JP2007265631A - Alkaline battery and manufacturing method of cathode used for it - Google Patents

Alkaline battery and manufacturing method of cathode used for it Download PDF

Info

Publication number
JP2007265631A
JP2007265631A JP2006085124A JP2006085124A JP2007265631A JP 2007265631 A JP2007265631 A JP 2007265631A JP 2006085124 A JP2006085124 A JP 2006085124A JP 2006085124 A JP2006085124 A JP 2006085124A JP 2007265631 A JP2007265631 A JP 2007265631A
Authority
JP
Japan
Prior art keywords
nickel
positive electrode
active material
amount
plated steel
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.)
Granted
Application number
JP2006085124A
Other languages
Japanese (ja)
Other versions
JP5147190B2 (en
Inventor
Yasuhiro Kudo
康洋 工藤
Makoto Ochi
誠 越智
Ikuko Harada
育幸 原田
Masao Takee
正夫 武江
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.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric Co Ltd
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 Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Priority to JP2006085124A priority Critical patent/JP5147190B2/en
Publication of JP2007265631A publication Critical patent/JP2007265631A/en
Application granted granted Critical
Publication of JP5147190B2 publication Critical patent/JP5147190B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkaline battery with a small Fe volume in a cathode, excellent in high output characteristics, and low-temperature charging characteristics, and therefore, easy to control charging cut, as well as a manufacturing method of a sintering type cathode to be incorporate in it. <P>SOLUTION: In the alkaline battery provided with a cathode with an active material mainly composed of nickel hydroxide filled in a porous nickel-sintered substrate with a nickel-plated steel plate as a conductive core, an anode, a separator and alkali electrolyte solution, a volume of the active material filled in the cathode is 850 g/m<SP>2</SP>or less, a volume of phosphorous in the nickel-plated steel plate is 110 ppm or less, a volume of manganese is 800 ppm or less, and a ΔV value is 0.07 V or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明はアルカリ蓄電池とそれに用いる正極の製造方法に関し、更に詳しくは、低温充電時でも充電カットを容易に制御することができ、過充電の恐れがなく、安全性の高いアルカリ蓄電池と、それに用いる焼結式正極の製造方法に関する。   The present invention relates to an alkaline storage battery and a method for producing a positive electrode used therefor, and more specifically, an alkaline storage battery that can easily control charge cut even during low-temperature charging, has no fear of overcharging, and has high safety. The present invention relates to a method for producing a sintered positive electrode.

近年、二次電池の用途が拡大し、たとえば携帯電話、パーソナルコンピュータ、電動工具、電動自転車、ハイブリッド自動車、電気自動車など広範囲に亘って二次電池が使用されている。
これら用途のうち、とくにハイブリッド自動車や電気自動車のような車両関係の用途においては、現に各種のアルカリ蓄電池が使用されているが、それらは高出力であることが要求される。また、車両関係の用途においては、高出力であることと並んで耐久性に優れることが要求されているが、この耐久性に関しては、焼結式正極が組み込まれている蓄電池の方が、非焼結式正極を組み込んだ蓄電池よりも有利である。
In recent years, the use of secondary batteries has expanded, and secondary batteries have been used in a wide range such as mobile phones, personal computers, electric tools, electric bicycles, hybrid cars, and electric cars.
Among these applications, in particular, various types of alkaline storage batteries are used in vehicle-related applications such as hybrid vehicles and electric vehicles, but they are required to have high output. In addition, in vehicle-related applications, it is required to have excellent durability as well as high output. Regarding this durability, a storage battery incorporating a sintered positive electrode is not suitable. It is more advantageous than a storage battery incorporating a sintered positive electrode.

ところで、アルカリ蓄電池に組み込まれる焼結式正極は、通常、次のようにして製造されている。まず、ニッケル粉末と例えばカルボキシメチルセルロースのような増粘剤と水とを所定の割合で混練して粘稠なスラリーを調製する。
ついで、このスラリーを導電性芯体の表面に塗着する。導電性芯体としては、通常、鋼板に所定厚みのニッケルめっきが施されたニッケルめっき鋼板が使用される。また、スラリーの各成分の混合割合やスラリーの塗着量は、最終的に正極に充填されるべき活物質の量との関係で適宜決められる。
By the way, the sintered positive electrode incorporated in an alkaline storage battery is normally manufactured as follows. First, a thick slurry is prepared by kneading nickel powder, a thickening agent such as carboxymethyl cellulose, and water at a predetermined ratio.
Next, this slurry is applied to the surface of the conductive core. As the conductive core, a nickel-plated steel sheet in which a predetermined thickness of nickel plating is applied to the steel sheet is usually used. Further, the mixing ratio of each component of the slurry and the coating amount of the slurry are appropriately determined in relation to the amount of the active material to be finally filled in the positive electrode.

ついで、スラリーが塗着されているニッケルめっき鋼板を、例えば水素のような還元性雰囲気中において所定温度で加熱して、塗着されているスラリーの焼結処理が施される。
この焼結処理時にスラリー中の増粘剤や水は揮散し、ニッケル粉末が相互に焼結することによって、スラリーは所定厚みの多孔質ニッケル焼結体に転化し、この多孔質ニッケル焼結体でニッケルめっき鋼板の表面が被覆されている多孔質ニッケル焼結基板が製造される。このときの焼結温度は当然ながらニッケルの融点より低い温度であり、通常800〜1100℃の温度が採用されている。
Next, the nickel-plated steel sheet to which the slurry is applied is heated at a predetermined temperature in a reducing atmosphere such as hydrogen, for example, and the applied slurry is sintered.
During this sintering process, the thickener and water in the slurry are volatilized and the nickel powder is sintered together, so that the slurry is converted into a porous nickel sintered body having a predetermined thickness. Thus, a porous nickel sintered substrate in which the surface of the nickel-plated steel sheet is coated is manufactured. The sintering temperature at this time is naturally lower than the melting point of nickel, and a temperature of 800 to 1100 ° C. is usually adopted.

ついで、多孔質ニッケル焼結基板の多孔質ニッケル焼結体の細孔内に水酸化ニッケルを主体とする活物質が充填される。具体的には、この焼結基板を例えば所定温度の硝酸ニッケル水溶液に浸漬して、細孔内に硝酸ニッケルを保持させ、ついで焼結基板を例えば所定温度の水酸化ナトリウム水溶液に浸漬して細孔内の硝酸ニッケルを水酸化ニッケルに転換させる。この操作を必要回数反復することにより、焼結基板の表面に目標量の水酸化ニッケル(活物質)を充填して正極にする。   Next, the active material mainly composed of nickel hydroxide is filled in the pores of the porous nickel sintered body of the porous nickel sintered substrate. Specifically, the sintered substrate is immersed in, for example, a nickel nitrate aqueous solution at a predetermined temperature to hold the nickel nitrate in the pores, and then the sintered substrate is immersed in, for example, a sodium hydroxide aqueous solution at a predetermined temperature. The nickel nitrate in the pores is converted to nickel hydroxide. By repeating this operation as many times as necessary, the surface of the sintered substrate is filled with a target amount of nickel hydroxide (active material) to form a positive electrode.

