JPH11102700A - Manufacture of nickel electrode for alkaline storage battery - Google Patents
Manufacture of nickel electrode for alkaline storage batteryInfo
- Publication number
- JPH11102700A JPH11102700A JP9262415A JP26241597A JPH11102700A JP H11102700 A JPH11102700 A JP H11102700A JP 9262415 A JP9262415 A JP 9262415A JP 26241597 A JP26241597 A JP 26241597A JP H11102700 A JPH11102700 A JP H11102700A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- hydroxide
- nitrate
- magnesium
- cobalt
- 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
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 238000003860 storage Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims abstract description 110
- 239000011777 magnesium Substances 0.000 claims abstract description 107
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 63
- 239000010941 cobalt Substances 0.000 claims abstract description 61
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011148 porous material Substances 0.000 claims abstract description 61
- 239000011149 active material Substances 0.000 claims abstract description 33
- 150000002815 nickel Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 238000007654 immersion Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 15
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract 8
- 238000000975 co-precipitation Methods 0.000 abstract 4
- 238000007598 dipping method Methods 0.000 abstract 3
- 238000005429 filling process Methods 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 92
- 239000007864 aqueous solution Substances 0.000 description 74
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 43
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 43
- 150000001875 compounds Chemical class 0.000 description 40
- 230000005484 gravity Effects 0.000 description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 13
- 239000000347 magnesium hydroxide Substances 0.000 description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は正極活物質として水
酸化ニッケルを用いたニッケル・水素蓄電池、ニッケル
・カドミウム蓄電池、ニッケル・亜鉛蓄電池などのアル
カリ蓄電池のニッケル電極の製造方法に係り、特に、こ
のニッケル電極の高作動電圧化に関するものである。The present invention relates to a method for producing a nickel electrode of an alkaline storage battery such as a nickel-hydrogen storage battery, a nickel-cadmium storage battery, and a nickel-zinc storage battery using nickel hydroxide as a positive electrode active material. The present invention relates to increasing the operating voltage of a nickel electrode.
【０００２】[0002]
【従来の技術】従来、アルカリ蓄電池のニッケル電極
は、活物質保持体としての多孔性ニッケル焼結板を硝酸
ニッケル等の酸性ニッケル塩含浸液に浸漬して、その基
板中に酸性ニッケル塩を含浸した後、この酸性ニッケル
塩をアルカリ溶液中で水酸化ニッケルに置換する工程を
繰り返して、酸性ニッケル塩を水酸化ニッケル活物質に
する活物質充填操作を行って、水酸化ニッケル電極を製
造していた。2. Description of the Related Art Conventionally, a nickel electrode of an alkaline storage battery is prepared by immersing a porous nickel sintered plate as an active material holding body in an acidic nickel salt impregnating liquid such as nickel nitrate and impregnating the substrate with an acidic nickel salt. After that, the step of replacing the acidic nickel salt with nickel hydroxide in an alkaline solution is repeated, and an active material filling operation for converting the acidic nickel salt into a nickel hydroxide active material is performed to manufacture a nickel hydroxide electrode. Was.
【０００３】近年、携帯用電子・通信機器の急速な普及
により従来に増して高性能な蓄電池が要請されている。
このような背景にあって、水酸化ニッケルを正極活物質
とするアルカリ蓄電池においても、高容量化とともに高
作動電圧化等の一層の高性能化が要望されている。そこ
で、例えば、高作動電圧化に対しては、特開昭６４−３
９５８号公報に提案されている。この特開昭６４−３９
５８号公報において提案されたものは、ニッケル焼結基
板に水酸化ニッケル活物質を充填した後、水酸化マグネ
シウムを追加充填して、放電電位および放電容量を向上
させようとするものである。[0003] In recent years, with the rapid spread of portable electronic and communication devices, there has been a demand for higher performance storage batteries than ever before.
Against this background, even alkaline storage batteries using nickel hydroxide as a positive electrode active material are required to have higher performance as well as higher capacity and higher operating voltage. Therefore, for example, Japanese Patent Laid-Open No.
No. 958 proposes this. Japanese Patent Application Laid-Open No. 64-39
No. 58 proposes to improve the discharge potential and discharge capacity by filling a nickel sintered substrate with a nickel hydroxide active material and then additionally filling with magnesium hydroxide.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、特開昭
６４−３９５８号公報で提案される方法においては、活
物質利用率を向上させる効果は少なく、逆に、多量の水
酸化マグネシウムを共沈させると、充放電反応に寄与す
る水酸化ニッケル活物質の充填量が相対的に減少するた
め、電池容量が低下するとともに、作動電圧が低下する
という問題を生じた。そこで、本発明は上記問題点に鑑
みてなされたものであり、作動電圧を低下させることな
く、かつ活物質利用率が向上したアルカリ蓄電池用ニッ
ケル電極を得ることにある。However, in the method proposed in JP-A-64-3958, the effect of improving the utilization rate of the active material is small, and conversely, a large amount of magnesium hydroxide is coprecipitated. In addition, since the amount of the nickel hydroxide active material that contributes to the charge / discharge reaction is relatively reduced, the battery capacity is reduced and the operating voltage is reduced. Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a nickel electrode for an alkaline storage battery in which the operating voltage is reduced without lowering the operating voltage.
