CN104037392A - Particle aggregate and method of producing the same - Google Patents

Particle aggregate and method of producing the same Download PDF

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Publication number
CN104037392A
CN104037392A CN201410076087.0A CN201410076087A CN104037392A CN 104037392 A CN104037392 A CN 104037392A CN 201410076087 A CN201410076087 A CN 201410076087A CN 104037392 A CN104037392 A CN 104037392A
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particle
cobalt
suspension
turbid liquid
hydroxide
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CN104037392B (en
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畑未来夫
高岛正洋
大草祐二
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Tanaka Of Co Ltd Chemistry Institute
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Tanaka Of Co Ltd Chemistry Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides a particle aggregate which has fewer fine particles and is useful as a positive active material of an alkaline storage battery, and a method of producing the same. The invention relates to a particle aggregate comprising particles including nickel hydroxide, the particle aggregate is obtained by a production method including a process (A), a process (B), a process (C) and a process (D) which are recorded in the specification, and the surfaces of the particles including nickel hydroxide are coated with cobalt compounds with cobalt having a average valence number of 2.1-3.0.

Description

Particle agglomeration and manufacture method thereof
Technical field
The content that the present invention relates to minuteness particle is few, as the useful particle agglomeration of the positive active material of alkaline battery and manufacture method thereof.
Background technology
In recent years, manufacturing paste spread type (ペ ー ス ト formula) during nickel electrode, implemented following scheme: by using surface to be there is the particle containing nickel hydroxide of the cobalt compound coating of high conductivity, thereby the current collection of electrode is improved, increase the utilance of active material.
For example, in patent documentation 1, recorded and at least there is nickel hydroxide and at cobalt and/or the cobalt compound of the inhomogeneous existence of particle surface, and stipulated the granular nickel electrode active material of the state of pore.In addition in the document, also recorded the manufacture method of active material for granular nickel electrode, the method possesses following operation: the inhomogeneous existence of cobalt forms operation, in this operation, in the suspension-turbid liquid of the cobalt compound that contains granular nickel hydroxide and dissolving, under stirring condition, slowly add the alkali of ormal weight, thereby form to inhomogeneous existence cobalt hydroxide on the surface of granular nickel hydroxide; Cobalt high-order (high order) chemical industry order, in this operation, under the existence of alkali-metal hydroxide and oxygen, heats the inhomogeneous nickel particles that exists of the cobalt of making, and makes the cobalt compound in above-mentioned particle become high-order (high order) cobalt/cobalt oxide.
In addition, for surface by cobalt compound coating containing the particle of nickel hydroxide, also reported that can solve what take cobalt compound layer is former thereby the positive active material of the problems such as self-discharge of generation.
For example, recorded a kind of anode active material for alkaline storage battery in patent documentation 2, it has: the particle containing nickel hydroxide that at least comprises magnesium with solid solution condition; And coating should be containing cobalt compound layer particle surface, that have special properties of nickel hydroxide.In addition in the document, also recorded a kind of manufacture method of anode active material for alkaline storage battery, the method possesses following operation: on one side in the aqueous solution comprising containing the particle of nickel hydroxide, supply with sodium hydrate aqueous solution pH value is remained on to 11.5～13.5 scope, air supply in the aqueous solution that comprises cobalt ions in supply on one side, thus on the surface of the above-mentioned particle containing nickel hydroxide, form cobalt compound layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-148145 communique
Patent documentation 2: TOHKEMY 2006-48954 communique.
Summary of the invention
The problem that invention will solve
As mentioned above, people's known surface is by particle and the manufacture method thereof containing nickel hydroxide of cobalt compound coating.
Yet if adopt method in the past to manufacture surface by the particle containing nickel hydroxide of cobalt compound coating, the particle agglomeration of gained contains the minuteness particle producing because of peeling off of cobalt compound in a large number sometimes.So, if modulate thickener by the particle agglomeration that contains a large amount of minuteness particles, easily become full-bodied thickener, thereby exist to make the problem that operability when anodal reduces or the conductivity of particle reduces.
The present invention is in view of the actual conditions of above-mentioned prior art and complete, and the content that the object of this invention is to provide a kind of minuteness particle is few, as the useful particle agglomeration of the positive active material of alkaline battery and manufacture method thereof.
Solve the means that problem is used
The inventor etc. conduct in-depth research in order to solve above-mentioned problem, found that, by containing for surface after the coating of α-cobalt hydroxide of the particle of nickel hydroxide, under nonoxidizing atmosphere, this α-cobalt hydroxide is transformed to β-cobalt hydroxide, then by this β-cobalt hydroxide is oxidized, thereby can with good efficiency, obtain comprising the particle agglomeration containing the particle of nickel hydroxide, the content that the described particle containing nickel hydroxide is minuteness particle is few, positive active material as alkaline battery is useful, surface is by the particle of cobalt compound (high-order cobalt/cobalt oxide) coating, completed thus the present invention.