このようにして製造された正極を用いてアルカリ蓄電池が組み立てられる。
まず、正極と例えば水素吸蔵合金電極から成る負極とを、例えばポリプロピレン製の不織布から成るセパレータを介して重ね合わせて全体を渦巻き状に巻回して電極群を製造する。
ついで、この電極群の正極と負極のそれぞれに正極集電体と負極集電体を取り付けたのち、この電極群を負極端子も兼ねる有底の外装缶の中に収納し、更に例えば水酸化カリウム水溶液のようなアルカリ電解液を所定量注液する。そして外装缶の開口部に封口体を配置したのち、例えば加締加工を行なって開口部を密閉することによりアルカリ蓄電池が組立られる。
An alkaline storage battery is assembled using the positive electrode manufactured in this way.
First, a positive electrode and a negative electrode made of, for example, a hydrogen storage alloy electrode are overlapped via a separator made of, for example, a polypropylene nonwoven fabric, and the whole is wound in a spiral shape to produce an electrode group.
Next, after attaching a positive electrode current collector and a negative electrode current collector to each of the positive electrode and the negative electrode of this electrode group, this electrode group is housed in a bottomed outer can that also serves as a negative electrode terminal. A predetermined amount of an alkaline electrolyte such as an aqueous solution is injected. And after arrange | positioning a sealing body to the opening part of an exterior can, an alkaline storage battery is assembled by performing caulking processing and sealing an opening part, for example.

ところで、車両関係用途のアルカリ蓄電池の場合、正極と負極の対向面積をできるだけ大きくして高出力を引き出すということが行われている。そのため、焼結式正極にあっては、前記した渦巻き状の電極群における正極の巻回量を増大させるために、当該正極の長さを長くし、また厚みを薄くする傾向にある。
しかしながら、その後の研究において、正極の厚みが薄くなると、低温充電時に電圧が上昇せず、そのため充電カットを制御することが困難であるという問題の生ずることが判明した。このような現象は、過充電を招く原因にもなり、安全性を重視する車両関係の用途にとっては解決しなければならない問題である。
By the way, in the case of an alkaline storage battery for vehicle-related applications, it is practiced to draw out a high output by increasing the facing area between the positive electrode and the negative electrode as much as possible. Therefore, in the sintered positive electrode, in order to increase the winding amount of the positive electrode in the spiral electrode group described above, the length of the positive electrode tends to be increased and the thickness is decreased.
However, in subsequent studies, it has been found that when the thickness of the positive electrode is reduced, the voltage does not increase during low-temperature charging, which makes it difficult to control the charge cut. Such a phenomenon also causes overcharging, and is a problem that must be solved for vehicle-related applications that place importance on safety.

本発明者らは、上記した問題を解決するために後述する実験を重ねた結果、低温充電時のピーク電圧と正極活物質中のFeの量が高い相関を有しているという事実を把握するに至った。すなわち、正極活物質中のFeが増量すると低温充電特性(ΔV)が低下するという知見を得た。
そして、本発明者らは、この正極活物質中のFeは、正極の製造時における焼結処理の過程で導電性芯体であるニッケルめっき鋼板から表面のニッケルめっき層を通過してニッケル焼結体に熱拡散し、そこに存在する正極活物質中に析出しているとの推論を立てた。
As a result of repeating experiments to be described later in order to solve the above problems, the present inventors grasp the fact that the peak voltage during low-temperature charging and the amount of Fe in the positive electrode active material have a high correlation. It came to. That is, it was found that the low-temperature charge characteristic (ΔV) decreases when the amount of Fe in the positive electrode active material is increased.
The inventors of the present invention have also found that the Fe in the positive electrode active material passes through the nickel plating layer on the surface from the nickel plated steel sheet, which is a conductive core, during the sintering process during the production of the positive electrode. It was inferred that it was thermally diffused in the body and deposited in the positive electrode active material present there.

そして、これらの知見と推論に基づき、本発明者らは、ニッケルめっき鋼板のFe成分を活物質中に移動させないための条件につき検討した結果、本発明の正極の製造方法を開発し、それが組み込まれているアルカリ蓄電池を開発するに至った。
すなわち、本発明は、低温充電時でも充電カットを容易に制御することができ、過充電の恐れがなく、安全性の高いアルカリ蓄電池と、それに組み込む焼結式正極の製造方法の提供を目的とする。
And based on these findings and inferences, the present inventors have developed a method for producing the positive electrode of the present invention as a result of examining conditions for preventing the Fe component of the nickel-plated steel sheet from moving into the active material. It has led to the development of built-in alkaline storage batteries.
That is, the present invention aims to provide a highly safe alkaline storage battery that can easily control the charge cut even during low-temperature charging, has no fear of overcharging, and a method for manufacturing a sintered positive electrode incorporated therein. To do.

上記した目的を達成するために、本発明においては、ニッケルめっき鋼板を導電性芯体とする多孔質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ている正極と、負極と、セパレータと、アルカリ電解液とを外装缶の中に具備するアルカリ蓄電池において、前記正極に充填されている前記活物質の量が850g/m2以下であり、かつ、前記ニッケルめっき鋼板におけるめっき厚が4.0μm以上であることを特徴とするアルカリ蓄電池が提供される。 In order to achieve the above-described object, in the present invention, a positive electrode in which a porous nickel sintered substrate having a nickel-plated steel sheet as a conductive core is filled with an active material mainly composed of nickel hydroxide, In the alkaline storage battery comprising a separator and an alkaline electrolyte in an outer can, the amount of the active material filled in the positive electrode is 850 g / m 2 or less, and the plating thickness in the nickel-plated steel sheet The alkaline storage battery is characterized in that is 4.0 μm or more.

好ましくは、前記ニッケルめっき鋼板におけるPの量が110ppm以下であり、かつMnの量が800ppm以下であるアルカリ蓄電池が提供される。
また本発明においては、ニッケル粉末と増粘剤と水とを混練してスラリーを調製し、前記スラリーをニッケルめっき鋼板に塗着し、ついで還元性雰囲気中で焼結処理を施して多孔質ニッケル焼結基板を製造したのち、前記多孔質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を充填する正極の製造方法において、
前記焼結処理時における温度を、前記多孔質ニッケル焼結基板の表面温度が1051℃以下となるように調整することを特徴とするアルカリ蓄電池用正極の製造方法が提供される。
Preferably, an alkaline storage battery in which the amount of P in the nickel-plated steel sheet is 110 ppm or less and the amount of Mn is 800 ppm or less is provided.
In the present invention, a nickel powder, a thickener, and water are kneaded to prepare a slurry, and the slurry is applied to a nickel-plated steel sheet and then subjected to a sintering treatment in a reducing atmosphere to obtain porous nickel. After manufacturing a sintered substrate, in the method for manufacturing a positive electrode in which the porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide,
There is provided a method for producing a positive electrode for an alkaline storage battery, characterized in that the temperature during the sintering treatment is adjusted so that the surface temperature of the porous nickel sintered substrate is 1051 ° C. or lower.