【０００５】[0005]
【課題を解決するための手段およびその作用・効果】上
記課題を解決するために、本発明のアルカリ蓄電池用ニ
ッケル電極の製造方法は、焼結基板の細孔内にコバルト
とマグネシウムの共沈水酸化物を生成させる共沈水酸化
物生成工程と、共沈水酸化物が生成された焼結基板に水
酸化ニッケルを主成分とする正極活物質を充填する活物
質充填工程とを備えるようにしたことを特徴としてい
る。In order to solve the above-mentioned problems, a method for producing a nickel electrode for an alkaline storage battery according to the present invention comprises the steps of: A co-precipitated hydroxide generating step of generating a material, and an active material filling step of filling the sintered substrate in which the co-precipitated hydroxide is generated with a positive electrode active material containing nickel hydroxide as a main component. Features.
【０００６】水酸化コバルトは活性度が低いため、単に
水酸化コバルトの単独層を活物質表面に設けても、その
後の充電による電気化学的酸化によってオキシ水酸化コ
バルトへの転化が効果的に行えず、水酸化ニッケル活物
質上にオキシ水酸化ニッケルを均一に覆うことができな
く、活物質利用率が向上しないとともに、作動電圧も上
昇しない。Since cobalt hydroxide has a low activity, even if a single layer of cobalt hydroxide is simply provided on the surface of the active material, it can be effectively converted to cobalt oxyhydroxide by electrochemical oxidation by subsequent charging. Therefore, the nickel oxyhydroxide cannot be uniformly covered on the nickel hydroxide active material, so that the active material utilization rate does not improve and the operating voltage does not increase.
【０００７】しかしながら、本発明のようにコバルトと
マグネシウムの共沈水酸化物を焼結基板の細孔内に生成
させた後、活物質化するようにすると、コバルトとマグ
ネシウムの共沈水酸化物と水酸化ニッケル活物質との固
層界面において固溶化が生じて、水酸化ニッケル活物質
の導電性が著しく向上し、作動電圧が上昇するとともに
活物質利用率が向上する。However, when the coprecipitated hydroxide of cobalt and magnesium is formed in the pores of the sintered substrate and then converted into an active material as in the present invention, the coprecipitated hydroxide of cobalt and magnesium is mixed with water. Solid solution occurs at the solid layer interface with the nickel oxide active material, so that the conductivity of the nickel hydroxide active material is significantly improved, the operating voltage is increased, and the active material utilization rate is improved.
【０００８】そして、本発明の活物質化処理は、共沈水
酸化物が生成された焼結基板を酸性ニッケル塩に浸漬し
て焼結基板内に酸性ニッケル塩を含浸する酸性ニッケル
塩浸漬工程と、この酸性ニッケル塩浸漬工程により酸性
ニッケル塩を含浸させた焼結基板をアルカリ溶液中に浸
漬して酸性ニッケル塩を水酸化ニッケルに置換するアル
カリ処理工程とを備え、酸性ニッケル塩浸漬工程とアル
カリ処理工程とを所定回数だけ繰り返して酸性ニッケル
塩を水酸化ニッケル活物質とするようにしている。[0008] The active material conversion treatment of the present invention includes the step of immersing the sintered substrate in which the coprecipitated hydroxide has been generated in an acidic nickel salt to impregnate the sintered substrate with the acidic nickel salt. An alkaline treatment step of immersing the sintered substrate impregnated with the acidic nickel salt in the acidic nickel salt immersion step in an alkaline solution to replace the acidic nickel salt with nickel hydroxide, and The treatment step is repeated a predetermined number of times to convert the acidic nickel salt into a nickel hydroxide active material.
【０００９】このように、共沈水酸化物の表面に酸性ニ
ッケル塩を含浸させた後、活物質化処理を行うと、共沈
水酸化物と水酸化ニッケル活物質との固層界面において
容易に固溶化が生じ、水酸化ニッケル活物質の導電性が
著しく向上する。このため、作動電圧が上昇するととも
に活物質利用率が向上する。As described above, when the surface of the coprecipitated hydroxide is impregnated with the acidic nickel salt and then subjected to the active material treatment, the solidified interface between the coprecipitated hydroxide and the nickel hydroxide active material is easily formed. Solubilization occurs and the conductivity of the nickel hydroxide active material is significantly improved. For this reason, the operating voltage increases and the active material utilization rate improves.
【００１０】また、共沈水酸化物のコバルトおよびマグ
ネシウムの比率が金属モル比率でマグネシウム／（コバ
ルト＋マグネシウム）を０．４から０．６の範囲になる
ように規定することが好ましい。このように規定する
と、共沈水酸化物と水酸化ニッケル活物質との固層界面
において最適な固溶化が生じ、水酸化ニッケル活物質の
導電性が著しく向上する。It is preferable that the ratio of cobalt and magnesium in the coprecipitated hydroxide is specified such that magnesium / (cobalt + magnesium) is in the range of 0.4 to 0.6 in terms of metal molar ratio. With such a definition, optimal solution formation occurs at the solid phase interface between the coprecipitated hydroxide and the nickel hydroxide active material, and the conductivity of the nickel hydroxide active material is significantly improved.
【００１１】[0011]
１．焼結基板の作製 ニッケル粉末にカルボキシメチルセルロース等の増粘剤
および水を混練してスラリーを調整し、このスラリーを
ニッケル多孔体からなる導電性芯体に塗着する。この
後、スラリーを塗着した導電性芯体を還元性雰囲気下で
焼結し、多孔度８０％の焼結基板を作製する。1. Production of Sintered Substrate A thickener such as carboxymethylcellulose and water are kneaded with nickel powder to prepare a slurry, and this slurry is applied to a conductive core made of a porous nickel material. Thereafter, the conductive core coated with the slurry is sintered in a reducing atmosphere to produce a sintered substrate having a porosity of 80%.