Like this, according to the present invention, provide the manufacture method of the particle agglomeration of following (1) and the particle agglomeration of (2).
(1) comprise the particle agglomeration containing the particle of nickel hydroxide, it is the particle agglomeration obtaining by having the manufacture method of following operation A～operation C, the cobalt compound coating that the surface of the described particle containing nickel hydroxide is 2.1～3.0 by the average valence mumber of cobalt
Operation A: under agitation, the pH value of the suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0 on one side, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating, described raw material particle agglomeration is the raw material particle agglomeration comprising containing the particle of nickel hydroxide, its particle diameter D50 is 10～15 μ m, particle diameter is that the cumulative frequency % value of the particle below 5 μ m is below 12.0%,
Process B: on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating;
Operation C: respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the operation of the suspension-turbid liquid of the particle that contains nickel hydroxide that obtains comprising the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt.
(2) comprise the manufacture method containing the particle agglomeration of the particle of nickel hydroxide, the method has following operation A～operation C, the cobalt compound coating that the surface of the described particle containing nickel hydroxide is 2.1～3.0 by the average valence mumber of cobalt,
Operation A: under agitation, the pH value of the suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0 on one side, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating, described raw material particle agglomeration is the raw material particle agglomeration comprising containing the particle of nickel hydroxide, its particle diameter D50 is 10～15 μ m, particle diameter is that the cumulative frequency % value of the particle below 5 μ m is below 12.0%,
Process B: on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating;
Operation C: respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the operation of the suspension-turbid liquid of the particle that contains nickel hydroxide that obtains comprising the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt.
The effect of invention
According to the present invention, provide the content of minuteness particle few, as the useful particle agglomeration of the positive active material of alkaline battery and manufacture method thereof.
Accompanying drawing explanation
Fig. 1: the electron micrograph that forms the particle of the particle agglomeration obtaining in embodiment 1.
Fig. 2: the electron micrograph that forms the particle of the particle agglomeration obtaining in comparative example 1.
Fig. 3: the electron micrograph that forms the particle of the particle agglomeration obtaining in Production Example 1.
Embodiment
Particle agglomeration of the present invention is the particle agglomeration obtaining by having the manufacture method of following operation A～operation C, the particle containing nickel hydroxide that it comprises the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt,
Operation A: under agitation, the pH value of the suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0 on one side, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating, described raw material particle agglomeration is the raw material particle agglomeration comprising containing the particle of nickel hydroxide, its particle diameter D50 is 10～15 μ m, particle diameter is that the cumulative frequency % value of the particle below 5 μ m is below 12.0%,
Process B: on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating;
Operation C: respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the operation of the suspension-turbid liquid of the particle that contains nickel hydroxide that obtains comprising the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt.
It is the particle containing nickel hydroxide (being sometimes referred to as below " containing the particle of Co/Ni ") of 2.1～3.0 cobalt compound coatings by the average valence mumber of cobalt that particle agglomeration of the present invention comprises surface.For for the particle of Co/Ni, not necessarily want the surface of nickel hydroxide particle all by cobalt compound, to be covered, can be for example in SEM image, 5 one-tenth above parts of the surface integral of nickel hydroxide particle are covered by above-mentioned cobalt compound.
Below, sometimes particle particle, nickel hydroxide containing Co/Ni is partly called to " core part ", the part consisting of above-mentioned cobalt compound of the particle containing Co/Ni is called to " high-order cobalt compound layer ".
In operation A～operation C, in order to make in reaction vessel evenly, conventionally with stirring vane etc., stir suspension-turbid liquid.There is no particular limitation for the size of stirring vane and rotation number thereof etc., can suitably determine according to object.
[operation A]
Operation A is, under agitation, on one side the pH value of the above-mentioned suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating.
Raw material particle agglomeration is the raw material particle agglomeration that the particle of take containing nickel hydroxide is main component.As the particle containing nickel hydroxide, can utilize positive active material or the known particle containing nickel hydroxide of its manufacture raw material as alkaline battery.
Particle containing nickel hydroxide also can contain one kind or two or more nickel metallic atom in addition.As this metallic atom, can enumerate: magnesium, aluminium, calcium, titanium, manganese, cobalt, iron, copper, zinc etc.Wherein, the particle that contains nickel hydroxide preferably at least contains magnesium, more preferably contains magnesium and cobalt.By at least containing magnesium with solid solution condition in the particle that makes to comprise nickel hydroxide, thereby can obtain efficient discharge characteristic and the good particle containing Co/Ni of output characteristic.
Used containing in the particle of nickel hydroxide in the present invention, the content of the metallic atom beyond nickle atom is generally below 15 % by mole with respect to metallic atom total amount, is preferably 1～10 % by mole.
The particle diameter D50 of raw material particle agglomeration is preferably 10～15 μ m, more preferably 11～14 μ m.By using the raw material particle agglomeration of particle diameter D50 in above-mentioned scope, thereby can obtain with good efficiency having the particle agglomeration of the particle that contains Co/Ni of target property.
