CN103204555A - Method for preparing spherical nickel hydroxide with surface coated by gamma-hydroxy cobaltous oxide - Google Patents
Method for preparing spherical nickel hydroxide with surface coated by gamma-hydroxy cobaltous oxide Download PDFInfo
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- CN103204555A CN103204555A CN2013101505935A CN201310150593A CN103204555A CN 103204555 A CN103204555 A CN 103204555A CN 2013101505935 A CN2013101505935 A CN 2013101505935A CN 201310150593 A CN201310150593 A CN 201310150593A CN 103204555 A CN103204555 A CN 103204555A
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Abstract
The invention provides a method for preparing spherical nickel hydroxide with the surface coated by gamma-hydroxy cobaltous oxide. The method comprises the steps of: firstly, preparing the spherical nickel hydroxide of which the surface is coated by cobaltous hydroxide, putting into a reactor, leading in oxygen under a stirring condition, pre-oxidizing until the color of a material inside the reactor stops changing, and controlling the temperature inside the reactor at 40-150 DEG C; adding an alkali metal hydroxide solution to the reactor; lastingly leading in oxygen under the stirring condition; and washing and baking an oxidized product by pure water after oxidizing reaction lasts for certain time, so as to obtain the spherical nickel hydroxide with the surface coated by the gama-hydroxy cobaltous oxide. By adopting the preparation method disclosed by the invention, a cobalt dissolved reaction at the initial stage of oxidization can be restrained; a lot of water is not generated in a preparation process; and the substances on a sieve when the materials are sieved are fewer.
Description
Technical field
The present invention relates to a kind of nickel-based battery preparation methods, particularly a kind of preparation method of ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide.
Background technology
What the positive electrode active materials of nickel metal hydride battery used at first is conventional ball-shape nickel hydroxide.Because nickel hydroxide itself is a kind of semi-conductor, in high-power application, the characteristic of its poorly conductive is the directly sex-limited high rate during charging-discharging of battery.In order to improve the electroconductibility of nickel hydroxide, people coat one deck β-Co (OH) at ball shape nickel hydroxide surface
2, developed the nickel hydroxide positive plate active substance that coats cobalt.This β-the Co (OH) that evenly is coated on the surface
2Oxidation generates β-CoOOH in charge and discharge process, can improve the homogeneity of conductive network, thus the utilization that can improve the nickel hydroxide active substance.But, the nickel-hydrogen secondary cell that uses this positive active material is in state such as heavy-current discharge, deep discharge, short circuit following time, the irrecoverable problem that positive electrode capacity is often arranged, major cause wherein mainly is when carrying out the deep discharge of nickel hydroxide, the conductive network material β-CoOOH of nickel hydroxide surface also can carry out the reduction reaction of part, divalent cobalt after its reduction can form cobalt in the electrolytic solution of battery complexing ion causes the dissolving of cobalt, thereby causes the imperfect of β-CoOOH conductive network.
Through further studies show that, γ-the CoOOH of another kind of crystal formation can form the state that is higher than 3.0 valencys, reduction potential in alkaline electrolyte is lower, be not easy to be restored to 2.0 valencys, so just can improve the integrity that nickel hydroxide surface covers the cobalt layer, patent CN101106193 has mentioned a kind of method of nickel hydroxide of coated gamma hydroxy cobalt oxide, under the condition of alkalescence, to the cobaltous hydroxide layer that nickel hydroxide surface coats, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide with oxygen.
But, among the preparation method described in the above-mentioned patent, the direct oxidation reaction meeting of cobaltous hydroxide according to around the temperature, humidity and the conditions such as concentration of oxygen different on every side of trickle when the handling particle self of making moist of concentration, the particle of the alkaline components that exists bigger variation is arranged, have complicated reaction trajectory, the cobalt that causes part to be covered in the cobalt layer can be by abundant oxidation.Particularly the generation water in the reaction process can cause the cobalt ball nickel that covers in the oxidation to be easy to caking, in the subsequent washing process, covers the cobalt layer and occurs breakage because of adhesion, and caking also can cause screen overflow more when sieving simultaneously.