【００１２】２．ニッケル電極の作製 （１）ニッケル電極Ａ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比でＣｏ：Ｍｇ＝１：１、つまり、Ｍｇ／（Ｃｏ＋
Ｍｇ）＝０．５となるように混合した硝酸塩混合水溶液
に浸漬して、硝酸塩混合水溶液を含浸させた後、乾燥さ
せて焼結基板の細孔の表面に硝酸コバルトと硝酸マグネ
シウムの共沈化合物を析出させる。この後、２５重量％
の水酸化ナトリウム水溶液に浸漬して、焼結基板の細孔
の表面に析出した硝酸コバルトと硝酸マグネシウムの共
沈化合物をコバルトとマグネシウムの共沈水酸化物に置
換する。2. Production of Nickel Electrode (1) Nickel Electrode A The sintered substrate having the porosity of 80% produced as described above was prepared by mixing a cobalt nitrate aqueous solution and a magnesium nitrate aqueous solution at a metal molar ratio of Co: Mg = 1: 1, that is, / (Co +
Mg) = 0.5, soaked in a nitrate mixed aqueous solution mixed so as to be 0.5, impregnated with the nitrate mixed aqueous solution, and then dried to form a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Is precipitated. After this, 25% by weight
, And the coprecipitated compound of cobalt nitrate and magnesium nitrate deposited on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium.
【００１３】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を２５重量％の水酸化ナトリウム水溶液中に浸漬し
て、コバルトとマグネシウムの共沈水酸化物の表面に析
出させた硝酸ニッケルを水酸化ニッケルに置換する。After replacing the coprecipitated compound of cobalt nitrate and magnesium nitrate with a coprecipitated hydroxide of cobalt and magnesium, the substrate is immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate has been deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace the nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００１４】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトと硝酸マグネシ
ウムの共沈化合物を析出させた後、この共沈化合物をコ
バルトとマグネシウムの共沈水酸化物に置換し、この共
沈水酸化物の表面に水酸化ニッケルを充填した電極をニ
ッケル電極Ａとする。このようにして作製したニッケル
電極Ａのコバルトとマグネシウムを化学分析により定量
して金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍｇ）
＝０．５となっていることが分かった。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate. Fill with nickel oxide. After depositing a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate in this way, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, An electrode having a surface filled with nickel hydroxide is referred to as a nickel electrode A. The cobalt and magnesium of the nickel electrode A thus produced were quantified by chemical analysis to measure the metal molar ratio, and the result was Mg / (Co + Mg).
= 0.5.
【００１５】（２）ニッケル電極Ｂ 上述のように作製した多孔度８０％の焼結基板を、硝酸
マグネシウム水溶液に浸漬して、焼結基板の細孔の表面
に硝酸マグネシウムを析出させる。この後、２５重量％
の水酸化ナトリウム水溶液に浸漬して、焼結基板の細孔
の表面に析出した硝酸マグネシウムを水酸化マグネシウ
ムに置換する。硝酸マグネシウムを水酸化マグネシウム
に置換した後、８０℃で比重１．７５の硝酸ニッケルを
主体とする水溶液に浸漬して、硝酸ニッケルを主体とす
る水溶液を含浸させた後、乾燥させて水酸化マグネシウ
ムの表面に硝酸ニッケルを析出させる。(2) Nickel electrode B The sintered substrate having the porosity of 80% produced as described above is immersed in an aqueous solution of magnesium nitrate to deposit magnesium nitrate on the surface of the pores of the sintered substrate. After this, 25% by weight
To replace the magnesium nitrate deposited on the surface of the pores of the sintered substrate with magnesium hydroxide. After substituting magnesium nitrate with magnesium hydroxide, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C., impregnated with an aqueous solution mainly composed of nickel nitrate, and then dried to obtain magnesium hydroxide. Nickel nitrate is deposited on the surface of.
【００１６】水酸化マグネシウムの表面に硝酸ニッケル
を析出させた焼結基板を、２５重量％の水酸化ナトリウ
ム水溶液中に浸漬して、硝酸ニッケルを水酸化ニッケル
に置換する。その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸マグネシウムを析出させ
た後、この硝酸マグネシウムを水酸化マグネシウムに置
換し、この水酸化マグネシウムの表面に水酸化ニッケル
を充填した電極をニッケル電極Ｂとする。The sintered substrate having nickel nitrate deposited on the surface of magnesium hydroxide is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate with nickel hydroxide. Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same operation as described above is repeated a predetermined number of times (for example, five times) to deposit nickel hydroxide in the pores of the sintered substrate. Fill. After magnesium nitrate was deposited on the surface of the pores of the sintered substrate in this manner, the magnesium nitrate was replaced with magnesium hydroxide, and the electrode with the surface of the magnesium hydroxide filled with nickel hydroxide was replaced with nickel electrode B. And
【００１７】（３）ニッケル電極Ｃ 上述のように作製した多孔度８０％の焼結基板を、８０
℃で比重１．７５の硝酸ニッケルを主体とする水溶液に
浸漬して、焼結基板の細孔内に硝酸ニッケルを含浸させ
た後、乾燥させて焼結基板の細孔内に硝酸ニッケルを析
出させる。硝酸ニッケルを析出させた焼結基板を、２５
重量％の水酸化ナトリウム水溶液中に浸漬して、細孔内
に析出させた硝酸ニッケルを水酸化ニッケルに置換す
る。(3) Nickel Electrode C The sintered substrate having the porosity of 80% produced as described above is
After immersion in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at a temperature of ℃, and impregnating the pores of the sintered substrate with nickel nitrate, drying the precipitate to deposit nickel nitrate in the pores of the sintered substrate. Let it. The sintered substrate on which nickel nitrate was deposited was 25
The nickel nitrate precipitated in the pores by being immersed in a weight% aqueous solution of sodium hydroxide is replaced with nickel hydroxide.