In raw material particle agglomeration, contained particle diameter is that the cumulative frequency % value of the particle below 5 μ m is preferably below 12.0%, more preferably 1～11.5%.By make particle diameter be the cumulative frequency % value of the particle below 5 μ m in above-mentioned scope, thereby can using good efficiency obtains the particle agglomeration as the particle that contains Co/Ni of target.
Here, " particle diameter is the cumulative frequency % value of the particle below 5 μ m " refers to, in particle agglomeration, in the cumulative volume % of contained particle, particle diameter is the 5.00 μ m summations of the volume distributed median frequency % of the particle of (being generally 0.01 μ m～5.00 μ m) below.
Particle diameter D50, particle diameter are that the cumulative frequency % value of the particle below 5 μ m is obtained as follows: use laser diffraction formula particle size distribution device, with volume reference, measure particle size distribution.
The BET specific area of raw material particle agglomeration is preferably 5～20m 2/ g, more preferably 8～15m 2/ g.
The tap density of raw material particle agglomeration (tap density) is preferably 1.5～2.5g/cm 3, 1.6～2.4g/cm more preferably 3.
The bulk density of raw material particle agglomeration (bulk density) is preferably 0.8～1.8g/cm 3, 0.9～1.7g/cm more preferably 3.
By making BET specific area, tap density and the bulk density of raw material particle agglomeration, be in above-mentioned scope, thereby can using good efficiency obtain the particle agglomeration as the particle that contains Co/Ni of target.
For raw material particle agglomeration, such as making by the known manufacture method that contains the particle of nickel hydroxide of recording in Japanese kokai publication hei 10-12237 communique, TOHKEMY 2006-48954 communique etc.
Particularly, the pH value of the liquid in reactive tank is adjusted to suitable scope on one side, under agitation nickel (II) saline solution is added in reactive tank on one side, make the Precipitation of nickel hydroxide, then filter the sediment of gained, washing, and then carry out as required processed, dry processing, can obtain raw material particle agglomeration by this.
As nickel used (II) salt, can enumerate: nickelous sulfate (II), nickel chloride (II), nickel nitrate (II), nickel acetate (II) etc., preferably sulfuric acid nickel (II).
Now, except nickel (II) salt, can also add the salt of magnesium, aluminium, calcium, titanium, manganese, cobalt, iron, copper, zinc etc.Wherein, except nickel (II) salt, preferably add magnesium (II) salt, more preferably add magnesium (II) salt and cobalt (II) salt.For the addition of magnesium (II) salt and cobalt (II) salt, with respect to 1 mole of nickel (II) salt, magnesium (II) salt (being its total amount in the situation of interpolation magnesium (II) salt and cobalt (II) salt) is 0～0.1 mole of left and right.
In addition, except nickel (II) salt, also use in the situation of other slaines such as magnesium salts, the anion of other slaine is preferably identical with the anion of nickel (II) salt.For example, while using nickelous sulfate (II), as magnesium (II) salt, preferably use magnesium sulfate (II).
In said method, by regulating pH value or the mixing speed of the liquid in reactive tank, can control the physical property of raw material particle agglomeration.Conventionally, by improving the pH value of the liquid in reactive tank, thereby make the particle diameter of the raw material particle of gained have the tendency diminishing, by accelerating mixing speed, thus the tendency that particle diameter is distributed with narrow down.
The content of the raw material particle agglomeration in the present invention in suspension-turbid liquid used has no particular limits.With respect to 1L water, the content of raw material particle agglomeration is generally 50～200g, is preferably 80～140g.
Can be by cobalt (II) salt be dissolved in water and be prepared to the aqueous solution that contains cobalt (II) salt adding in the suspension-turbid liquid that contains raw material particle agglomeration.
As cobalt used (II) salt, can enumerate: cobaltous sulfate (II), cobalt nitrate (II), cobalt chloride (II) etc.Preferably sulfuric acid cobalt (II) wherein.
While using sulfate as above-mentioned cobalt (II) salt, the content of the sulfate radical in the particle agglomeration of gained is generally below 1.0 % by weight, is preferably 0.01～0.5 % by weight.By making the content of sulfate radical, be below 1.0 % by weight, when using obtain by adopting particle agglomeration of the present invention anodal, sulfate radical is difficult to enter into the crystallization of cobalt compound, therefore can suppress to reduce because of the crystallinity of cobalt compound the self-discharge producing.
The concentration of the aqueous solution that contains cobalt (II) salt is generally 0.1～2.0 mole/L, is preferably 0.6～1.8 mole/L.
The pH value of the aqueous solution that contains cobalt (II) salt is generally 0.5～6.0, is preferably 1.0～5.0.PH value by the aqueous solution that makes to contain cobalt (II) salt, within the scope of this, is separated out precipitation thereby can be suppressed in the aqueous solution containing cobalt.
The pH value of the aqueous solution that contains cobalt (II) salt can regulate with known acid compound or alkali compounds as required.