Summary of the invention
But the present invention aims to provide a kind of preparation technology that can reduce to the generation of water in the dependence inhibited reaction process of environment, the method for the ball-shape nickel hydroxide of the preparation coated gamma hydroxy cobalt oxide of raising material integrity and conductive network electroconductibility.The present invention realizes by following scheme:
A kind of method for preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, at first by the existing method that coats the cobaltous hydroxide ball-shape nickel hydroxide for preparing, water-soluble salt, alkali metal hydroxide, ammoniacal liquor and water with ball-shape nickel hydroxide, cobalt are raw material, prepare the ball-shape nickel hydroxide that the surface coats cobaltous hydroxide; Afterwards, the ball-shape nickel hydroxide that the surface that obtains is coated cobaltous hydroxide joins in the reactor, under agitation condition, adds oxygenant in reactor, and preoxidation material color to the reactor stops to change, and reactor temperature is controlled to be 40～150 ℃; Add alkali hydroxide soln again in reactor afterwards, under the agitation condition, add oxygenant again, behind the lasting oxidizing reaction certain hour, the product that oxidation is obtained washs with pure water again---and dry, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
Generally in application, described preoxidation is adopted identical oxygenant with lasting two stages of oxidation.The preferred oxygen of oxygenant.The flow range of described oxygen can feed 0.1～10L/ minute standard by material in every kilogram of reactor.
And in order to improve the electrical property of ball-shape nickel hydroxide, behind described lasting oxidation certain hour, adding concentration in the products therefrom is the lithium hydroxide solution of 5～20g/L, under agitation condition, 30～100 ℃ of control temperature, reaction times is 0.5～2.0 hour, and the product that reaction is obtained washs with pure water again---oven dry, the final product that obtains is the nickel hydroxide of mixing the coated gamma hydroxy cobalt oxide of lithium.
Compared with prior art, the present invention has following advantage:
1. adopt preparation method of the present invention that the cobalt solubilizing reaction at inhibited oxidation initial stage is had positive effect, it shows as the generation that does not occur big water gaging in preparation process, material screen overflow when sieving is less, poly-the phenomenon that is the material in the preparation process is few, caking is few, thereby the cobalt surface layer breakage of product is little.
2. the product that adopts the present invention to prepare has reduced its BET, and to go out the cobalt average valence that the surface coats cobalt by iodometric determination be 3.35 ± 0.1.
Embodiment
Embodiment 1
A kind of method for preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, according to the following steps:
(1) stock liquid preparation: the 1mol/L cobalt sulfate solution, contain the sodium hydroxide solution of ammonia, wherein concentration sodium hydroxide is 5.0mol/L, and the concentration of ammonia is 0.5mol/L, 50% sodium hydroxide solution.
(2) cobaltous hydroxide coats:
The ball-shape nickel hydroxide matrix is put into reactor, add pure water, regulate pH value to 10.5 with the sodium hydroxide solution that contains ammonia, under 200 rev/mins agitation condition, continuous adding cobalt sulfate solution and the sodium hydroxide solution that contains ammonia, the control temperature is 60 ℃, in 4 hours reaction times, the cobalt liquor amount that adds in the reaction accounts for 5% of nickel hydroxide matrix by the cobaltous hydroxide amount that coats.With the material filtering after coating, wash to pH be 7.0, namely obtain the nickel hydroxide that the surface coats cobaltous hydroxide 60 ℃ of following oven dry again.
(3) preoxidation:
The ball-shape nickel hydroxide that coats cobaltous hydroxide is added in the reactor, under agitation condition, aerating oxygen carries out preoxidation, the control temperature is 75 ℃, oxygen flow is material minute in the 5.0L/kg reactor, in the reaction process, the material color successively experiences white---yellow-white---yellow-green colour, 4 hours time in the reactor.
(4) oxidation:
After the material color becomes yellow-green colour and no longer changes in reactor, slowly add temperature in the reactor and be 80 ℃ 50% sodium hydroxide solution, add-on be in the reactor ball-shape nickel hydroxide material total mass 4.0%; Under the agitation condition, continue aerating oxygen, oxygen flow is: material minute in the 5.0L/kg reactor, keep 80 ℃ of reactor temperatures, and react and stop after 20 minutes.