【００１８】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に水酸化ニッケルを充填した焼
結基板を硝酸マグネシウム水溶液に浸漬して、水酸化ニ
ッケルの表面に硝酸マグネシウムを析出させる。この
後、２５重量％の水酸化ナトリウム水溶液中に浸漬し
て、硝酸マグネシウムを水酸化マグネシウムに置換す
る。このようにして焼結基板の細孔の表面に水酸化ニッ
ケルを充填し、この水酸化ニッケルの表面に水酸化マグ
ネシウムを析出させた電極をニッケル電極Ｃとする。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same processing operation as described above is repeated a predetermined number of times (for example, five times). Fill with nickel oxide. Thus, the sintered substrate in which the surface of the pores of the sintered substrate is filled with nickel hydroxide is immersed in an aqueous solution of magnesium nitrate to precipitate magnesium nitrate on the surface of the nickel hydroxide. Thereafter, the substrate is immersed in a 25% by weight aqueous sodium hydroxide solution to replace magnesium nitrate with magnesium hydroxide. The electrode in which nickel hydroxide is filled in the surface of the pores of the sintered substrate and magnesium hydroxide is deposited on the surface of the nickel hydroxide is referred to as nickel electrode C.
【００１９】（４）ニッケル電極Ｄ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液に浸漬して、焼結基板の細孔の表面に硝
酸コバルトを析出させる。この後、２５重量％の水酸化
ナトリウム水溶液に浸漬して、焼結基板の細孔の表面に
析出した硝酸コバルトを水酸化コバルトに置換する。硝
酸コバルトを水酸化コバルトに置換した後、８０℃で比
重１．７５の硝酸ニッケルを主体とする水溶液に浸漬し
て、焼結基板の細孔内に硝酸ニッケルを主体とする水溶
液を含浸させた後、乾燥させて水酸化コバルトの表面に
硝酸ニッケルを析出させる。硝酸ニッケルを析出させた
焼結基板を、２５重量％の水酸化ナトリウム水溶液中に
浸漬して、硝酸ニッケルを水酸化ニッケルに置換する。(4) Nickel electrode D The sintered substrate having the porosity of 80% prepared as described above is immersed in an aqueous solution of cobalt nitrate to deposit cobalt nitrate on the surface of the pores of the sintered substrate. Thereafter, the substrate is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace cobalt nitrate deposited on the surface of the pores of the sintered substrate with cobalt hydroxide. After replacing cobalt nitrate with cobalt hydroxide, the substrate was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. to impregnate the pores of the sintered substrate with an aqueous solution mainly composed of nickel nitrate. Thereafter, drying is performed to deposit nickel nitrate on the surface of the cobalt hydroxide. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous sodium hydroxide solution to replace nickel nitrate with nickel hydroxide.
【００２０】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトを析出させた
後、この硝酸コバルトを水酸化コバルトに置換し、この
水酸化コバルトの表面に水酸化ニッケルを充填した電極
をニッケル電極Ｄとする。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same operation as described above is repeated a predetermined number of times (for example, five times), so that water enters the pores of the sintered substrate. Fill with nickel oxide. After depositing cobalt nitrate on the surface of the pores of the sintered substrate in this manner, the cobalt nitrate is replaced with cobalt hydroxide, and the electrode having the surface of the cobalt hydroxide filled with nickel hydroxide is a nickel electrode D And
【００２１】（５）ニッケル電極Ｅ 上述のように作製した多孔度８０％の焼結基板を、８０
℃で比重１．７５の硝酸ニッケルを主体とする水溶液に
浸漬して、焼結基板の細孔内に硝酸ニッケルを主体とす
る水溶液を含浸させた後、乾燥させて焼結基板の細孔内
に硝酸ニッケルを析出させる。硝酸ニッケルを析出させ
た焼結基板を、２５重量％の水酸化ナトリウム水溶液中
に浸漬して、細孔内に析出させた硝酸ニッケルを水酸化
ニッケルに置換する。その後、再び焼結基板を硝酸ニッ
ケルを主体とする水溶液に浸漬する処理操作に戻り、上
記と同様な処理操作を所定回数（例えば５回）繰り返し
て焼結基板の細孔内に水酸化ニッケルを充填する。この
ようにして焼結基板の細孔の表面に水酸化ニッケルを充
填した電極をニッケル電極Ｅとする。(5) Nickel Electrode E The sintered substrate having the porosity of 80% produced as described above is
After being immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at a temperature of 0 ° C., and impregnated with an aqueous solution mainly composed of nickel nitrate in the pores of the sintered substrate, dried and dried in the pores of the sintered substrate. Is precipitated with nickel nitrate. The sintered substrate on which nickel nitrate has been deposited is immersed in a 25% by weight aqueous sodium hydroxide solution to replace the nickel nitrate deposited in the pores with nickel hydroxide. Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same operation as described above is repeated a predetermined number of times (for example, five times) to deposit nickel hydroxide in the pores of the sintered substrate. Fill. The electrode in which the surface of the pores of the sintered substrate is filled with nickel hydroxide in this manner is referred to as a nickel electrode E.