本発明のアルカリ蓄電池に組み込まれる焼結式正極では、芯体であるニッケルめっき鋼板のめっき厚が4.0μm以上になっているので、また焼結処理時における基板の焼結温度を基板の表面温度が1051℃以下となるように制御しているので、得られた焼結基板に正極活物質を充填する際に、正極へのFeの混入が抑制される。そのため、この正極が組み込まれているアルカリ蓄電池では、低温充電特性が向上し、充電カットの制御が容易になり、過充電の恐れが解消する。   In the sintered positive electrode incorporated in the alkaline storage battery of the present invention, the plating thickness of the nickel-plated steel sheet as the core is 4.0 μm or more, and the sintering temperature of the substrate during the sintering process is set to the surface of the substrate. Since the temperature is controlled to be 1051 ° C. or lower, when the obtained sintered substrate is filled with the positive electrode active material, the mixing of Fe into the positive electrode is suppressed. Therefore, in the alkaline storage battery in which this positive electrode is incorporated, the low-temperature charge characteristics are improved, the charge cut control is facilitated, and the risk of overcharge is eliminated.

また、正極における活物質の充填量を850g/m2以下に設定したので、アルカリ蓄電池には高率放電特性が確保されている。
更に、ニッケルめっき鋼板のP量とMn量をそれぞれ110ppm以下、800ppm以下と規制することにより、正極へのFeの混入を抑制し、もって低温充電特性の向上が可能となる。
Further, since the filling amount of the active material in the positive electrode is set to 850 g / m 2 or less, high rate discharge characteristics are secured in the alkaline storage battery.
Furthermore, by restricting the P content and the Mn content of the nickel-plated steel sheet to 110 ppm or less and 800 ppm or less, respectively, mixing of Fe into the positive electrode can be suppressed, thereby improving the low-temperature charging characteristics.

本発明のアルカリ蓄電池には、正極とセパレータと負極とから成る電極群がアルカリ電解液とともに、外装缶の中に密封された構造であることは、前記した従来のアルカリ蓄電池の場合と変わることはないが、組み込まれている焼結式正極が後述する構成をとるところに最大の特徴がある。
用いる正極において、まず、表面の多孔質ニッケル焼結体に充填される活物質の量が正極の単位面積(m2)当たり850g以下に規定されている。
The alkaline storage battery of the present invention has a structure in which an electrode group composed of a positive electrode, a separator, and a negative electrode is sealed in an outer can together with an alkaline electrolyte, which is different from the conventional alkaline storage battery described above. However, the greatest feature is that the built-in sintered positive electrode has a configuration described later.
In the positive electrode to be used, first, the amount of the active material filled in the porous nickel sintered body on the surface is regulated to 850 g or less per unit area (m 2 ) of the positive electrode.

活物質の量が850g/m2より多い場合は、組み立てた蓄電池の高率放電特性が劣化して、高出力が要求されている車両関係の動力源としては性能不足になるからである。
また、正極の導電性芯体としてはニッケルめっき鋼板が使用されるが、その場合のニッケルめっきの厚みは4.0μm以上に設定される。
ニッケルのめっき厚が4.0μmよりも薄い場合は、正極の製造時における焼結処理の過程で、コアである鋼板からのFeの熱拡散を有効に阻止するバリアとしての機能が低下し、その結果、活物質中へのFeの析出が増量して組み立てた蓄電池の低温充電特性が劣化する。
This is because when the amount of the active material is larger than 850 g / m 2, the high rate discharge characteristics of the assembled storage battery deteriorate, and the performance becomes insufficient as a vehicle-related power source that requires high output.
In addition, a nickel-plated steel sheet is used as the conductive core of the positive electrode. In this case, the thickness of the nickel plating is set to 4.0 μm or more.
When the nickel plating thickness is less than 4.0 μm, the function as a barrier for effectively preventing the thermal diffusion of Fe from the steel sheet as the core is reduced during the sintering process during the production of the positive electrode. As a result, the low-temperature charging characteristics of the storage battery assembled by increasing the amount of Fe deposited in the active material deteriorate.

しかし、ニッケルめっきの厚みが厚くなりすぎると、正極の薄長化に逆行するだけではなく、めっき層の蓄積歪みが大きくなって鋼板との間での剥離やめっき層のクラック発生などの不都合が起こりやすくなるので、めっき厚は最大でも20μmに規制することが好ましい。
また、芯体であるニッケルめっき鋼板としては、鋼板におけるP量とMn量がそれぞれ110ppm以下、800ppm以下であるものを用いることが好ましい。
However, if the thickness of the nickel plating becomes too thick, it not only goes against the thinning of the positive electrode, but also increases the accumulated strain of the plating layer, causing inconveniences such as peeling from the steel plate and cracking of the plating layer. Since this is likely to occur, it is preferable to limit the plating thickness to 20 μm at the maximum.
Further, as the nickel-plated steel sheet as the core, it is preferable to use steel sheets having P and Mn contents of 110 ppm or less and 800 ppm or less, respectively.

P量とMn量が上記した値より多いニッケルめっき鋼板を用いると、正極活物質中のFe量が増量して低温充電特性の劣化を招くからである。
この現象は、鋼板のP量とMn量が多い場合には、正極の製造時における焼結過程でニッケルめっき層に粒界割れが発生してその粒界割れから鋼板が部分的に露出し、活物質の充填過程で用いるニッケル塩溶液やアルカリ水溶液にFeが溶解し、更に、活物質中に析出するからであると考えられる。
This is because if a nickel-plated steel sheet having more P and Mn than the above values is used, the amount of Fe in the positive electrode active material is increased and the low-temperature charge characteristics are deteriorated.
This phenomenon is caused when the P content and Mn content of the steel sheet are large, grain boundary cracks occur in the nickel plating layer during the sintering process during the production of the positive electrode, and the steel sheet is partially exposed from the grain boundary cracks, This is probably because Fe is dissolved in a nickel salt solution or an alkaline aqueous solution used in the filling process of the active material and further precipitated in the active material.

このような正極は、次のようにして製造される。
まず、上記したニッケルめっき鋼板の表面に、常法に従ってニッケル粉末と増粘剤と水を混錬して成るスラリーを塗着する。
このときのそれぞれの成分の混練割合やスラリーの塗着量は、活物質の目標充填量との関係で適宜調整されることは従来の場合と同様である。
Such a positive electrode is manufactured as follows.
First, a slurry obtained by kneading nickel powder, a thickener, and water is applied to the surface of the above-described nickel-plated steel sheet according to a conventional method.
The kneading ratio of each component and the coating amount of the slurry at this time are appropriately adjusted in relation to the target filling amount of the active material as in the conventional case.

