JPH08236108A - Manufacture of nickel positive electrode for alkaline storage battery - Google Patents
Manufacture of nickel positive electrode for alkaline storage batteryInfo
- Publication number
- JPH08236108A JPH08236108A JP7040853A JP4085395A JPH08236108A JP H08236108 A JPH08236108 A JP H08236108A JP 7040853 A JP7040853 A JP 7040853A JP 4085395 A JP4085395 A JP 4085395A JP H08236108 A JPH08236108 A JP H08236108A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- aqueous solution
- hydroxide
- slurry
- positive electrode
- 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 37
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000003860 storage Methods 0.000 title claims abstract description 15
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 19
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000011149 active material Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000002344 surface layer Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- -1 ammonium ions Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 abstract 3
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000013585 weight reducing 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]
【産業上の利用分野】本発明は、ニッケル−カドミウム
蓄電池等に用いられるアルカリ蓄電池用ニッケル正極の
製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nickel positive electrode for an alkaline storage battery used in a nickel-cadmium storage battery or the like.
【０００２】[0002]
【従来の技術】近年、ポータブル機器などの軽量化に伴
い、その電源であるニッケル−カドミウム蓄電池、ニッ
ケル−水素蓄電池などの二次電池の高エネルギー密度化
が要望されている。従来のアルカリ蓄電池の電極は、焼
結式が主流であるがエネルギー密度に限界があり、焼結
体の製造、活物質の充填において工程が複雑であること
から焼結式に代わって多孔度の大きいスポンジ状金属多
孔体を活物質支持体として用い、これにペースト状にし
た水酸化ニッケルを主体とする活物質を直接充填する方
法が開発された。2. Description of the Related Art In recent years, along with the weight reduction of portable devices and the like, there has been a demand for higher energy density of secondary batteries such as nickel-cadmium storage batteries and nickel-hydrogen storage batteries which are power sources thereof. Sintering method is the mainstream for the electrodes of conventional alkaline storage batteries, but the energy density is limited, and the process of manufacturing sintered bodies and filling active materials is complicated. A method has been developed in which a large sponge-like metal porous body is used as an active material support and a paste-like active material mainly composed of nickel hydroxide is directly filled therein.
【０００３】この方法において使用される水酸化ニッケ
ルの製造法に関しては、特公昭６３−１６５５５号公
報、特公平２−６３４０号公報に見られるように連続的
な製造法が提案されている。また、このペースト式極板
においては、基板の細孔径が大きいために、焼結式極板
の基板よりも活物質に対する集電性が乏しいので、ペー
スト式極板の活物質利用率は焼結式と比較し大幅に低い
という欠点がある。このような問題を解決するために特
公昭６２−２３４８６７号公報、特公昭６３−１５２８
６６号公報に見られるように水酸化ニッケルの表面に水
酸化コバルトの被覆層を形成させることにより、活物質
の利用率を向上させるという方法が提案されている。As a method for producing nickel hydroxide used in this method, a continuous production method has been proposed as shown in Japanese Patent Publication No. 63-16555 and Japanese Patent Publication No. 2-6340. Also, in this paste type electrode plate, since the pore size of the substrate is large, the current collecting ability of the paste type electrode plate for the active material is poorer than that of the substrate. It has the disadvantage of being significantly lower than the formula. In order to solve such a problem, Japanese Examined Patent Publication No. 62-234867 and Japanese Examined Patent Publication No. 63-1528.
As disclosed in Japanese Patent Publication No. 66, a method has been proposed in which a coating layer of cobalt hydroxide is formed on the surface of nickel hydroxide to improve the utilization rate of the active material.
【０００４】[0004]
【発明が解決しようとする課題】しかし、水酸化ニッケ
ルの製造を連続的に行っても、活物質としてはその利用
率向上のために水酸化ニッケル以外にコバルトまたはコ
バルト化合物などの粉末を相当量添加する必要がある。
従来のニッケル正極用活物質の製造工程では図２に示す
ように水酸化ニッケル、水酸化コバルトなどの粉末に関
してそれぞれ水洗、および乾燥してから水を添加して練
合する工程を行っており、活物質当たりの生産エネルギ
ーコストが高く、反面生産性が低いという欠点を有して
いる。However, even if nickel hydroxide is continuously produced, a considerable amount of powder of cobalt or cobalt compound other than nickel hydroxide is used as the active material in order to improve the utilization rate thereof. Need to be added.