【００２２】３．電極電位の測定 上述のように作成したニッケル電極Ａ〜Ｅを、比重１．
２０の水酸化カリウム水溶液中でニッケル板を対極とし
て理論容量の５時間率で充電した後、３時間率で放電し
て、放電時間毎の各ニッケル電極Ａ〜Ｅの単極電位を参
照電極（Ｈｇ／ＨｇＯ）を用いて測定すると図１に示す
ような結果となった。3. Measurement of Electrode Potential Nickel electrodes A to E prepared as described above were subjected to a specific gravity of 1.
After charging at a 5 hour rate of the theoretical capacity with a nickel plate as a counter electrode in an aqueous potassium hydroxide solution of 20 and discharging at a 3 hour rate, the unipolar potential of each of the nickel electrodes A to E for each discharge time was determined as a reference electrode ( Hg / HgO), the result was as shown in FIG.
【００２３】図１より明らかなように、焼結基板の細孔
の表面に生成したコバルトとマグネシウムの共沈水酸化
物の表面に水酸化ニッケルを充填したニッケル電極Ａ
は、焼結基板の細孔の表面に生成した水酸化マグネシウ
ムの表面に水酸化ニッケルを充填したニッケル電極Ｂ、
焼結基板の細孔の表面に水酸化ニッケルを充填しこの水
酸化ニッケルの表面に水酸化マグネシウムを析出させた
ニッケル電極Ｃ、焼結基板の細孔の表面に生成した水酸
化コバルトの表面に水酸化ニッケルを充填したニッケル
電極Ｄ、焼結基板の細孔の表面に水酸化ニッケルを充填
したニッケル電極Ｅより、それぞれ高い単極電位となっ
た。As apparent from FIG. 1, a nickel electrode A in which nickel hydroxide was filled on the surface of a coprecipitated hydroxide of cobalt and magnesium formed on the surface of the pores of the sintered substrate.
Is a nickel electrode B filled with nickel hydroxide on the surface of magnesium hydroxide generated on the surface of the pores of the sintered substrate,
Nickel electrode C in which nickel hydroxide is filled into the surface of the pores of the sintered substrate and magnesium hydroxide is deposited on the surface of the nickel hydroxide, and the surface of the cobalt hydroxide formed on the surface of the pores of the sintered substrate The nickel electrode D filled with nickel hydroxide and the nickel electrode E filled with nickel hydroxide on the surface of the pores of the sintered substrate had higher monopolar potentials.
【００２４】この理由は次のように考えることができ
る。即ち、水酸化コバルトおよび水酸化マグネシウムは
導電性が低い物質であることを考慮すると、ニッケル焼
結基板の表面のコバルトとマグネシウムの共沈水酸化物
を生成させ、この共沈水酸化物の表面に水酸化ニッケル
活物質を充填すると、コバルトとマグネシウムの共沈水
酸化物と水酸化ニッケル活物質との固相界面において固
溶化が起こり、この固溶化が水酸化ニッケル活物質の導
電性を著しく向上させているものと考えることができ
る。The reason can be considered as follows. That is, considering that cobalt hydroxide and magnesium hydroxide are substances having low conductivity, a coprecipitated hydroxide of cobalt and magnesium is generated on the surface of the nickel sintered substrate, and the surface of the coprecipitated hydroxide is formed with water. When the nickel oxide active material is filled, solid solution occurs at the solid phase interface between the cobalt and magnesium coprecipitated hydroxide and the nickel hydroxide active material, and this solid solution significantly improves the conductivity of the nickel hydroxide active material. You can think that there is.
【００２５】４．金属コバルトと金属マグネシウムの比
率の検討 （１）ニッケル電極Ａ１ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．２となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。4. Investigation of the ratio of metallic cobalt to metallic magnesium (1) Nickel electrode A1 The sintered substrate having the porosity of 80% produced as described above was prepared by mixing a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate with Mg / (Co + Mg). = 0.2, and a coprecipitated compound of cobalt nitrate and magnesium nitrate is precipitated on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００２６】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After replacing the coprecipitated compound of cobalt nitrate and magnesium nitrate with a coprecipitated hydroxide of cobalt and magnesium, it is immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００２７】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトと硝酸マグネシ
ウムの共沈化合物を析出させた後、この共沈化合物をコ
バルトとマグネシウムの共沈水酸化物に置換し、この共
沈水酸化物の表面に水酸化ニッケルを充填した電極をニ
ッケル電極Ａ１とする。このようにして作製したニッケ
ル電極Ａ１のコバルトとマグネシウムを化学分析により
定量して金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍ
ｇ）＝０．２となっていることが分かった。Thereafter, the process returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate. Fill with nickel oxide. After depositing a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate in this way, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, The electrode whose surface is filled with nickel hydroxide is referred to as a nickel electrode A1. Cobalt and magnesium of the nickel electrode A1 thus manufactured were quantified by chemical analysis to measure the metal molar ratio. As a result, Mg / (Co + M
g) = 0.2 was found.