When the aqueous solution that contains cobalt (II) salt is added in suspension-turbid liquid, the pH value of suspension-turbid liquid easily regulates, therefore preferred continuous adding constant basis.
When the aqueous solution that contains cobalt (II) salt is added in the suspension-turbid liquid that contains raw material particle agglomeration, under agitation keeping the pH value of suspension-turbid liquid is 8.0～11.0, is preferably 8.5～10.5.
By the pH value of suspension-turbid liquid being remained in 8.0～11.0 scope, thus can be with good α-cobalt hydroxide coating for efficiency the surface containing the particle of nickel hydroxide.From can contain more equably the surperficial viewpoint of the particle of nickel hydroxide with the coating of α-cobalt hydroxide, the pH value of suspension-turbid liquid preferably remains constant value in above-mentioned scope.Should illustrate, " pH value is constant value " refer to pH value regulation value positive and negative 0.1 in.
The alkaline aqueous solution that the pH value of suspension-turbid liquid regulates the addition of the aqueous solution that can contain cobalt (II) salt by basis to add appropriate amount carries out.
Alkali compounds used in preparation as alkaline aqueous solution, can enumerate: the hydroxide of alkali-metal hydroxide or carbonate, alkaline-earth metal or carbonate etc.The wherein hydroxide of preferred as alkali or carbonate.
As alkali-metal hydroxide, can enumerate: lithium hydroxide, NaOH, potassium hydroxide etc.
As alkali-metal carbonate, can enumerate: lithium carbonate, sodium carbonate, potash etc.
As the hydroxide of alkaline-earth metal, can enumerate: magnesium hydroxide, calcium hydroxide, barium hydroxide etc.
As the carbonate of alkaline-earth metal, can enumerate: magnesium carbonate, calcium carbonate, brium carbonate etc.
The pH value of alkaline aqueous solution is generally 9～13, is preferably 10～13.
In addition, when the aqueous solution that contains cobalt (II) salt is added in suspension-turbid liquid, the dissolved oxygen concentration of suspension-turbid liquid must be remained below 0.5mg/L, preferably remain 0.01～0.1mg/L.
By the dissolved oxygen concentration of suspension-turbid liquid is remained below 0.5mg/L, thereby can avoid the oxidation of α-cobalt hydroxide, prevent from generating and almost do not have punctulate high-order cobalt compound.
As the dissolved oxygen concentration of suspension-turbid liquid is remained to the method below 0.5mg/L, can enumerate following method: use the low water of dissolved oxygen concentration, prepare suspension-turbid liquid, the aqueous solution of (II) salt that contains cobalt, the method for reacting under inert gas atmosphere; On one side in suspension-turbid liquid, be blown into (bubbling) inert gas, on one side add the aqueous solution that contains cobalt (II) salt etc. method.
As inert gas used, can enumerate: nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas etc.
The dissolved oxygen concentration of suspension-turbid liquid can utilize the DO determination meter possessing in reaction vessel to measure.
The addition of the aqueous solution that contains cobalt (II) salt is to be 2～10 weight portions with respect to 100 weight portion above-mentioned raw materials particle agglomeration, is preferably the amount of 3～9 weight portions.
Carry out the time of operation A, as long as can have no particular limits on the surface containing the particle of nickel hydroxide with the coating of α-cobalt hydroxide, be generally 10 minutes～2 hours, be preferably 30 minutes～1 hour.
The reaction temperature of operation A is generally 10～80 ℃, is preferably 20～60 ℃.
By operation A, can obtain comprising surface by the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating.
The cobaltous hydroxide layer that comprises α-cobalt hydroxide is compared with the cobaltous hydroxide layer that comprises β-cobalt hydroxide, more excellent for the adaptation of the particle surface containing nickel hydroxide.
[process B]
Process B is, on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating.
In process B, by the pH value of suspension-turbid liquid being adjusted in 11.5～13.5 scope, thereby can α-cobalt hydroxide be transformed to β-cobalt hydroxide with good efficiency.
From being transformed to more equably the viewpoint of β-cobalt hydroxide, preferably the pH value of suspension-turbid liquid is remained to constant value in above-mentioned scope.
The pH value of suspension-turbid liquid can regulate by add alkaline aqueous solution in suspension-turbid liquid.
As alkaline aqueous solution used, the alkaline aqueous solution illustrating in operation A before can enumerating.
In process B, by the dissolved oxygen concentration of suspension-turbid liquid is remained below 0.5mg/L, preferably remain 0.01～0.1mg/L, can suppress α-cobalt hydroxide oxidized, can be transformed to equably β-cobalt hydroxide with good efficiency.
As making dissolved oxygen concentration, be the method below 0.5mg/L, the method illustrating in operation A before can using.
Carry out the time of process B, as long as α-cobalt hydroxide can be transformed to β-cobalt hydroxide, have no particular limits.Be generally 10 minutes～2 hours, be preferably 30 minutes～1 hour.
The reaction temperature of process B is generally 10～80 ℃, is preferably 20～60 ℃.