ついで、還元性雰囲気中でスラリーに焼結処理を施す。この焼結処理を下記のように行うことが、本発明の製造方法における特徴である。
すなわち、スラリーが塗着されているニッケルめっき鋼板を、例えばN2雰囲気炉に挿入して加熱する。そのとき、鋼板の表面温度が1051℃以下となるように、ニッケルめっき鋼板の加熱温度が調整される。
Next, the slurry is sintered in a reducing atmosphere. It is a feature of the production method of the present invention that this sintering treatment is performed as follows.
That is, the nickel-plated steel sheet to which the slurry is applied is inserted into a N 2 atmosphere furnace and heated. At that time, the heating temperature of the nickel-plated steel sheet is adjusted so that the surface temperature of the steel sheet is 1051 ° C. or lower.

表面温度が1051℃よりも高くなると、最終的に得られた正極における法物質中のFe量が増加して蓄電池の低温充電特性は劣化する。しかし、焼結時の温度が低すぎると、スラリーのニッケル粉末の焼結が充分に進まないので、焼結温度としては、表面温度が最低でも800℃を示すような温度に設定されている。
焼結時間は、格別限定されるものではないが、通常5〜8分間程度であればよい。
When the surface temperature is higher than 1051 ° C., the amount of Fe in the legal substance in the positive electrode finally obtained increases and the low-temperature charge characteristics of the storage battery deteriorate. However, if the sintering temperature is too low, the sintering of the nickel powder in the slurry does not proceed sufficiently, so the sintering temperature is set to a temperature at which the surface temperature is at least 800 ° C.
Although the sintering time is not particularly limited, it may normally be about 5 to 8 minutes.

このようにして製造された多孔質ニッケル焼結基板に対して、その細孔に常法に従って活物質の所定量が充填されて、目的とする正極が得られる。
そしてその正極とセパレータから電極群を製造し、それをアルカリ電解液とともに外装缶の中に密封することにより、本発明のアルカリ蓄電池が得られる。
The porous nickel sintered substrate thus manufactured is filled with a predetermined amount of the active material in the pores in accordance with a conventional method, and the intended positive electrode is obtained.
And the alkaline storage battery of this invention is obtained by manufacturing an electrode group from the positive electrode and a separator, and sealing it in an exterior can with an alkaline electrolyte.

1.正極の製造
公称容量6.0Ahのニッケル水素蓄電池に組込むべき正極を次のようにして製造した。
まず、幅は同じであるが、厚みと長さが異なる値に制御されている複数の鋼板(SPCC−1B)を用意した。そして、各鋼板の両面にニッケルめっきを施こし、表1で示した厚み(片面の厚みを表示)のニッケルめっき層が形成されているニッケルめっき鋼板を製造した。
1. Production of positive electrode A positive electrode to be incorporated into a nickel-metal hydride storage battery having a nominal capacity of 6.0 Ah was produced as follows.
First, a plurality of steel plates (SPCC-1B) having the same width but controlled to have different thicknesses and lengths were prepared. And nickel plating was given to both surfaces of each steel plate, and the nickel plating steel plate in which the nickel plating layer of the thickness (displaying the thickness of one side) shown in Table 1 was formed was manufactured.

このニッケルめっき鋼板から、後述するように、多孔質ニッケル焼結鋼板が製造され、その表面には容量6.0Ahに相当する一定量の活物質が充填されるわけであるが、その場合、全ての正極でその容量は同じであるが、用いたニッケルめっき鋼板の厚みと表面寸法が異なっているので、各正極における単位面積当りの活物質の充填量(g/m)はそれぞれ異なってくる。 As described later, a porous nickel sintered steel sheet is produced from this nickel-plated steel sheet, and its surface is filled with a certain amount of active material corresponding to a capacity of 6.0 Ah. The capacity of the positive electrode is the same, but since the thickness and surface dimensions of the nickel-plated steel sheet used are different, the filling amount (g / m 2 ) of the active material per unit area in each positive electrode is different. .

一方、ニッケル粉末(フィッシャーサイズ2.2〜2.8μm)とカルボキシメチルセルロースと水を質量比100:5:125で混練してスラリーを調製した。
このスラリーをニッケルめっき鋼板に塗着したのち、N雰囲気炉中で焼結処理を行なった。このとき、鋼板の表面温度が表1で示した温度になるように炉運転を行なった。処理時間は6分間とした。
On the other hand, nickel powder (Fischer size 2.2 to 2.8 μm), carboxymethylcellulose and water were kneaded at a mass ratio of 100: 5: 125 to prepare a slurry.
This slurry was applied to a nickel-plated steel sheet, and then sintered in an N 2 atmosphere furnace. At this time, the furnace operation was performed so that the surface temperature of the steel sheet became the temperature shown in Table 1. The treatment time was 6 minutes.

表面に多孔度約85%のニッケル焼結体が形成されている多孔質ニッケル焼結基板が得られた。
ついで、硝酸ニッケルと硝酸コバルトが溶解している水溶液(比重1.75、ニッケルとコバルトの濃度は原子比で10:1)を調製し、ここに、各焼結基板を浸漬してその細孔内に硝酸ニッケルと硝酸コバルトを保持させた。
A porous nickel sintered substrate having a nickel sintered body with a porosity of about 85% formed on the surface was obtained.
Next, an aqueous solution in which nickel nitrate and cobalt nitrate are dissolved (specific gravity 1.75, the concentration of nickel and cobalt is 10: 1 by atomic ratio) is prepared, and each sintered substrate is immersed in the pores. Inside, nickel nitrate and cobalt nitrate were retained.

ついで、各焼結基板を、濃度25%の水酸化ナトリウム水溶液に浸漬して、細孔内の硝酸ニッケルと硝酸コバルトをそれぞれ水酸化ニッケルと水酸化コバルトに転換したのち、充分に水洗し、更に乾燥して水酸化ニッケルを主体とする活物質を充填した。
各焼結基板につき、容量6.0Ahに相当する活物質量が充填されるまで上記した一連の操作を反復し、充填されている活物質の絶対量は全て同じである各種の正極を製造した。
Next, each sintered substrate is immersed in an aqueous solution of sodium hydroxide having a concentration of 25% to convert nickel nitrate and cobalt nitrate in the pores to nickel hydroxide and cobalt hydroxide, respectively, and then sufficiently washed with water. It was dried and filled with an active material mainly composed of nickel hydroxide.
For each sintered substrate, the series of operations described above was repeated until the amount of active material corresponding to a capacity of 6.0 Ah was filled, and various positive electrodes having the same absolute amount of the filled active material were produced. .

そして、各正極における活物質の充填量を以下のようにして測定した。
すなわち、後述するようにして蓄電池を組立てたのち、当該電池を解体して正極のみを取出し、ついで当該正極を所定寸法(50mm×50mm)に切断し、その切断片を、マスプラット液(酢酸アンモニウム1mol/L、アンモニア水5mol/Lの混合水溶液)に浸漬して活物質を溶出させ、浸漬前後における質量差を測定し、その値を切断片の表面積で除算した。その結果を表1に示した。
And the filling amount of the active material in each positive electrode was measured as follows.
That is, after assembling the storage battery as described later, the battery is disassembled and only the positive electrode is taken out, and then the positive electrode is cut into a predetermined dimension (50 mm × 50 mm). The active material was eluted by immersing it in a 1 mol / L, aqueous solution of 5 mol / L of ammonia water), the mass difference before and after immersion was measured, and the value was divided by the surface area of the cut piece. The results are shown in Table 1.