In the conventional manufacturing process of the active material for a nickel positive electrode, as shown in FIG. 2, powders of nickel hydroxide, cobalt hydroxide and the like are respectively washed with water, dried, and then added with water and kneaded. The production energy cost per active material is high and, on the other hand, the productivity is low.
【０００５】また、水酸化ニッケルの表面に水酸化コバ
ルトの被覆層を形成させる方法にしても活物質利用率は
向上するが、同じく図２に示すように水酸化ニッケル粉
末生成過程における水洗、および乾燥という工程と表面
に被覆層を形成後乾燥工程を行っている。この乾燥は一
連のニッケル極製造工程において最もエネルギーを消費
する工程であり、全体の工程を煩雑にし、製造コストの
著しい上昇を来すものである。The utilization rate of the active material is also improved by forming a coating layer of cobalt hydroxide on the surface of nickel hydroxide, but as shown in FIG. The step of drying and the step of drying after forming the coating layer on the surface are performed. This drying is the most energy consuming process in a series of nickel electrode manufacturing processes, complicates the whole process, and significantly increases the manufacturing cost.
【０００６】本発明は、上記の問題を解決するもので、
充填に至るまでの乾燥工程を不要とし、さらにその表面
層に水酸化コバルトを生成した水酸化ニッケルを連続的
に製造し、低エネルギーコストで生産性の高い、高性能
のアルカリ蓄電池用ニッケル正極の製造法を提供するこ
とを目的とする。The present invention solves the above problems,
A nickel positive electrode for a high-performance alkaline storage battery that does not require a drying step up to filling and continuously produces nickel hydroxide that has produced cobalt hydroxide on its surface layer and has high productivity at low energy cost. The purpose is to provide a manufacturing method.
【０００７】[0007]
【課題を解決するための手段】上記のような目的を達成
するために本発明では、次のようにアルカリ蓄電池用ニ
ッケル正極を製造するものである。第一の工程ではニッ
ケル塩の水溶液にアンモニウムイオンを混入した混合溶
液に、アルカリ金属水酸化物水溶液を連続的に反応させ
るように供給し、生成した水酸化ニッケルを連続的に取
り出して、これをろ過及び水洗する。第二の工程では第
一の工程で得られた水酸化ニッケルのスラリーにコバル
ト塩の水溶液、アルカリ金属水酸化物水溶液を連続的に
供給し、ろ過及び水洗を行うことにより、水酸化コバル
トを表面層に生成させた水酸化ニッケルを連続的に得
る。さらに第三の工程では第二の工程で得られたスラリ
ーを主体としこれに添加物を混練したペーストを金属基
板または支持体内部に充填または塗着する。In order to achieve the above object, the present invention is to produce a nickel positive electrode for an alkaline storage battery as follows. In the first step, a mixed solution prepared by mixing ammonium ions in an aqueous solution of a nickel salt is supplied so as to continuously react an aqueous solution of an alkali metal hydroxide, and the produced nickel hydroxide is continuously taken out. Filter and wash with water. In the second step, the cobalt hydroxide aqueous solution and the alkali metal hydroxide aqueous solution are continuously supplied to the nickel hydroxide slurry obtained in the first step, and the cobalt hydroxide is surface-treated by filtering and washing with water. The nickel hydroxide formed in the layer is continuously obtained. Furthermore, in the third step, the paste obtained by mainly kneading the slurry obtained in the second step with additives is filled or applied inside the metal substrate or the support.
【０００８】[0008]
【作用】この製造方法によれば、表面層に水酸化コバル
トを生成した水酸化ニッケルを連続的に製造し、それを
導電性基板に充填または塗着する工程において、水酸化
ニッケル粉末製造工程における乾燥、及び水酸化コバル
ト被覆層を形成した水酸化ニッケル粉末製造工程におけ
る乾燥という二つの乾燥工程を省くことができる。According to this manufacturing method, in the step of continuously manufacturing nickel hydroxide in which cobalt hydroxide is generated in the surface layer and filling or coating the conductive layer with the conductive substrate, in the nickel hydroxide powder manufacturing step. It is possible to omit the two drying steps of drying and drying in the nickel hydroxide powder manufacturing step in which the cobalt hydroxide coating layer is formed.