By process B, can containing the not oxidized condition down conversion of surperficial α-cobalt hydroxide of the particle of nickel hydroxide, be β-cobalt hydroxide in coating.β-cobalt hydroxide is the compound that is suitable as the precursor while forming high-order cobalt compound layer.
[operation C]
Operation C is, respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the cobalt compound that the average valence mumber that is transformed to cobalt atom is 2.1～3.0, obtains comprising the operation of suspension-turbid liquid of the particle containing nickel hydroxide of the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt by this.
In operation C, the pH value of suspension-turbid liquid is adjusted to 11.5～13.5, is preferably 12.0～13.0.By the pH value of suspension-turbid liquid being adjusted in 11.5～13.5 scope, can promote the oxidation of β-cobalt hydroxide.
From the viewpoint that can be oxidized more equably, pH value preferably remains constant value in above-mentioned scope.Here, " pH value is constant value " refer to pH value regulation value positive and negative 0.1 in.
In operation C, the dissolved oxygen concentration of suspension-turbid liquid is adjusted to 1.0～15.0mg/L, is preferably 2.0～14.0mg/L.
By the dissolved oxygen concentration of suspension-turbid liquid is adjusted in above-mentioned scope, make coating contain surperficial β-cobalt hydroxide oxidation of the particle of nickel hydroxide, the good efficiency of take is transformed to the cobalt compound that the average valence mumber of cobalt atom is 2.1～3.0.
As the method that makes dissolved oxygen concentration in above-mentioned scope, can enumerate to being blown into air, oxygen in suspension-turbid liquid, with inert gas dilution oxygen and the method for mist.
Carry out the time of operation C, as long as energy oxidation of beta-cobalt hydroxide obtains the cobalt compound that the average valence mumber of cobalt atom is 2.1～3.0, have no particular limits.Be generally 10 minutes to 2 hours, be preferably 30 minutes to 1 hour.
The reaction temperature of operation C is generally 10～80 ℃, is preferably 20～60 ℃.
After operation C, for the sediment of gained, by known processing such as suitably filtering, wash, be dried, can the separated particle agglomeration that comprises cobalt compound coating nickel hydroxide as target.
[particle agglomeration]
Particle agglomeration of the present invention is the particle agglomeration making by having the manufacture method of above-mentioned operation A～operation C, and it contains the particle containing Co/Ni being difficult to from sur-face peeling high-order cobalt compound layer.The content of the particle containing Co/Ni in particle agglomeration of the present invention is preferably 95～99 % by weight more than being generally 90 % by weight.
The cobalt compound that is 2.1～3.0 by the average valence mumber of cobalt atom containing the high-order cobalt compound layer of the particle of Co/Ni forms.The cobalt compound that the average valence mumber of cobalt atom is 2.1～3.0 is the high-order oxide of β-cobalt hydroxide (II), typically is alkali formula cobalt hydroxide.
The average valence mumber of the cobalt atom of the cobalt compound of formation high-order cobalt compound layer, such as regulating by analytical methods such as iodimetric titration.Particularly, utilize ICP luminesceence analysis to measure containing contained cobalt amount in the particle of Co/Ni, then with hypo solution, come titration to make to be dissolved in containing particle and the KI of Co/Ni the solution making in hydrochloric acid, can calculate by this average valence mumber of cobalt atom.
By making the average valence mumber of cobalt atom be more than 2.1, be preferably more than 2.6, thereby can suppress to become large because of the ratio of the high alkali formula cobalt hydroxide of the charging conductivity that electrochemical oxidation forms in battery.Can suppress the reduction of self-discharge characteristic by this.In addition, by making the average valence mumber of cobalt, be below 3.0, can keep the balance of the electric charge in the crystallization of cobalt compound, make cobalt compound stable.Therefore, can suppress and the reacting of alkaline electrolyte in battery, suppress the cations such as sodium ion, potassium ion and enter into crystallization.Can suppress the rising of the electron conduction of cobalt compound by this, and then make self-discharge characteristic become good.
There is no particular limitation for the average thickness of high-order cobalt compound layer, is generally 0.01～1.0 μ m, is preferably 0.1～0.5 μ m.By making the average thickness of high-order cobalt compound layer in above-mentioned scope, thereby further improve the adaptation with the core part of particle containing Co/Ni.
The particle diameter D50 of particle agglomeration of the present invention is preferably 10～15 μ m, more preferably 11～14 μ m.During particle diameter D50 less than 10 μ m, there is the tendency contain a large amount of large volume particles, thus by particle agglomeration during as positive active material capacity density easily reduce.On the other hand, if particle diameter D50 surpasses 15 μ m, while particle agglomeration being used as to positive active material, be sometimes difficult to improve compactedness.
In particle agglomeration of the present invention, contained particle diameter is that the cumulative frequency % value of the particle below 5 μ m is preferably below 12.0%, more preferably below 11.5%.By making particle diameter, be that cumulative frequency % value below 5 μ m is below 12.0%, thereby when preparing thickener, be difficult for becoming full-bodied thickener, improve the operability of making when anodal.