【００２８】（２）ニッケル電極Ａ２ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．３となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(2) Nickel Electrode A2 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.3 in terms of a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００２９】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After the coprecipitated compound of cobalt nitrate and magnesium nitrate was replaced with a coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００３０】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトと硝酸マグネシ
ウムの共沈化合物を析出させた後、この共沈化合物をコ
バルトとマグネシウムの共沈水酸化物に置換し、この共
沈水酸化物の表面に水酸化ニッケルを充填した電極をニ
ッケル電極Ａ２とする。このようにして作製したニッケ
ル電極Ａ２のコバルトとマグネシウムを化学分析により
定量して金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍ
ｇ）＝０．３となっていることが分かった。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same processing operation as described above is repeated a predetermined number of times (for example, 5 times). Fill with nickel oxide. After depositing a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate in this way, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, An electrode having a surface filled with nickel hydroxide is referred to as a nickel electrode A2. Cobalt and magnesium of the nickel electrode A2 thus manufactured were quantified by chemical analysis to measure the metal molar ratio, and it was found that Mg / (Co + M
g) = 0.3 was found.
【００３１】（３）ニッケル電極Ａ３ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．４となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(3) Nickel Electrode A3 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.4 in a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００３２】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After substituting the coprecipitated compound of cobalt nitrate and magnesium nitrate with the coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００３３】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトと硝酸マグネシ
ウムの共沈化合物を析出させた後、この共沈化合物をコ
バルトとマグネシウムの共沈水酸化物に置換し、この共
沈水酸化物の表面に水酸化ニッケルを充填した電極をニ
ッケル電極Ａ３とする。このようにして作製したニッケ
ル電極Ａ３のコバルトとマグネシウムを化学分析により
定量して金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍ
ｇ）＝０．４となっていることが分かった。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate, and the same operation as described above is repeated a predetermined number of times (for example, 5 times), so that water enters the pores of the sintered substrate. Fill with nickel oxide. After depositing a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate in this way, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, The electrode having the surface filled with nickel hydroxide is referred to as a nickel electrode A3. Cobalt and magnesium of the nickel electrode A3 thus produced were quantified by chemical analysis to measure the metal molar ratio. As a result, Mg / (Co + M
g) = 0.4.
【００３４】（４）ニッケル電極Ａ４ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．５となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(4) Nickel Electrode A4 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.5 in a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００３５】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After the coprecipitated compound of cobalt nitrate and magnesium nitrate was replaced with a coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００３６】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面にコバルトとマグネシウムの共
沈化合物を析出させた後、この共沈化合物をコバルトと
マグネシウムの共沈水酸化物に置換し、この共沈水酸化
物の表面に水酸化ニッケルを充填した電極をニッケル電
極Ａ４とする。このようにして作製したニッケル電極Ａ
４のコバルトとマグネシウムを化学分析により定量して
金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍｇ）＝
０．５となっていることが分かった。Thereafter, the process returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate. Fill with nickel oxide. After depositing the coprecipitated compound of cobalt and magnesium on the surface of the pores of the sintered substrate in this manner, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, and the surface of the coprecipitated hydroxide is removed. The electrode filled with nickel hydroxide is referred to as a nickel electrode A4. Nickel electrode A thus produced
4 was determined by chemical analysis to determine the metal molar ratio, and Mg / (Co + Mg) =
It turned out to be 0.5.
【００３７】（５）ニッケル電極Ａ５ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．６となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(5) Nickel electrode A5 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.6 in terms of a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００３８】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After substituting the coprecipitated compound of cobalt nitrate and magnesium nitrate with the coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００３９】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面にコバルトとマグネシウムの共
沈化合物を析出させた後、この共沈化合物をコバルトと
マグネシウムの共沈水酸化物に置換し、この共沈水酸化
物の表面に水酸化ニッケルを充填した電極をニッケル電
極Ａ５とする。このようにして作製したニッケル電極Ａ
５のコバルトとマグネシウムを化学分析により定量して
金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍｇ）＝
０．６となっていることが分かった。Thereafter, the operation returns to the operation of immersing the sintered substrate again in an aqueous solution mainly containing nickel nitrate, and the same processing operation as described above is repeated a predetermined number of times (for example, five times). Fill with nickel oxide. After depositing the coprecipitated compound of cobalt and magnesium on the surface of the pores of the sintered substrate in this manner, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, and the surface of the coprecipitated hydroxide is removed. The electrode filled with nickel hydroxide is referred to as a nickel electrode A5. Nickel electrode A thus produced
When the molar ratio of metal was determined by quantifying cobalt and magnesium by chemical analysis, Mg / (Co + Mg) =
It turned out to be 0.6.
【００４０】（６）ニッケル電極Ａ６ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．７となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(6) Nickel Electrode A6 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.7 in terms of a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００４１】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After replacing the coprecipitated compound of cobalt nitrate and magnesium nitrate with the coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００４２】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面にコバルトとマグネシウムの共
沈化合物を析出させた後、この共沈化合物をコバルトと
マグネシウムの共沈水酸化物に置換し、この共沈水酸化
物の表面に水酸化ニッケルを充填した電極をニッケル電
極Ａ６とする。このようにして作製したニッケル電極Ａ
６のコバルトとマグネシウムを化学分析により定量して
金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍｇ）＝
０．７となっていることが分かった。Thereafter, the process returns to the operation of immersing the sintered substrate again in an aqueous solution mainly containing nickel nitrate, and the same processing operation as described above is repeated a predetermined number of times (for example, five times), so that water enters the pores of the sintered substrate. Fill with nickel oxide. After depositing the coprecipitated compound of cobalt and magnesium on the surface of the pores of the sintered substrate in this manner, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, and the surface of the coprecipitated hydroxide is removed. The electrode filled with nickel hydroxide is referred to as a nickel electrode A6. Nickel electrode A thus produced
6 was determined by chemical analysis to determine the metal molar ratio, and Mg / (Co + Mg) =
It turned out to be 0.7.