【０００９】このことにより、生産時のエネルギーコス
トが低減でき、生産性の高いアルカリ蓄電池用正極が得
られる。As a result, the energy cost during production can be reduced and a highly productive positive electrode for an alkaline storage battery can be obtained.
【００１０】[0010]
（実施例１）以下、本発明の実施例について図１を参照
しながら説明する。(Embodiment 1) Hereinafter, an embodiment of the present invention will be described with reference to FIG.
【００１１】図中１は反応槽であり、ここでは二重隔壁
を有する１００ｌのタンクである。ニッケル塩、アルカ
リ金属水酸化物、及びアンモニウムイオン供給体として
は、それぞれ濃度１８０ｇ／ｌの硫酸ニッケル水溶液、
２０重量％の水酸化ナトリウム水溶液、及び１８重量％
のアンモニア水を用いた。この反応槽１内へ硫酸ニッケ
ル水溶液を１．５ｌ／ｈｒ、アンモニア水を０．２１ｌ
／ｈｒの流量となるようパイプライン３で供給する。一
方定量ポンプ５によりノズル内で十分混合しながらｐＨ
１１．５±０．３、槽内温度を４０±２℃の一定に保持
しつつ、水酸化ナトリウムをパイプライン４より反応槽
１の内側に供給し、槽内にセンサをもったｐＨコントロ
ーラと連動させて前記ｐＨを保持するように撹拌機９で
撹拌しつつ水酸化ナトリウムを間欠的に反応液に添加し
て水酸化ニッケルを生成させた。７は槽内にセンサをも
った温度コントローラである。生成した水酸化ニッケル
は二重隔壁外部にオーバーフローさせてパイプライン８
で吸引してタンク１０に取り出した。これに純水１２を
連続的に供給してパイプ１１でロータリーフィルター１
３に送り、ここで循環式ろ過水洗と脱水を行い、含水率
２５％のスラリーに調整して、予備タンク１５に供給す
る。反応槽１と同様なタンクである反応槽１６のタンク
内へ前記の水酸化ニッケルのスラリーを予備タンク１５
から５０ｌ供給した後、１２重量％の硫酸コバルト水溶
液を１．０ｌ／ｈｒの一定速度で定量ポンプ５によりｐ
Ｈ１１．５±０．３、槽内温度を４０±２℃の一定に保
持した十分撹拌されている槽内に添加し、ｐＨコントロ
ーラと連動させて設定されたｐＨを保持するように２０
重量％の水酸化ナトリウム水溶液を間欠的に添加した。
硫酸コバルト水溶液が３０ｌ入った時点で、硫酸コバル
ト水溶液と水酸化ナトリウムの供給を止めて生成物を取
り出した。In the figure, reference numeral 1 is a reaction tank, here a 100 l tank having a double partition wall. The nickel salt, the alkali metal hydroxide, and the ammonium ion supplier are nickel sulfate aqueous solution having a concentration of 180 g / l,
20% by weight aqueous sodium hydroxide solution, and 18% by weight
Of ammonia water was used. 1.5 l / hr of nickel sulfate aqueous solution and 0.21 l of ammonia water were put into this reaction tank 1.
It is supplied by the pipeline 3 so that the flow rate becomes / hr. On the other hand, the metering pump 5 mixes the pH well in the nozzle
11.5 ± 0.3, while keeping the temperature inside the tank constant at 40 ± 2 ° C, sodium hydroxide was supplied to the inside of the reaction tank 1 through the pipeline 4, and a pH controller with a sensor inside the tank was used. Sodium hydroxide was intermittently added to the reaction liquid while stirring with a stirrer 9 so as to keep the pH in a coordinated manner to generate nickel hydroxide. Reference numeral 7 is a temperature controller having a sensor in the tank. The generated nickel hydroxide overflows to the outside of the double partition and is pipeline 8
It was sucked in and taken out to the tank 10. Pure water 12 is continuously supplied to the rotary filter 1 with a pipe 11.
3, the circulating filtration water washing and dehydration are performed here, the slurry having a water content of 25% is adjusted, and the slurry is supplied to the spare tank 15. The above nickel hydroxide slurry is stored in a preliminary tank 15 in a reaction tank 16 which is the same tank as the reaction tank 1.
After supplying 50 liters from the above, a 12 wt% cobalt sulfate aqueous solution was added by a metering pump 5 at a constant rate of 1.0 liter / hr.
