° C. for 1 hour to perform a hydrothermal treatment. The obtained slurry was filtered and washed with water. Next, the obtained precipitate was calcined at 400 ° C. for 2 hours to obtain an additive powder for an alkaline battery (average particle size: 4.71 μm). The obtained powder was subjected to composition analysis and apparent dissolution in a 6N potassium hydroxide solution in the same manner as in Example 1. Table 1 shows the results.

【００２９】実施例６ 塩化イットリウム溶液を塩化ランタン溶液に代えた以外
は実施例４と同様にアルカリ電池用添加剤粉末を得た。
得られた粉末について組成分析及び６Ｎ水酸化カリウム
溶液に対する見かけ上の溶解量を測定した。結果を表１
に示す。 Example 6 An alkaline battery additive powder was obtained in the same manner as in Example 4 except that the yttrium chloride solution was replaced with a lanthanum chloride solution.
The resulting powder was analyzed for composition and the apparent amount dissolved in a 6N potassium hydroxide solution. Table 1 shows the results
Shown in

【００３０】比較例１ 酸化イットリウム１００ｇを純水５００ｍｌに投入し、
撹拌しながら１００℃で４時間処理した。次いで、得ら
れた溶液を２０℃に冷却した後、Ｎｏ．５Ｃの定量ろ紙
(アドバンテック社製)で濾過、洗浄を行なった。得られ
た濾過物を１１０℃の乾燥器中で乾燥して、アルカリ電
池用添加剤粉末(平均粒径４．７３μｍ)を製造した。得
られた粉末について組成分析及び６Ｎ水酸化カリウム溶
液に溶解した際の見かけ上の溶解量を実施例１と同様に
測定した。結果を表１に示す。 Comparative Example 1 100 g of yttrium oxide was charged into 500 ml of pure water.
The mixture was treated at 100 ° C. for 4 hours with stirring. Then, after cooling the obtained solution to 20 ° C., 5C quantitative filter paper
(Advantech) and filtration and washing were performed. The obtained filtrate was dried in a dryer at 110 ° C. to produce an additive powder for an alkaline battery (average particle size: 4.73 μm). The obtained powder was analyzed for composition and the apparent amount dissolved in a 6N potassium hydroxide solution was measured in the same manner as in Example 1. Table 1 shows the results.

【００３１】比較例２ 酸化イットリウム１００ｇを５ｍｏｌ／ｌの水酸化カリ
ウム溶液５００ｍｌに投入し、撹拌しながら１００℃で
４時間処理した。次いで、得られた溶液を比較例１と同
様に処理して、アルカリ電池用添加剤粉末(平均粒径
５．６８μｍ)を製造した。得られた粉末について組成
分析及び６Ｎ水酸化カリウム溶液に溶解した際の見かけ
上の溶解量を実施例１と同様に測定した。結果を表１に
示す。 Comparative Example 2 100 g of yttrium oxide was charged into 500 ml of a 5 mol / l potassium hydroxide solution, and treated at 100 ° C. for 4 hours with stirring. Next, the resulting solution was treated in the same manner as in Comparative Example 1 to produce an additive powder for an alkaline battery (average particle size: 5.68 μm). The obtained powder was analyzed for composition and the apparent amount dissolved in a 6N potassium hydroxide solution was measured in the same manner as in Example 1. Table 1 shows the results.

【表１】 [Table 1]