2.電極の製造
組成がNd0.9Mg0.1(Ni0.9Co0.03Al0.073.5となるように各金属原料を秤量して全体を混合し、その混合物を高周波溶解炉で溶解したのち冷却して水素吸蔵合金のインゴットを製造した。
2. Production of electrode Each metal raw material is weighed so that the composition is Nd 0.9 Mg 0.1 (Ni 0.9 Co 0.03 Al 0.07 ) 3.5, and the whole is mixed. The mixture is melted in a high-frequency melting furnace and then cooled and cooled to form a hydrogen storage alloy. An ingot was manufactured.

このインゴットを温度1000℃のAr雰囲気において10時間加熱して結晶構造を調整したのち、不活性雰囲気中で機械的に粉砕し、更に分級して粒度が400メッシュ〜200メッシュの合金粉末を得た。
なお、この合金粉末は、レーザ回折・散乱式粒度分布測定装置を用いて重量積分50%にあたる平均粒径(D50値)を測定したところ25μmであった。
The ingot was heated in an Ar atmosphere at a temperature of 1000 ° C. for 10 hours to adjust the crystal structure, then mechanically pulverized in an inert atmosphere, and further classified to obtain an alloy powder having a particle size of 400 mesh to 200 mesh. .
The alloy powder had an average particle diameter (D 50 value) of 50% by weight integrated with a laser diffraction / scattering particle size distribution measuring device, and was 25 μm.

この合金粉末100質量部に対し、非水溶性結着材としてスチレンブタジエンラテックス0.5質量部、増粘剤としてカルボキシメチルセルロース0.3質量部、そして適量の純水を加えて全体を混練してスラリーを調製した。
そしてこのスラリーをパンチングニッケルシートに塗着し、室温で乾燥したのち圧延、裁断して負極を製造した。
To 100 parts by mass of the alloy powder, 0.5 part by mass of styrene butadiene latex as a water-insoluble binder, 0.3 part by mass of carboxymethyl cellulose as a thickener, and an appropriate amount of pure water are added to knead the whole. A slurry was prepared.
The slurry was applied to a punching nickel sheet, dried at room temperature, rolled and cut to produce a negative electrode.

3.セパレータの製造
芯材がポリプロピレンから成り、鞘材が低融点ポリエチレンからなる熱接着性の芯鞘型複合繊維と、高強度ポリプロピレン繊維とを用いて漉きあげたウェブを約130℃の乾燥温度(結合温度)で乾燥させる湿式法で、目付量50g/mの不織布を製造し、これをセパレータとして用いた。
4.ニッケル水素蓄電池の組立て
各正極と負極の間にセパレータを介装した状態で渦巻状に巻回して電極群を製造した。
3. Manufacture of separators A web made from a heat-adhesive core-sheath composite fiber, whose core material is made of polypropylene, and whose sheath material is low-melting polyethylene, and high-strength polypropylene fiber, is dried at a temperature of about 130 ° C (bonding) A non-woven fabric having a weight per unit area of 50 g / m 2 was manufactured by a wet method of drying at a temperature), and this was used as a separator.
4). Assembling of the nickel-metal hydride storage battery An electrode group was manufactured by spirally winding a separator between each positive electrode and negative electrode.

このとき、電極群の一端からは正極の導電性芯体であるニッケルめっき鋼板の端部が突出し、他端からは負極のパンチングニッケルシートの端部が突出するように巻回作業を行なった。
この電極群の一端から突出するニッケルめっき鋼板の端部には、面内に多数の開口を有する円板状の正極集電体を溶接して取付け、他端から突出するパンチングニッケルシートの端部には、同じく多数の開口を有する円板状の負極集電体を溶接して取付けた。
At this time, the winding operation was performed so that the end of the nickel-plated steel sheet as the positive electrode conductive core protruded from one end of the electrode group and the end of the punched nickel sheet of the negative electrode protruded from the other end.
At the end of the nickel-plated steel sheet protruding from one end of this electrode group, a disk-shaped positive electrode current collector having a large number of openings in the plane is welded and attached, and the end of the punching nickel sheet protruding from the other end A disk-shaped negative electrode current collector having a large number of openings was attached by welding.

そして、正極集電体の直径上に、ニッケルから成り、断面が長円形状をしたパイプ(肉厚は0.3mm)で、両端部が斜めに切り落とされた形状の筒状体を正極リードとして配置し、その下面をスポット溶接した。
この電極群を、負極集電体を下にして上部が開口する有底外装缶の中に収納し、外装缶の底面に負極集電体を溶接した。ついで、濃度30質量%の水酸化カリウム水溶液を電解液として外装缶に減圧注液したのち、正極リードの上面に、蓋板、絶縁ガスケット、弁体、圧縮コイルばね、および正極端子を備えている封口体を配置し、蓋板と正極リードの上面を溶接した。
Then, the positive electrode current collector is a pipe made of nickel and having an oval cross section (thickness is 0.3 mm), and a cylindrical body whose both ends are cut off obliquely is used as a positive electrode lead. The bottom surface was spot welded.
This electrode group was housed in a bottomed outer can opened at the top with the negative electrode current collector facing down, and the negative electrode current collector was welded to the bottom surface of the outer can. Next, after a 30% by weight potassium hydroxide aqueous solution is injected under reduced pressure into the outer can as an electrolyte, a cover plate, an insulating gasket, a valve body, a compression coil spring, and a positive electrode terminal are provided on the upper surface of the positive electrode lead. The sealing body was arrange | positioned and the upper surface of the cover plate and the positive electrode lead was welded.

ついで、封口体を電極群に向けて押圧し、筒状体の正極リードを圧縮変形させるとともに、外装缶の上部開口を内方に加締め加工して密閉構造を形成し、公称容量6.0Ahの円筒型ニッケル水素蓄電池にした。
5.測定
(1)高率放電特性の評価
表1の各正極が組込まれているニッケル水素蓄電池につき、下記の仕様で出力を測定し、各蓄電池の高率放電特性を評価した。
Next, the sealing body is pressed toward the electrode group to compress and deform the positive electrode lead of the cylindrical body, and the upper opening of the outer can is crimped inward to form a sealed structure with a nominal capacity of 6.0 Ah A cylindrical nickel-metal hydride storage battery.
5). Measurement (1) Evaluation of High Rate Discharge Characteristics For the nickel hydride storage battery in which each positive electrode of Table 1 is incorporated, the output was measured according to the following specifications, and the high rate discharge characteristics of each storage battery were evaluated.