【００４３】（７）ニッケル電極Ａ７ 上述のように作製した多孔度８０％の焼結基板を、硝酸
コバルト水溶液と硝酸マグネシウム水溶液からなる金属
モル比で、Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．９となるように
混合した硝酸塩混合水溶液に浸漬して、焼結基板の細孔
の表面に硝酸コバルトと硝酸マグネシウムの共沈化合物
を析出させる。この後、２５重量％の水酸化ナトリウム
水溶液に浸漬して、焼結基板の細孔の表面に析出した硝
酸コバルトと硝酸マグネシウムの共沈化合物をコバルト
とマグネシウムの共沈水酸化物に置換する。(7) Nickel electrode A7 The sintered substrate having the porosity of 80% produced as described above was used to obtain Mg / (Co + Mg) = 0.9 in a metal molar ratio of an aqueous solution of cobalt nitrate and an aqueous solution of magnesium nitrate. Is immersed in the mixed aqueous solution of nitrate to precipitate a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate. Thereafter, the coprecipitated compound of cobalt nitrate and magnesium nitrate precipitated on the surface of the pores of the sintered substrate is replaced with a coprecipitated hydroxide of cobalt and magnesium by immersion in a 25% by weight aqueous sodium hydroxide solution.
【００４４】硝酸コバルトと硝酸マグネシウムの共沈化
合物をコバルトとマグネシウムの共沈水酸化物に置換し
た後、８０℃で比重１．７５の硝酸ニッケルを主体とす
る水溶液に浸漬して、焼結基板の細孔内に硝酸ニッケル
を主体とする水溶液を含浸させた後、乾燥させてコバル
トとマグネシウムの共沈水酸化物の表面に主として硝酸
ニッケルを析出させる。硝酸ニッケルを析出させた焼結
基板を、２５重量％の水酸化ナトリウム水溶液中に浸漬
して、コバルトとマグネシウムの共沈水酸化物の表面に
析出させた硝酸ニッケルを水酸化ニッケルに置換する。After substituting the coprecipitated compound of cobalt nitrate and magnesium nitrate with the coprecipitated hydroxide of cobalt and magnesium, it was immersed in an aqueous solution mainly composed of nickel nitrate having a specific gravity of 1.75 at 80 ° C. The pores are impregnated with an aqueous solution mainly composed of nickel nitrate and then dried to deposit nickel nitrate mainly on the surface of the coprecipitated hydroxide of cobalt and magnesium. The sintered substrate on which nickel nitrate is deposited is immersed in a 25% by weight aqueous solution of sodium hydroxide to replace nickel nitrate deposited on the surface of the coprecipitated hydroxide of cobalt and magnesium with nickel hydroxide.
【００４５】その後、再び焼結基板を硝酸ニッケルを主
体とする水溶液に浸漬する処理操作に戻り、上記と同様
な処理操作を所定回数（例えば５回）繰り返して焼結基
板の細孔内に水酸化ニッケルを充填する。このようにし
て焼結基板の細孔の表面に硝酸コバルトと硝酸マグネシ
ウムの共沈化合物を析出させた後、この共沈化合物をコ
バルトとマグネシウムの共沈水酸化物に置換し、この共
沈水酸化物の表面に水酸化ニッケルを充填した電極をニ
ッケル電極Ａ７とする。このようにして作製したニッケ
ル電極Ａ７のコバルトとマグネシウムを化学分析により
定量して金属モル比率を測定すると、Ｍｇ／（Ｃｏ＋Ｍ
ｇ）＝０．９となっていることが分かった。Thereafter, the process returns to the operation of immersing the sintered substrate again in an aqueous solution mainly composed of nickel nitrate. Fill with nickel oxide. After depositing a coprecipitated compound of cobalt nitrate and magnesium nitrate on the surface of the pores of the sintered substrate in this way, the coprecipitated compound is replaced with a coprecipitated hydroxide of cobalt and magnesium, The electrode having the surface filled with nickel hydroxide is referred to as a nickel electrode A7. Cobalt and magnesium of the nickel electrode A7 thus manufactured were quantified by chemical analysis to measure the metal molar ratio. As a result, Mg / (Co + M
g) = 0.9 was found.
【００４６】上述のように作成したニッケル電極Ａ１〜
Ａ７を、比重１．２０の水酸化カリウム水溶液中でニッ
ケル板を対極として理論容量の５時間率で充電した後、
３時間率で放電して、放電時間毎の各ニッケル電極Ａ１
〜Ａ７の単極電位を参照電極（Ｈｇ／ＨｇＯ）を用いて
測定すると図２に示すような結果となった。The nickel electrodes A1 to A1 prepared as described above
A7 was charged in a potassium hydroxide aqueous solution having a specific gravity of 1.20 at a theoretical capacity of 5 hours with a nickel plate as a counter electrode.
Each nickel electrode A1 was discharged at a rate of 3 hours and discharged every discharge time.
When the monopolar potentials of A7 to A7 were measured using the reference electrode (Hg / HgO), the results shown in FIG. 2 were obtained.