Add H11.5 ± 0.3 into the well-stirred tank with the tank temperature kept constant at 40 ± 2 ° C, and maintain the set pH in conjunction with the pH controller.
A wt% aqueous sodium hydroxide solution was added intermittently.
When 30 l of the cobalt sulfate aqueous solution had been added, the supply of the cobalt sulfate aqueous solution and sodium hydroxide was stopped and the product was taken out.
【００１２】これを連続的にロータリーフィルターで循
環ろ過水洗を行い、さらに脱水により含水率２５％のス
ラリーに調整した後、これに金属コバルトの粉末を前記
スラリーにおける水酸化ニッケル１００ｇ当たり５ｇ混
合し、水を加えて含水率を２７％にした活物質スラリー
をよく撹拌し、発泡状ニッケル多孔体（多孔度９５％）
に充填した。This was continuously circulated and filtered with a rotary filter, washed with water, adjusted to a slurry having a water content of 25% by dehydration, and 5 g of metallic cobalt powder was mixed with 100 g of nickel hydroxide in the slurry, A foamed nickel porous body (porosity 95%) was obtained by thoroughly stirring the active material slurry in which water was added to make the water content 27%.
Was filled.
【００１３】こうして得られたニッケル正極を乾燥した
後、一定の条件で加圧プレス後４０×５５ｍｍに裁断
し、本発明の実施例によるニッケル正極Ａを得た。この
正極を用いて、負極として公知のカドミウム負極と組み
合わせて、本発明の実施例である公称容量７００ｍＡｈ
のＡＡサイズの密閉型ニッケルカドミウム蓄電池Ａを作
製した。The nickel positive electrode thus obtained was dried, pressed under a certain condition, and then cut into 40 × 55 mm to obtain a nickel positive electrode A according to an embodiment of the present invention. Using this positive electrode, in combination with a known negative electrode of cadmium as a negative electrode, a nominal capacity of 700 mAh, which is an example of the present invention, was obtained.
AA size sealed nickel cadmium storage battery A was manufactured.
【００１４】比較例として、実施例と同様に反応槽１で
の工程、つまり水酸化ニッケルの製造を行い、これをろ
過水洗を行った後、乾燥を行い水酸化ニッケル粉末を得
た。この水酸化ニッケル粉末に金属コバルト粉末を水酸
化ニッケル粉末１００ｇ当たり５ｇと、水酸化コバルト
粉末を図１の反応槽１６での反応により生成する水酸化
コバルトと水酸化ニッケル粉末当たりで等量添加し、水
を加えて含水率を２７％にしたものを充填して得た正極
を比較例によるニッケル正極Ｂとし、実施例と同様にし
てＡＡサイズの密閉型ニッケルカドミウム蓄電池Ｂを作
製した。As a comparative example, nickel hydroxide powder was obtained by carrying out the process in the reaction vessel 1 in the same manner as in the example, that is, producing nickel hydroxide, filtering and washing it, and then drying. To this nickel hydroxide powder, 5 g of metallic cobalt powder was added per 100 g of nickel hydroxide powder, and an equal amount of cobalt hydroxide powder was added per cobalt hydroxide and nickel hydroxide powder produced by the reaction in the reaction vessel 16 of FIG. Then, the positive electrode obtained by filling the one with water added to have a water content of 27% was used as a nickel positive electrode B according to a comparative example, and an AA size sealed nickel cadmium storage battery B was produced in the same manner as in the example.
【００１５】また、実施例と同様にして第二工程のろ過
及び水洗まで同様にして行った後、乾燥して表面に水酸
化コバルトを有する水酸化ニッケル粉末を得た。この粉
末１００ｇに対して金属コバルトを５ｇ混合し、水を加
えてペースト状にし、発泡状ニッケル多孔体に充填し、
乾燥後一定条件で加圧プレス後上記寸法に裁断を行い、
比較によるニッケル正極Ｃを得た。この正極を用いて実
施例と同様にしてＡＡサイズの密閉型ニッケルカドミウ
ム蓄電池を作製し、比較例による電池Ｃを得た。Further, the second step of filtration and washing with water were carried out in the same manner as in the example, and then dried to obtain a nickel hydroxide powder having cobalt hydroxide on the surface. To 100 g of this powder, 5 g of metallic cobalt was mixed, water was added to form a paste, and the foamed nickel porous body was filled.