The BET specific area of particle agglomeration of the present invention is preferably 5～20m 2/ g, more preferably 8～15m 2/ g.BET specific area deficiency 5m 2when the particle agglomeration of/g is used as positive active material, may reduce the ionic conduction while discharging and recharging.On the other hand, for BET specific area, surpass 20m 2the particle agglomeration of/g, because the moisture in atmosphere is easily adsorbed onto particle surface, during therefore as positive active material, alkaline battery may be deteriorated.
The tap density of particle agglomeration of the present invention is preferably 1.5～2.5g/cm 3, 1.6～2.4g/cm more preferably 3.Tap density deficiency 1.5g/cm 3particle agglomeration when the positive active material, may be difficult to improve compactedness.In addition, tap density is more high better, but is conventionally difficult to obtain over 2.5g/cm 3tap density.
The bulk density of particle agglomeration of the present invention is preferably 0.8～1.8g/cm 3, 0.9～1.7g/cm more preferably 3.Bulk density deficiency 0.8g/cm 3particle agglomeration when the positive active material, may be difficult to improve compactedness.In addition, bulk density is more high better, but is conventionally difficult to obtain over 1.8g/cm 3bulk density.
BET specific area, tap density and the bulk density of particle agglomeration of the present invention can adopt the known determination method of recording in embodiment to obtain.
For particle agglomeration of the present invention, in using the Alpha-ray X-ray diffraction mensuration of CuK, near 2 θ=37～40 °, observe the 1st peak (peak 1), near 2 θ=64～67 °, observe the 2nd peak (peak 2), and the half breadth at above-mentioned peak 1 is preferably 0.7～1.2 °, the half breadth at peak 2 and is preferably below 1.5 °.
Think that peak 1 is the peak of nickel hydroxide contained in the core part being derived from containing the particle of Co/Ni.Therefore, the half breadth at peak 1 represents the crystallinity of nickel hydroxide.The half breadth at peak 1 is 0.7 ° when above, and the crystallinity of nickel hydroxide is not too high state.Therefore, by this particle agglomeration is used as to positive active material, sufficient diffusion of protons can be carried out, the positive pole of good flash-over characteristic can be obtained having.On the other hand, the half breadth at peak 1 is 1.2 ° when following, and the crystallinity of nickel hydroxide be not too low state, means that the core of the particle that contains Co/Ni partly has high density.Therefore,, by this particle agglomeration is used as to positive active material, can obtain the positive pole that capacity density is high.
Think that peak 2 is peaks of alkali formula cobalt hydroxide contained in the high-order cobalt compound layer being derived from containing the particle of Co/Ni.Therefore, the half breadth at peak 2 represents the crystallinity of alkali formula cobalt hydroxide.The half breadth at peak 2 is 1.5 ° when following, and the crystallinity of alkali formula cobalt hydroxide is not too low state, and the conductivity of alkali formula cobalt hydroxide does not become too high.Therefore, by this particle agglomeration is used as to positive active material, the positive pole that can obtain being difficult to self-discharge.The lower limit of the half breadth at peak 2 is not particularly limited, and is generally more than 0.5 °.By making the half breadth at peak 2, be more than 0.5 °, thereby make alkali formula cobalt hydroxide there is suitable conductivity, can improve the utilance of active material.
As mentioned above, particle agglomeration of the present invention makes by having the manufacture method of operation A～operation C.In particle agglomeration of the present invention, the content of minuteness particle is few, so the particle agglomeration of the application of the invention, can obtain having the thickener of proper viscosity, and the operability while making positive pole is excellent.In addition, form particle agglomeration of the present invention, surface by the coating of high-order cobalt compound containing the particle of nickel hydroxide because high-order cobalt compound is difficult to peel off, thereby conductivity is difficult to reduce.Owing to having these characteristics, particle agglomeration of the present invention is useful as the positive active material of alkaline battery.
Embodiment
Illustrate in greater detail the present invention with comparative example by the following examples.But the present invention is not subject to any restriction of following examples.
Being analyzed as follows of the particle agglomeration of gained carried out.
(a) form
Use ICP apparatus for analyzing luminosity (リガ Network society system, CIROS-120 EOP) to analyze the composition of particle.
(b) the average valence mumber of cobalt
Carry out ICP luminesceence analysis, measure cobalt amount.Then, sample and KI are dissolved in hydrochloric acid, prepare sample solution, with this sample solution of sodium thiosulfate solution titrated.Based on said determination result, calculate the average valence mumber of cobalt.
(c) particle diameter
With laser diffraction granularity, distribute and count (hole field makes society of institute system, LA-950), use pure water as decentralized medium, measuring particle diameter is amount and the particle diameter D50 of the particle below 5 μ m.
(d) BET specific area
Use specific area measuring device (マウ ンテック society system, Macsorb), by single-point BET method, measure.