各蓄電池につき、1Itの充電電流で、10サイクル目の容量に対して電池容量の50%、すなわちSOC(State of charge:充電深度)が50%に到達するまで30分間充電した。その後、40Aで放電→40Aで充電→80Aで放電→80Aで充電→120Aで放電→120Aで充電→160Aで放電→160Aで充電の順に充放電を反復した。
このとき、各ステップの間に10分間の休止期間を設け、各放電ステップを実施したのち10分間の休止を置いて10秒間ずつ放電を行ない、この10秒間経過点における電池電圧を放電電流に対してプロットし、最小2乗法に基づいて求めた直線が0.9Vに達するときの電流値を出力とした。
Each storage battery was charged for 30 minutes at a charging current of 1 It until 50% of the battery capacity with respect to the capacity of the 10th cycle, that is, SOC (State of charge: depth of charge) reached 50%. Thereafter, charging and discharging were repeated in the order of discharging at 40A → charging at 40A → discharging at 80A → charging at 80A → charging at 120A → charging at 120A → charging at 160A → discharging at 160A → charging at 160A.
At this time, a 10-minute rest period is provided between each step, and after each discharge step is performed, a 10-minute rest is performed for 10 seconds to discharge, and the battery voltage at the 10-second elapsed point is determined with respect to the discharge current. The current value when the straight line obtained on the basis of the least square method reaches 0.9 V was defined as the output.

そして、正極1が組込まれている蓄電池の出力を100としたときの各蓄電池の出力の比率を計算して高率放電性を評価した。以上の結果を表1に示した。
(2)正極活物質中のFe量の測定
各正極から表面層の部分(ニッケル焼結体の部分)を1.5g採取し、これを塩酸で完全に溶解したのち、溶解液を100mLに希釈した。そしてこの希釈液を原子吸光分析にかけ、Fe量を定量した。
And the ratio of the output of each storage battery when the output of the storage battery in which the positive electrode 1 was incorporated was set to 100 was calculated, and high rate discharge property was evaluated. The above results are shown in Table 1.
(2) Measurement of the amount of Fe in the positive electrode active material 1.5 g of the surface layer portion (nickel sintered body portion) was sampled from each positive electrode, completely dissolved in hydrochloric acid, and the solution was diluted to 100 mL. did. Then, this diluted solution was subjected to atomic absorption analysis, and the amount of Fe was quantified.

結果を表1に示した。またニッケルめっき鋼板のめっき厚、焼結時の表面温度とFe量との関係を図1に示した。
(3)低温充電特性の測定
各蓄電池を温度−10℃の環境に3時間放置したのち、1Itの充電電流で電池容量の100%まで充電した。SOC40%充電時における電圧Vと、ピーク電圧Vとの電圧差をΔVとして算出した。
The results are shown in Table 1. The relationship between the plating thickness of the nickel-plated steel sheet, the surface temperature during sintering, and the amount of Fe is shown in FIG.
(3) Measurement of low-temperature charge characteristics Each battery was left in an environment at a temperature of -10 ° C for 3 hours, and then charged to 100% of the battery capacity with a charge current of 1 It. The voltages V 1 at SOC 40% during charging, the voltage difference between the peak voltage V 2 was calculated as [Delta] V.

結果を表1に示した。また、ニッケルめっき鋼板のニッケルめっき厚、焼結時における表面温度、およびΔV値との関係を図2に、正極中のFe量とΔV値との関係を図3に示した。   The results are shown in Table 1. The relationship between the nickel plating thickness of the nickel-plated steel sheet, the surface temperature during sintering, and the ΔV value is shown in FIG. 2, and the relationship between the amount of Fe in the positive electrode and the ΔV value is shown in FIG.

Figure 2007265631
Figure 2007265631

(4)P量、Mn量の影響
製造ロットが異なる鋼板(SPCC−1B)を3種類用意した。各鋼板の表面に、厚み3.98μmのニッケルめっきを施し、ニッケルめっき鋼板にした。
(4) Influence of P amount and Mn amount Three types of steel plates (SPCC-1B) with different production lots were prepared. The surface of each steel plate was nickel-plated with a thickness of 3.98 μm to form a nickel-plated steel plate.

各ニッケルめっき鋼板につき、ICPでP量とM量を定量した。その結果を表2に示した。
ついで、各ニッケルめっき鋼板を水素雰囲気中で表面温度を1051℃に保持した状態で5分間加熱したのち、冷却をまって表面状態をEPMAで観測し、Fe/Ni比を測定した。結果を表2に示した。
About each nickel plating steel plate, P amount and M amount were quantified by ICP. The results are shown in Table 2.
Next, each nickel-plated steel sheet was heated in a hydrogen atmosphere with the surface temperature maintained at 1051 ° C. for 5 minutes, then cooled, the surface state was observed with EPMA, and the Fe / Ni ratio was measured. The results are shown in Table 2.

また、ニッケルめっき鋼板a,cにつき、加熱処理後の表面の顕微鏡写真を図4,図5に示した。   Moreover, the micrograph of the surface after heat processing was shown in FIG. 4, FIG. 5 about the nickel plating steel plates a and c.

Figure 2007265631
Figure 2007265631

6.評価と考察
以上のことから次のことが明らかである。
(1)まず、表1の正極1,正極2,正極3を対比して明らかなように、単位面積当たりの活物質の量が少なくなればなるほど、それを組み込んだ蓄電池の高率放電特性は向上している。
6). Evaluation and discussion From the above, the following is clear.
(1) First, as is clear by comparing the positive electrode 1, the positive electrode 2, and the positive electrode 3 in Table 1, the smaller the amount of active material per unit area, the higher the rate of discharge characteristics of the storage battery incorporating it. It has improved.

これは、単位面積当たりの活物質の量が少ない正極ほど薄長化しているので、電極群における反応対向面積が増加しているからである。
そして、高出力特性が要求される、例えば自動車関連用途を考えると、活物質の量が1400g/m2である正極1を用いた蓄電池では高率放電特性が不足している。このようなことから、正極における活物質の量は、正極1を用いた蓄電池に比べて160以上の高率放電特性を発揮させるために、850g/m2以下に設定されるべきである。
(2)表1から明らかなように、正極中のFe量はニッケルめっき鋼板のめっき厚と焼結処理時の表面温度の影響を受けている。すなわち、正極中のFe量は焼結処理時の表面温度が高くなるほど、まためっき厚が薄くなるほど増加している。
This is because the positive electrode with a smaller amount of active material per unit area is made thinner, so that the reaction facing area in the electrode group is increased.
Considering, for example, automobile-related applications where high output characteristics are required, high-rate discharge characteristics are insufficient in the storage battery using the positive electrode 1 with an active material amount of 1400 g / m 2 . For this reason, the amount of the active material in the positive electrode should be set to 850 g / m 2 or less in order to exhibit a high rate discharge characteristic of 160 or more as compared with the storage battery using the positive electrode 1.
(2) As is clear from Table 1, the amount of Fe in the positive electrode is affected by the plating thickness of the nickel-plated steel sheet and the surface temperature during the sintering process. That is, the amount of Fe in the positive electrode increases as the surface temperature during the sintering process increases and as the plating thickness decreases.