【００４７】図２より明らかなように、ニッケル電極Ａ
３（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．４）、ニッケル電極Ａ
４（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．５）、ニッケル電極Ａ
５（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．６）は、ニッケル電極
Ａ１（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．２）、ニッケル電極
Ａ２（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．３）、ニッケル電極
Ａ６（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．７）、ニッケル電極
Ａ７（Ｍｇ／（Ｃｏ＋Ｍｇ）＝０．９）より高い電極電
位が得られることが分かった。このことから、Ｍｇ／
（Ｃｏ＋Ｍｇ）＝０．４〜０．６の範囲になるように規
定することが好ましい。As apparent from FIG. 2, the nickel electrode A
3 (Mg / (Co + Mg) = 0.4), nickel electrode A
4 (Mg / (Co + Mg) = 0.5), nickel electrode A
5 (Mg / (Co + Mg) = 0.6) corresponds to the nickel electrode A1 (Mg / (Co + Mg) = 0.2), the nickel electrode A2 (Mg / (Co + Mg) = 0.3), and the nickel electrode A6 (Mg / (Co + Mg) = 0.7) and higher electrode potential than nickel electrode A7 (Mg / (Co + Mg) = 0.9). From this, Mg /
It is preferable to define the ratio so that (Co + Mg) = 0.4 to 0.6.
【図１】 放電時間毎の各ニッケル電極Ａ，Ｂ，Ｃ，
Ｄ，Ｅの参照電極（Ｈｇ／ＨｇＯ）に対する電極電位の
関係を示す図である。FIG. 1 shows each nickel electrode A, B, C,
It is a figure which shows the relationship of the electrode potential with respect to the reference electrode (Hg / HgO) of D and E.
【図２】 放電時間毎の各ニッケル電極Ａ１，Ａ２，Ａ
３，Ａ４，Ａ５，Ａ６，Ａ７の参照電極（Ｈｇ／Ｈｇ
Ｏ）に対する電極電位の関係を示す図である。FIG. 2 shows each nickel electrode A1, A2, A for each discharge time
3, A4, A5, A6, A7 reference electrodes (Hg / Hg
It is a figure which shows the relationship of an electrode potential with respect to O).
Claims (3)
る正極活物質を充填するアルカリ蓄電池用ニッケル電極
の製造方法であって、 前記焼結基板の細孔内にコバルトとマグネシウムの共沈
水酸化物を生成させる共沈水酸化物生成工程と、 前記共沈水酸化物が生成された焼結基板に水酸化ニッケ
ルを主成分とする正極活物質を充填する活物質充填工程
とを備えたことを特徴とするアルカリ蓄電池用ニッケル
電極の製造方法。1. A method for producing a nickel electrode for an alkaline storage battery, comprising filling a sintered substrate with a positive electrode active material containing nickel hydroxide as a main component, wherein co-precipitated water of cobalt and magnesium is formed in pores of the sintered substrate. A coprecipitated hydroxide generating step of generating an oxide, and an active material filling step of filling the sintered substrate in which the coprecipitated hydroxide is generated with a positive electrode active material containing nickel hydroxide as a main component. A method for producing a nickel electrode for an alkaline storage battery.
塩に浸漬して前記焼結基板内に酸性ニッケル塩を含浸す
る酸性ニッケル塩浸漬工程と、 前記酸性ニッケル塩浸漬工程により酸性ニッケル塩を含
浸させた前記焼結基板をアルカリ溶液中に浸漬して前記
酸性ニッケル塩を水酸化ニッケルに置換するアルカリ処
理工程とを備え、 前記酸性ニッケル塩浸漬工程と前記アルカリ処理工程と
を所定回数だけ繰り返して前記酸性ニッケル塩を水酸化
ニッケル活物質とするようにしたことを特徴とする請求
項１に記載のアルカリ蓄電池用ニッケル電極の製造方
法。2. The method according to claim 1, wherein the step of filling the active material includes immersing the sintered substrate in which the coprecipitated hydroxide is generated in an acidic nickel salt to impregnate the sintered substrate with the acidic nickel salt. An alkaline treatment step of immersing the sintered substrate impregnated with the acidic nickel salt in the acidic nickel salt immersion step in an alkaline solution to replace the acidic nickel salt with nickel hydroxide, The method for producing a nickel electrode for an alkaline storage battery according to claim 1, wherein the acidic nickel salt is used as a nickel hydroxide active material by repeating the step and the alkali treatment step a predetermined number of times.
ネシウムの比率が金属モル比率でマグネシウム／（コバ
ルト＋マグネシウム）を０．４から０．６の範囲になる
ように規定したことを特徴とする請求項１または請求項
２に記載のアルカリ蓄電池用ニッケル電極の製造方法。3. A method according to claim 1, wherein the ratio of cobalt and magnesium of said coprecipitated hydroxide is such that magnesium / (cobalt + magnesium) is in the range of 0.4 to 0.6 in terms of metal molar ratio. The method for producing a nickel electrode for an alkaline storage battery according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26241597A JP3495576B2 (en) | 1997-09-26 | 1997-09-26 | Method for producing nickel electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26241597A JP3495576B2 (en) | 1997-09-26 | 1997-09-26 | Method for producing nickel electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11102700A true JPH11102700A (en) | 1999-04-13 |
| JP3495576B2 JP3495576B2 (en) | 2004-02-09 |
Family
ID=17375474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26241597A Expired - Fee Related JP3495576B2 (en) | 1997-09-26 | 1997-09-26 | Method for producing nickel electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3495576B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6805785B2 (en) | 2001-08-01 | 2004-10-19 | Matsushita Electric Industrial Co., Ltd. | Production method of sintered-type nickel positive electrode for alkaline secondary battery |
-
1997
- 1997-09-26 JP JP26241597A patent/JP3495576B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6805785B2 (en) | 2001-08-01 | 2004-10-19 | Matsushita Electric Industrial Co., Ltd. | Production method of sintered-type nickel positive electrode for alkaline secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3495576B2 (en) | 2004-02-09 |
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