After drying, pressurizing and pressing under certain conditions and then cutting to the above dimensions,
A nickel positive electrode C for comparison was obtained. Using this positive electrode, an AA size sealed nickel-cadmium storage battery was produced in the same manner as in the example, and a battery C according to a comparative example was obtained.
【００１６】これらの電池を作製するに当たり、用いた
ニッケル正極を作製するのに要する１Ａｈ当たりの消費
エネルギーを（表１）に示す。The energy consumption per 1 Ah required for producing the nickel positive electrode used for producing these batteries is shown in (Table 1).
【００１７】[0017]
【表１】 [Table 1]
【００１８】（表１）から明らかなように表面層に水酸
化コバルトを生成した水酸化ニッケルを製造する工程に
おいて、乾燥を省略してスラリーのまま充填工程を行う
だけでも、消費エネルギーにして２０％程度低く抑える
ことができ、低エネルギーコストで生産性の高い正極が
得られる。As is clear from (Table 1), in the process of producing nickel hydroxide in which cobalt hydroxide is produced in the surface layer, even if the drying process is omitted and only the filling process is performed as a slurry, the energy consumption is reduced to 20. %, It is possible to obtain a positive electrode having high productivity with low energy cost.
【００１９】また、これらの電池を２０℃の一定温度で
０．１Ｃで１５時間充電し、０．２Ｃで１．０Ｖ迄放電
するサイクルを繰り返し、２サイクル目の放電容量で電
池特性を評価した。これらの結果も（表１）に示す。
（表１）より明らかなように、電池Ａでは水酸化コバル
トを水酸化ニッケル表面層に形成させたことにより、水
酸化コバルト粉末を単独で添加した比較例電池Ｂよりも
利用率が高い。これは、水酸化ニッケル表面層に水酸化
コバルトを形成させることにより、活物質粉末にコバル
ト粉末を単独で添加した場合よりも、コバルトと水酸化
ニッケルとの接触面積が大きく、コバルト添加による活
物質の利用率の向上が極めて大きくなるためと考えられ
る。なお、本実施例では導電性基板として発泡状ニッケ
ル多孔体を用いたが、パンチングメタルにニッケルをメ
ッキしたものに塗着した場合でも同様の効果が得られる
ことはいうまでもない。Further, these batteries were charged at 0.1 ° C. for 15 hours at a constant temperature of 20 ° C., and the cycle of discharging at 0.2 C to 1.0 V was repeated, and the battery characteristics were evaluated by the discharge capacity at the second cycle. . These results are also shown in (Table 1).
As is clear from (Table 1), in Battery A, since cobalt hydroxide was formed on the nickel hydroxide surface layer, the utilization rate was higher than that of Comparative Battery B in which cobalt hydroxide powder was added alone. This is because by forming cobalt hydroxide on the nickel hydroxide surface layer, the contact area between cobalt and nickel hydroxide is larger than when cobalt powder is added alone to the active material powder. It is considered that the improvement of the utilization rate of is extremely large. Although the foamed nickel porous body is used as the conductive substrate in this embodiment, it is needless to say that the same effect can be obtained even when the punched metal is coated with nickel.
【００２０】[0020]
【発明の効果】以上のように本発明は、基板への充填ま
たは塗着に至るまでに乾燥工程を不要とし、さらにその
表面層に水酸化コバルトを生成した水酸化ニッケルを連
続的に製造し、低エネルギーコストで生産性が高く高性
能のアルカリ蓄電池用ニッケル正極の製造法を提供する
ことができる。INDUSTRIAL APPLICABILITY As described above, the present invention does not require a drying step until filling or coating on a substrate, and further continuously produces nickel hydroxide having cobalt hydroxide formed on its surface layer. It is possible to provide a method for producing a nickel positive electrode for an alkaline storage battery, which has low energy cost, high productivity, and high performance.
【図１】本発明に使用する反応装置の一例を示すフロー
チャートFIG. 1 is a flowchart showing an example of a reaction apparatus used in the present invention.
【図２】従来のニッケル極製造工程を示すフローチャー
トFIG. 2 is a flowchart showing a conventional nickel electrode manufacturing process.