したがって、正極中のFe量を低減するためには、ニッケルめっき鋼板のめっき厚を厚くし、また焼結処理時に基板の表面温度が低くなるように焼結温度を調節すればよいことになる。
(3)表1から明らかなように、ΔV値は正極中のFe量、ニッケルめっき鋼板のめっき厚、焼結処理時の表面温度の影響を受けている。
Therefore, in order to reduce the amount of Fe in the positive electrode, it is only necessary to increase the plating thickness of the nickel-plated steel sheet and to adjust the sintering temperature so that the surface temperature of the substrate is lowered during the sintering process.
(3) As is apparent from Table 1, the ΔV value is affected by the amount of Fe in the positive electrode, the plating thickness of the nickel-plated steel sheet, and the surface temperature during the sintering process.

まず、図3から明らかなように、正極中のFe量が増加するにつれてΔV値は小さくなって低温充電特性が劣化していく。また図2から明らかなように、めっき厚が薄くなり、焼結処理時の表面温度が高くなるにつれて、やはりΔV値は小さくなって低温充電特性が劣化する。
このようなことから、低温充電特性を高めるためには、正極中のFe量を低減することが必要であり、それはめっき厚を厚くし、また焼結処理時に表面温度が低い状態で焼結することが必要であることがわかる。
First, as is apparent from FIG. 3, as the amount of Fe in the positive electrode increases, the ΔV value decreases and the low-temperature charging characteristics deteriorate. Further, as apparent from FIG. 2, as the plating thickness is reduced and the surface temperature during the sintering process is increased, the ΔV value is also decreased and the low-temperature charging characteristics are deteriorated.
For this reason, in order to improve the low-temperature charging characteristics, it is necessary to reduce the amount of Fe in the positive electrode, which increases the plating thickness and sinters at a low surface temperature during the sintering process. It turns out that it is necessary.

そして、車両関係用途では、充電カットの信頼性を確保するためには、−10℃環境下でもΔV値が0.07(V)以上の低温充電特性が必要とされることを考えると、図3から明らかなように、正極中のFe量を65ppmより少なくすべきであることがわかる。
そして、また、図2から明らかなように、めっき厚は4.0μm以上で、焼結処理時の表面温度は1051℃以下に制御されるべきであることがわかる。
For vehicle-related applications, in order to ensure the reliability of the charge cut, considering that low temperature charge characteristics with a ΔV value of 0.07 (V) or higher are required even in an environment of −10 ° C., from FIG. As can be seen, the amount of Fe in the positive electrode should be less than 65 ppm.
As can be seen from FIG. 2, the plating thickness should be 4.0 μm or more, and the surface temperature during the sintering process should be controlled to 1051 ° C. or less.

(4)表2のニッケルめっき鋼板a,b,cを対比して明らかなように、鋼板中のP量とMn量が増加するにつれて、加熱処理後のめっき層表面におけるFe量は増加していく。一方、図4と図5を対比して明らかなように、P量とMn量が少ないニッケルめっき鋼板aの場合、加熱処理後におけるめっき層の表面粒界の割れは認められないが、P量とMn量が多いニッケルめっき鋼板cの場合、数多くの大きな粒界割れがめっき層に認められる。 (4) As is apparent from the comparison of the nickel-plated steel sheets a, b, and c in Table 2, as the P content and Mn content in the steel sheet increase, the Fe content on the surface of the plated layer after heat treatment increases. Go. On the other hand, as is apparent from the comparison between FIG. 4 and FIG. 5, in the case of the nickel-plated steel sheet a having a small amount of P and Mn, cracks in the surface grain boundaries of the plated layer after the heat treatment are not observed, but the amount of P In the case of the nickel-plated steel sheet c having a large amount of Mn, many large grain boundary cracks are observed in the plated layer.

したがって、鋼板中のP,Mnが多い場合は、それを用いたニッケルめっき鋼板では焼結処理の過程でめっき層に多数の大きな粒界割れが発生し、そこから鋼板が部分的に露出するものと考えられる。そのため、活物質の充填作業を行うと、そのときに用いる硝酸ニッケルなどの薬液で露出する鋼板のFeが溶解し、それが活物質に析出するものと考えられる。   Therefore, when there are a lot of P and Mn in the steel sheet, a large number of large grain boundary cracks occur in the plating layer during the sintering process in the nickel-plated steel sheet using it, and the steel sheet is partially exposed from there. it is conceivable that. Therefore, it is considered that when the filling operation of the active material is performed, the Fe of the steel sheet exposed by the chemical solution such as nickel nitrate used at that time dissolves and precipitates on the active material.

このようなことから、用いるニッケルめっき鋼板としては、鋼板中のP量とMn量ができるだけ少ないもの、具体的には、P量は110ppm以下、Mn量は800ppm以下であることが好ましいものと考えられる。   For this reason, it is considered that the nickel-plated steel sheet to be used preferably has as little P and Mn content as possible in the steel sheet. Specifically, the P content is preferably 110 ppm or less and the Mn content is preferably 800 ppm or less. It is done.

本発明のアルカリ蓄電池は、高率放電特性が確保されており、かつ、低温充電特性が優れていて充電カットの制御が容易に実施できるので、ハイブリッド自動車や電気自動車など車両関係の駆動源として有用である。   The alkaline storage battery of the present invention is useful as a vehicle-related drive source such as a hybrid vehicle and an electric vehicle because it has high rate discharge characteristics and excellent low-temperature charging characteristics and can easily control charge cut. It is.

正極中のFe量と正極の導電性芯体であるニッケルめっき鋼板のめっき厚との関係を示すグラフである。It is a graph which shows the relationship between the amount of Fe in a positive electrode, and the plating thickness of the nickel plating steel plate which is a conductive core of a positive electrode. 低温充電特性の指標であるΔV値と正極の導電性芯体であるニッケルめっき鋼板のめっき厚との関係を示すグラフである。It is a graph which shows the relationship between (DELTA) V value which is a parameter | index of a low-temperature charge characteristic, and the plating thickness of the nickel plating steel plate which is a conductive core of a positive electrode. 低温充電特性の指標であるΔV値と正極中のFe量との関係を示すグラフである。It is a graph which shows the relationship between (DELTA) V value which is a parameter | index of a low-temperature charge characteristic, and the amount of Fe in a positive electrode. 加熱処理後のニッケルめっき鋼板aの表面状態を示す顕微鏡写真である。It is a microscope picture which shows the surface state of the nickel plating steel plate a after heat processing. 加熱処理後のニッケルめっき鋼板bの表面状態を示す顕微鏡写真である。It is a microscope picture which shows the surface state of the nickel plating steel plate b after heat processing.