(e) tap density
Use タ ッ プ デ Application サ ー (セイシン society system, KYT-4000), adopt the constant volume determination method in the method for recording in JIS R1628 to measure.
(f) bulk density
Sample is freely fallen and be filled in container, by the volume of container and the quality of sample, calculate bulk density.
(g) X-ray diffraction
Use X-ray diffraction device (リガ Network society system, RINT2200), with following condition, measure.
X ray: CuK α/40kV/40mA
Slit: DS/SS=1 °, RS=0.3mm
Scan pattern: FT measures
Sampling time (Sampling Time): 0.4 second
Step-length (Step Width): 0.01 °
(h) electron microscope observation
Use electron microscope (Hitachi society system, S-3400) to observe particle surface.Electron micrograph while observing with 20000 times of multiplying powers is shown in Fig. 1～Fig. 3.
Being analyzed as follows of suspension-turbid liquid carried out.
(a) oxygen concentration determination
Use DO determination meter (HORIBA society system, OM-051-L1) to measure the dissolved oxygen concentration of suspension-turbid liquid.
(b) pH pH-value determination pH
Use pH meter (HORIBA society system, D-51S) to measure the pH value of suspension-turbid liquid.
[Production Example 1] is containing the manufacture of the particle of nickel hydroxide
The aqueous solution with supplying with continuously metal ion with the flow of 15.0mL/ minute respectively in the reactive tank of mixer to volume 40L (be take nickel ion: cobalt ions: the ratio that the mol ratio of magnesium ion is 95: 2: 3 contains nickelous sulfate (II), cobaltous sulfate (II) and magnesium sulfate (II), concentration of metal ions is the aqueous solution of 2.4 moles/L), the sodium hydrate aqueous solution of 5.5 moles/L is, the ammonia spirit of 6.0 moles/L, in stirred tank, temperature is maintained to 50 ℃ simultaneously.
In reaction system, reach stable state (steady state that the pH value of the proportions constant of the concentration of the particle of concentration of metal ions and generation, suspension-turbid liquid is 12.5) afterwards, by overflow pipe, take out the suspension-turbid liquid in reactive tank, it is temporarily stored, then wash, processed, obtain thus comprising the pie containing the particle of nickel hydroxide.
A part for pie is dry, measure the physical property containing the particle of nickel hydroxide.Measurement result is illustrated in table 1 as a reference.
In addition, carry out the X-ray diffraction of the particle containing nickel hydroxide of gained and measure, result can be confirmed the collection of illustrative plates and JCPDS inorganic substances reference number of a document of gained: the XRD collection of illustrative plates of recording in 14-117 is consistent, is β-Ni (OH) 2the individual layer of type, cobalt, magnesium are solid-solubilized in nickel hydroxide.
[embodiment 1]
To add in the reactive tank with mixer of volume 40L in Production Example 1, make comprise pie (containing particle weight, the 5600g of nickel hydroxide) containing the particle of nickel hydroxide and the warm water of 50 ℃, stir, obtain suspension-turbid liquid.The temperature of suspension-turbid liquid is maintained to 50 ℃.In addition, by adding the sodium hydrate aqueous solution of 5.5 moles/L, the pH value of suspension-turbid liquid is adjusted to 9.0, by be blown into nitrogen in suspension-turbid liquid, the dissolved oxygen concentration of suspension-turbid liquid is adjusted to 0.2mg/L.
The temperature of suspension-turbid liquid, pH value, dissolved oxygen concentration are maintained respectively to above-mentioned value on one side, on one side to cobaltous sulfate (II) aqueous solution 2.08L that adds continuously 1.5 moles/L in suspension-turbid liquid, in order to regulate pH value, add discontinuously the sodium hydrate aqueous solution of 5.5 moles/L, continue to stir 120 minutes simultaneously.
Then, Yi Bian maintain respectively temperature and the dissolved oxygen concentration of suspension-turbid liquid, Yi Bian add the sodium hydrate aqueous solution of 5.5 moles/L to make the pH value of suspension-turbid liquid be elevated to 12.0 in suspension-turbid liquid, keep this state to continue to stir 60 minutes.Then, Yi Bian maintain respectively temperature and the pH value of suspension-turbid liquid, Yi Bian the dissolved oxygen concentration of suspension-turbid liquid is brought up to 3.0mg/L by be blown into air in suspension-turbid liquid, keep this state to continue to stir 120 minutes.Then sediment is filtered, dewaters, is dried and processes, obtain the particle agglomeration as target.
The characteristic of the particle agglomeration of gained is shown in table 1.
In addition, adopt X-ray diffraction to measure high-order cobalt compound layer is investigated, result can be confirmed as JCPDS inorganic substances reference number of a document: the layer structure of six sides that record in 7-169-water chestnut face crystalline substance is the alkali formula cobalt hydroxide that crystallinity is high.