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 希土類元素と、塩素及び／又は硝酸根と
を含む希土類酸化物、希土類水酸化物、希土類炭酸塩又
はこれらの混合物からなり、塩素及び／又は硝酸根を希
土類元素に対して０．０１〜２００原子％含むことを特
徴とするアルカリ電池用希土類添加剤。1. A rare earth oxide, a rare earth hydroxide, a rare earth carbonate, or a mixture thereof containing a rare earth element and chlorine and / or nitrate, wherein chlorine and / or nitrate are added to the rare earth element in an amount of 0%. Rare earth additives for alkaline batteries, characterized by containing 0.1 to 200 atomic%. 【請求項２】 塩素及び／又は硝酸根を０．０１重量％
以上含有する、ｐＨ５以下の酸溶液、若しくは１０-2ｍ
ｏｌ／ｌ以上のアルカリ溶液中に、希土類酸化物、希土
類水酸化物、希土類炭酸塩又はこれらの混合物を浸漬
し、４０℃以上に保持することを特徴とする請求項１記
載のアルカリ電池用希土類添加剤の製造方法。2. Chlorine and / or nitrate content of 0.01% by weight
An acid solution containing a pH of 5 or less, or 10 -2 m
2. The rare earth element for an alkaline battery according to claim 1, wherein the rare earth oxide, the rare earth hydroxide, the rare earth carbonate or a mixture thereof is immersed in an alkaline solution of at least ol / l and maintained at 40 [deg.] C. or more. Manufacturing method of additives. 【請求項３】 希土類元素イオンと、塩素及び／又は硝
酸根とを含有する水溶液に、尿素を混合し、得られる混
合溶液のｐＨを５以下に調整した後、１気圧以上、１０
０℃以上の条件で水熱処理することを特徴とする請求項
１記載のアルカリ電池用希土類添加剤の製造方法。3. An aqueous solution containing a rare earth element ion and chlorine and / or nitrate is mixed with urea, the pH of the resulting mixed solution is adjusted to 5 or less, and the pressure is adjusted to 1 atmosphere or more.
The method for producing a rare earth additive for an alkaline battery according to claim 1, wherein the hydrothermal treatment is performed at a temperature of 0 ° C or higher. 【請求項４】 水酸化カリウムを含むアルカリ溶液に、
請求項１記載のアルカリ電池用希土類添加剤を実質的に
溶解させた電解液であって、希土類元素が金属換算で５
ｍｇ／ｌ以上見かけ上溶解していることを特徴とするア
ルカリ電池用電解液。4. An alkaline solution containing potassium hydroxide,
An electrolytic solution in which the rare earth additive for an alkaline battery according to claim 1 is substantially dissolved, wherein the rare earth element is 5 in metal conversion.
An electrolyte for an alkaline battery, wherein the electrolyte is apparently dissolved in an amount of at least mg / l.
JP11210978A 1999-07-26 1999-07-26 Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery Pending JP2001035524A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP11210978A JP2001035524A (en) 1999-07-26 1999-07-26 Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP11210978A JP2001035524A (en) 1999-07-26 1999-07-26 Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery

Publications (1)

Publication Number Publication Date
JP2001035524A true JP2001035524A (en) 2001-02-09

Family

ID=16598290

Family Applications (1)

Application Number Title Priority Date Filing Date
JP11210978A Pending JP2001035524A (en) 1999-07-26 1999-07-26 Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery

Country Status (1)

Country Link
JP (1) JP2001035524A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7156888B2 (en) * 2002-03-22 2007-01-02 Mitsui Mining & Smelting Co., Ltd. Cerium-based abrasive material and method for preparation thereof
JP2012204150A (en) * 2011-03-25 2012-10-22 Sumitomo Osaka Cement Co Ltd Method of producing electrode active material and electrode active material, electrode, and battery
CN104681880A (en) * 2013-12-03 2015-06-03 北京科技大学 Additive for electrolyte of lead-acid storage battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7156888B2 (en) * 2002-03-22 2007-01-02 Mitsui Mining & Smelting Co., Ltd. Cerium-based abrasive material and method for preparation thereof
JP2012204150A (en) * 2011-03-25 2012-10-22 Sumitomo Osaka Cement Co Ltd Method of producing electrode active material and electrode active material, electrode, and battery
CN104681880A (en) * 2013-12-03 2015-06-03 北京科技大学 Additive for electrolyte of lead-acid storage battery

Similar Documents

Publication Publication Date Title
CN1090389C (en) Method for mfg. alkaline cells and its positive electrode
JPWO2004064180A1 (en) Material for positive electrode of lithium secondary battery and manufacturing method thereof
KR100882403B1 (en) Alkaline cell
EP1699099A1 (en) Alkaline battery and positive electrode material for alkaline battery
CN114436344B (en) Preparation method and application of positive electrode material precursor with large channel
CN116053444A (en) Doped layered anode material and application thereof in sodium ion battery
JP4234418B2 (en) Manganese nickel composite hydroxide particles
JP4457213B2 (en) Method for producing lithium ferrite composite oxide
JP2008053222A (en) Nickel hydroxide powder, nickel oxyhydroxide powder, manufacturing method of these and alkaline dry battery
CN107968201A (en) A kind of preparation method of anode material for lithium-ion batteries and its presoma
JP2001322817A (en) Manganese solid solution nickel hydroxide particle and its manufacturing method
CN116573680A (en) Lithium cobaltate material and preparation method and application thereof
JP2001035524A (en) Addition agent for alkaline battery and manufacture of the same, and electrolyte for alkaline battery
JP4046449B2 (en) Cathode active material for sealed alkaline storage battery
CN116979039A (en) Perovskite type conductor coated ternary positive electrode material and preparation method thereof
JP3934777B2 (en) Nickel hydroxide for nickel oxyhydroxide production
JP5218900B2 (en) Alkaline storage battery
CN113629239B (en) Ternary positive electrode material precursor, preparation method thereof, ternary positive electrode material and battery
JP4423391B2 (en) Lithium ferrite composite oxide and method for producing the same
KR100740758B1 (en) Alkaline battery
US20170062802A1 (en) Polynary composite oxide, preparation method and use thereof
JP6440065B2 (en) Electrode catalyst and method for producing the same
JPH10172558A (en) Hydride secondary battery
JP2023527493A (en) Process for delithiation of transition metal oxides
JP2005071991A (en) Alkaline battery