Claims (3)

ニッケルめっき鋼板を導電性芯体とする多孔質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ている正極と、負極と、セパレータと、アルカリ電解液とを外装缶の中に具備するアルカリ蓄電池において、
前記正極に充填されている前記活物質の量が850g/m2以下であり、かつ、前記ニッケルめっき鋼板におけるめっき厚が4.0μm以上であることを特徴とするアルカリ蓄電池。
A positive electrode, a negative electrode, a separator, and an alkaline electrolyte filled with an active material mainly composed of nickel hydroxide in a porous nickel sintered substrate having a nickel-plated steel plate as a conductive core are placed in an outer can. In the alkaline storage battery provided,
The alkaline storage battery, wherein the amount of the active material filled in the positive electrode is 850 g / m 2 or less, and the plating thickness of the nickel-plated steel sheet is 4.0 μm or more.
前記ニッケルめっき鋼板におけるリンの量が110ppm以下であり、かつマンガンの量が800ppm以下である請求項1のアルカリ蓄電池。   The alkaline storage battery according to claim 1, wherein the amount of phosphorus in the nickel-plated steel sheet is 110 ppm or less and the amount of manganese is 800 ppm or less. ニッケル粉末と増粘剤と水とを混練してスラリーを調製し、前記スラリーをニッケルめっき鋼板に塗着し、ついで還元性雰囲気中で焼結処理を施して多孔質ニッケル焼結基板を製造したのち、前記多孔質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を充填する正極の製造方法において、
前記焼結処理時における温度を、前記多孔質ニッケル焼結基板の表面温度が1051℃以下となるように調整することを特徴とするアルカリ蓄電池用正極の製造方法。
Nickel powder, thickener and water were kneaded to prepare a slurry, and the slurry was applied to a nickel-plated steel sheet, and then sintered in a reducing atmosphere to produce a porous nickel sintered substrate. Then, in the method for producing a positive electrode in which the porous nickel sintered substrate is filled with an active material mainly composed of nickel hydroxide,
A method for producing a positive electrode for an alkaline storage battery, wherein the temperature during the sintering treatment is adjusted so that the surface temperature of the porous nickel sintered substrate is 1051 ° C. or lower.
JP2006085124A 2006-03-27 2006-03-27 Alkaline storage battery and method for producing positive electrode used therefor Active JP5147190B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006085124A JP5147190B2 (en) 2006-03-27 2006-03-27 Alkaline storage battery and method for producing positive electrode used therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006085124A JP5147190B2 (en) 2006-03-27 2006-03-27 Alkaline storage battery and method for producing positive electrode used therefor

Publications (2)

Publication Number Publication Date
JP2007265631A true JP2007265631A (en) 2007-10-11
JP5147190B2 JP5147190B2 (en) 2013-02-20

Family

ID=38638432

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006085124A Active JP5147190B2 (en) 2006-03-27 2006-03-27 Alkaline storage battery and method for producing positive electrode used therefor

Country Status (1)

Country Link
JP (1) JP5147190B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013015424A1 (en) 2011-07-28 2013-01-31 株式会社Gsユアサ Negative electrode for alkali storage battery, external container for alkali storage battery and alkali storage battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10241697A (en) * 1997-02-21 1998-09-11 Matsushita Electric Ind Co Ltd Alkaline storage battery electrode and manufacture thereof
JP2000106191A (en) * 1998-09-29 2000-04-11 Sanyo Electric Co Ltd Electrode for alkaline storage battery and the alkaline storage battery
JP2000268847A (en) * 1999-03-16 2000-09-29 Sanyo Electric Co Ltd Alkaline storage battery and its manufacture
JP2000311680A (en) * 1999-04-26 2000-11-07 Matsushita Electric Ind Co Ltd Sintered type positive electrode plate for nickel- hydrogen battery, its manufacture and nickel-hydrogen battery
WO2002071527A1 (en) * 2001-03-05 2002-09-12 Yuasa Corporation Method for manufacturing nickel hydrogen battery
JP2004031293A (en) * 2002-06-28 2004-01-29 Sanyo Electric Co Ltd Alkaline storage battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10241697A (en) * 1997-02-21 1998-09-11 Matsushita Electric Ind Co Ltd Alkaline storage battery electrode and manufacture thereof
JP2000106191A (en) * 1998-09-29 2000-04-11 Sanyo Electric Co Ltd Electrode for alkaline storage battery and the alkaline storage battery
JP2000268847A (en) * 1999-03-16 2000-09-29 Sanyo Electric Co Ltd Alkaline storage battery and its manufacture
JP2000311680A (en) * 1999-04-26 2000-11-07 Matsushita Electric Ind Co Ltd Sintered type positive electrode plate for nickel- hydrogen battery, its manufacture and nickel-hydrogen battery
WO2002071527A1 (en) * 2001-03-05 2002-09-12 Yuasa Corporation Method for manufacturing nickel hydrogen battery
JP2004031293A (en) * 2002-06-28 2004-01-29 Sanyo Electric Co Ltd Alkaline storage battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013015424A1 (en) 2011-07-28 2013-01-31 株式会社Gsユアサ Negative electrode for alkali storage battery, external container for alkali storage battery and alkali storage battery
US9525166B2 (en) 2011-07-28 2016-12-20 Gs Yuasa International Ltd. Negative electrode for alkaline secondary battery, outer case for alkaline secondary battery and alkaline secondary battery
US9748560B2 (en) 2011-07-28 2017-08-29 Gs Yuasa International Ltd. Negative electrode for alkaline secondary battery, outer case for alkaline secondary battery and alkaline secondary battery

Also Published As

Publication number Publication date
JP5147190B2 (en) 2013-02-20

Similar Documents

Publication Publication Date Title
JP5241188B2 (en) Alkaline storage battery system
JP5196938B2 (en) Alkaline storage battery system
JP5743780B2 (en) Cylindrical nickel-hydrogen storage battery
JP2008084649A (en) Hydrogen storage alloy for alkaline storage battery, alkaline storage battery and its manufacturing method
JP4496704B2 (en) Manufacturing method of nickel metal hydride battery
JP5322392B2 (en) Hydrogen storage alloy electrode, method for producing the same, and alkaline storage battery
JP4698291B2 (en) Alkaline storage battery
JP5354970B2 (en) Hydrogen storage alloy and alkaline storage battery
US20100081053A1 (en) Negative electrode for alkaline storage battery, alkaline storage battery, and method of manufacturing alkaline storage battery
JP2012238565A (en) Alkaline storage battery
JP5147190B2 (en) Alkaline storage battery and method for producing positive electrode used therefor
JP4497828B2 (en) Nickel-hydrogen storage battery and battery pack
JP5213312B2 (en) Alkaline storage battery
JP5147235B2 (en) Nickel metal hydride storage battery
JP2005108610A (en) Alkaline storage battery and battery pack
JP2013196991A (en) Alkali storage battery
JP2004281289A (en) Alkaline storage battery
JP3895985B2 (en) Nickel / hydrogen storage battery
JP3639494B2 (en) Nickel-hydrogen storage battery
JP3895984B2 (en) Nickel / hydrogen storage battery
JP7128069B2 (en) Positive electrode for alkaline secondary battery and alkaline secondary battery provided with this positive electrode
JP2003168422A (en) Square-shaped alkaline storage battery
WO2012165519A1 (en) Alkaline storage cell and alkaline storage cell system
JP4233234B2 (en) Method for producing alkaline storage battery
JP2005183339A (en) Nickel electrode for alkaline storage battery and alkaline storage battery

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20090325

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20120327

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120516

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120702

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20121031

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20121127

R151 Written notification of patent or utility model registration

Ref document number: 5147190

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20151207

Year of fee payment: 3