[comparative example 1]
To add in the reactive tank with mixer of volume 40L in Production Example 1, make comprise pie (containing particle weight, the 5600g of nickel hydroxide) containing the particle of nickel hydroxide and the warm water of 50 ℃, stir, obtain suspension-turbid liquid.The temperature of suspension-turbid liquid is maintained to 50 ℃ on one side, on one side by adding the sodium hydrate aqueous solution of 5.5 moles/L that the pH value of suspension-turbid liquid is adjusted to 12.5, by be blown into air in suspension-turbid liquid, the dissolved oxygen concentration of suspension-turbid liquid is adjusted to 3.0mg/L.
The temperature of suspension-turbid liquid, pH value, dissolved oxygen concentration are maintained respectively to above-mentioned value on one side, on one side to cobaltous sulfate (II) aqueous solution 2.08L that adds continuously 1.5 moles/L in suspension-turbid liquid, in order to regulate pH value, add discontinuously the sodium hydrate aqueous solution of 5.5 moles/L, continue to stir 120 minutes simultaneously.
Then sediment is filtered, dewaters, is dried and processes, obtain particle agglomeration.
The physical property of the particle agglomeration of gained is shown in table 1.
[table 1]
In the manufacture method of embodiment 1, the pH value of suspension-turbid liquid and the pH value of comparative example 1 when cobalt hydroxide is separated out on the surface of the particle containing nickel hydroxide are compared lower.In the particle agglomeration obtaining in embodiment 1, particle diameter is that the content of the particle below 5 μ m is few, and in the raw material particle agglomeration of its amount and reference example, particle diameter is that the content of the particle below 5 μ m is compared further minimizing.
On the other hand, in the pH value of the suspension-turbid liquid of cobalt hydroxide when separating out containing the surface of the particle of nickel hydroxide particle agglomeration higher than the pH value of embodiment 1, that obtain in comparative example 1, particle diameter is that the content of the particle below 5 μ m is many, and it measures particle diameter in the raw material particle agglomeration with reference example is that the content of the particle below 5 μ m is compared further increase.
When the SEM image of the particle of the comparative example 1 shown in the SEM image of embodiment illustrated in fig. 11 particle and Fig. 2 is compared, the state of known particle surface differs widely.Think by the increasing proportion that the crystalline growth of cobalt compound is fully carried out, thus embodiment 1 containing in the particle of Co/Ni, the cobalt compound on surface becomes and is difficult to peel off.

Claims (2)

1. comprise the particle agglomeration containing the particle of nickel hydroxide, it is the particle agglomeration obtaining by having the manufacture method of following operation A～operation C, the cobalt compound coating that the surface of the described particle containing nickel hydroxide is 2.1～3.0 by the average valence mumber of cobalt,
Operation A: under agitation, the pH value of the suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0 on one side, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating, described raw material particle agglomeration is the raw material particle agglomeration comprising containing the particle of nickel hydroxide, its particle diameter D50 is 10～15 μ m, particle diameter is that the cumulative frequency % value of the particle below 5 μ m is below 12.0%,
Process B: on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating;
Operation C: respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the operation of the suspension-turbid liquid of the particle that contains nickel hydroxide that obtains comprising the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt.
2. comprise the manufacture method containing the particle agglomeration of the particle of nickel hydroxide, the method has following operation A～operation C, the cobalt compound coating that the surface of the described particle containing nickel hydroxide is 2.1～3.0 by the average valence mumber of cobalt,
Operation A: under agitation, the pH value of the suspension-turbid liquid that contains raw material particle agglomeration is remained on to 8.0～11.0 on one side, dissolved oxygen concentration is remained on below 0.5mg/L, on one side to adding in described suspension-turbid liquid, to contain with respect to 100 weight portion above-mentioned raw materials particle agglomeration be the aqueous solution of cobalt (II) salt of the amount of 2～10 weight portions, thereby obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of α-cobalt hydroxide coating, described raw material particle agglomeration is the raw material particle agglomeration comprising containing the particle of nickel hydroxide, its particle diameter D50 is 10～15 μ m, particle diameter is that the cumulative frequency % value of the particle below 5 μ m is below 12.0%,
Process B: on one side the dissolved oxygen concentration of the suspension-turbid liquid obtaining in operation A is remained on below 0.5mg/L, the pH value of above-mentioned suspension-turbid liquid is adjusted to 11.5～13.5 on one side, thereby the surperficial α-cobalt hydroxide that makes coating contain the particle of nickel hydroxide is transformed to β-cobalt hydroxide, obtain comprising surface by the operation of the suspension-turbid liquid of the particle containing nickel hydroxide of β-cobalt hydroxide coating;
Operation C: respectively the pH value that obtains suspension-turbid liquid in process B is adjusted to 11.5～13.5, dissolved oxygen concentration is adjusted to 1.0～15.0mg/L, thereby the surperficial β-cobalt hydroxide oxidation by coating containing the particle of nickel hydroxide, the operation of the suspension-turbid liquid of the particle that contains nickel hydroxide that obtains comprising the cobalt compound coating that surface is 2.1～3.0 by the average valence mumber of cobalt.
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