１ 反応槽 ２ 二重隔壁 ３ アンモニウムイオン混合ニッケル塩水溶液供給ライ
ン ４ アルカリ金属水酸化物水溶液供給ライン ５ 定量ポンプ ６ ｐＨコントローラ ７ 温度コントローラ ８ 水酸化ニッケル粒子含有液取り出しライン ９ 撹拌機 １０ 水酸化ニッケル粒子含有液用タンク １１ 水酸化ニッケル粒子含有液供給ライン １２ 純水供給ライン １３ 循環ろ過水洗装置 １４ ろ液排出ライン １５ 脱水後水酸化ニッケル粒子含有液用タンク １６ 反応槽 １７ コバルト塩水溶液供給ライン １８ 脱水後水酸化ニッケル粒子含有液供給ライン １９ 反応生成物取り出しライン1 Reaction Tank 2 Double Partition 3 Ammonium Ion Mixed Nickel Salt Aqueous Solution Supply Line 4 Alkali Metal Hydroxide Aqueous Solution Supply Line 5 Metering Pump 6 pH Controller 7 Temperature Controller 8 Nickel Hydroxide Particle-Containing Liquid Extraction Line 9 Stirrer 10 Nickel Hydroxide Particle-containing liquid tank 11 Nickel hydroxide particle-containing liquid supply line 12 Pure water supply line 13 Circulating filtration water washing device 14 Filtrate discharge line 15 Dehydrated nickel hydroxide particle-containing liquid tank 16 Reaction tank 17 Cobalt salt aqueous solution supply line 18 Liquid supply line containing nickel hydroxide particles after dehydration 19 Reaction product take-out line
Claims (1)
混合した水溶液に、アルカリ金属水酸化物水溶液を連続
的に供給し、生成した水酸化ニッケル粒子を連続的に取
り出し、ろ過及び水洗を連続的に行う第１の工程と、第
１の工程で得られた水酸化ニッケルのスラリーにコバル
ト塩水溶液、アルカリ金属水酸化物水溶液を連続的に供
給して、前記水酸化ニッケルの表面層に水酸化コバルト
を生成したスラリーを連続的にろ過及び水洗する第２の
工程と、第２の工程で得られたスラリーを主体とする活
物質を導電性基板に充填または塗着する第３の工程とか
らなるアルカリ蓄電池用ニッケル正極の製造法。1. An alkali metal hydroxide aqueous solution is continuously supplied to an aqueous solution of a nickel salt aqueous solution mixed with ammonium ions, the nickel hydroxide particles produced are continuously taken out, and filtration and washing are continuously performed. A cobalt salt aqueous solution and an alkali metal hydroxide aqueous solution are continuously supplied to the first step and the nickel hydroxide slurry obtained in the first step to add cobalt hydroxide to the surface layer of the nickel hydroxide. Alkali comprising a second step of continuously filtering and washing the produced slurry and water, and a third step of filling or coating the conductive substrate with the active material mainly containing the slurry obtained in the second step Manufacturing method of nickel positive electrode for storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04085395A JP3287165B2 (en) | 1995-02-28 | 1995-02-28 | Manufacturing method of nickel positive electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04085395A JP3287165B2 (en) | 1995-02-28 | 1995-02-28 | Manufacturing method of nickel positive electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236108A true JPH08236108A (en) | 1996-09-13 |
| JP3287165B2 JP3287165B2 (en) | 2002-05-27 |
Family
ID=12592130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04085395A Expired - Fee Related JP3287165B2 (en) | 1995-02-28 | 1995-02-28 | Manufacturing method of nickel positive electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3287165B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129902A (en) * | 1997-02-03 | 2000-10-10 | Matsushita Electric Industrial Co., Ltd. | Manufacturing method of active materials for the positive electrode in alkaline storage batteries |
| CN1333480C (en) * | 2005-10-26 | 2007-08-22 | 浙江工业大学 | Positive electrode material of metal hydride-nickel battery and its preparation method |
-
1995
- 1995-02-28 JP JP04085395A patent/JP3287165B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129902A (en) * | 1997-02-03 | 2000-10-10 | Matsushita Electric Industrial Co., Ltd. | Manufacturing method of active materials for the positive electrode in alkaline storage batteries |
| US6284215B1 (en) | 1997-02-03 | 2001-09-04 | Matsushita Electric Industrial Co., Ltd. | Manufacturing method of active materials for the positive electrode in alkaline storage batteries |
| CN1333480C (en) * | 2005-10-26 | 2007-08-22 | 浙江工业大学 | Positive electrode material of metal hydride-nickel battery and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3287165B2 (en) | 2002-05-27 |
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