(5) drying:
The oxidation products therefrom is washed neutrality with pure water, and 110 ℃ of oven dry down, 200 orders sieve, and namely obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
In reaction process, the phenomenon of moist caking does not appear in material in the reactor, and when product sieved, screen overflow seldom.
After testing, the powder impedance of the above-mentioned nickel hydroxide active substance for preparing is 3.0 Ω cm, and BET is 9.75m
2/ g, the cobalt average valence that goes out coating cobalt in surface by iodometric determination is 3.35.
Embodiment 2:
The oxidation products that embodiment 1 obtains is done further to mix, and step is:
Gained material after the oxidizing reaction is joined in the lithium hydroxide solution of 10g/L, making the solids concn of nickel hydroxide active substance in solution is 200g/L, under agitation condition, keep 60 ℃ of temperature of reaction system, reaction times is 30min, the material that to handle filters, washs to neutral with pure water again, namely obtains the nickel hydroxide of the coated gamma hydroxy cobalt oxide of elements doped lithium again 110 ℃ of following oven dry.
The product powder impedance that embodiment 2 obtains is 1.5 Ω cm, and BET is 9.79m
2/ g, the cobalt average valence that goes out coating cobalt in surface by iodometric determination is 3.35; The content of Li in the nickel hydroxide active substance is 0.30%.
Claims (5)
1. method for preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, at first water-soluble salt, alkali metal hydroxide, ammoniacal liquor and the water with ball-shape nickel hydroxide, cobalt is raw material, prepare the ball-shape nickel hydroxide of surface coating cobaltous hydroxide, it is characterized in that: afterwards, the ball-shape nickel hydroxide that the surface that obtains is coated cobaltous hydroxide joins in the reactor, under agitation condition, in reactor, add oxygenant, preoxidation material color to the reactor stops to change, and reactor temperature is controlled to be 40～150 ℃; Add alkali hydroxide soln again in reactor afterwards, under the agitation condition, add oxygenant again, behind the lasting oxidizing reaction certain hour, the product that oxidation is obtained washs with pure water again---and dry, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
2. the method for the ball-shape nickel hydroxide of preparation coated gamma hydroxy cobalt oxide as claimed in claim 1 is characterized in that: described preoxidation and the identical oxygenant of lasting two stages of oxidation employing.
3. the method for the ball-shape nickel hydroxide of preparation coated gamma hydroxy cobalt oxide as claimed in claim 2 is characterized in that: the preferred oxygen of described oxygenant.
4. the method for the ball-shape nickel hydroxide of preparation coated gamma hydroxy cobalt oxide as claimed in claim 3 is characterized in that: the flow of described oxygen feeds by the standard that material in every kilogram of reactor fed 0.1～10L/ minute.
5. as the method for the ball-shape nickel hydroxide of the described preparation coated gamma hydroxy cobalt oxide of one of claim 1～4, it is characterized in that: behind described lasting oxidation certain hour, adding concentration in the products therefrom is the lithium hydroxide solution of 5～20g/L, under agitation condition, 30～100 ℃ of control temperature, reaction times is 0.5～2.0 hour, and the product that reaction is obtained washs with pure water again---oven dry.
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| CN201310150593.5A CN103204555B (en) | 2013-04-26 | 2013-04-26 | Prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752688A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | Spherical nickel hydroxide coated with Co(OH)2 on surface and preparation method thereof |
| CN107452955A (en) * | 2016-06-01 | 2017-12-08 | 中国科学院大连化学物理研究所 | A kind of hexa-prism hydroxy cobalt oxide material with hollow structure and preparation method thereof |
| CN112136235A (en) * | 2018-05-21 | 2020-12-25 | 丰田自动车株式会社 | Positive electrode active material, positive electrode, alkaline storage battery, and method for producing positive electrode active material |
| EP3799166A4 (en) * | 2018-05-21 | 2022-03-09 | Toyota Jidosha Kabushiki Kaisha | Positive electrode active material, positive electrode, alkaline battery, and method for producing positive electrode active material |
| CN115697913A (en) * | 2020-06-18 | 2023-02-03 | 株式会社田中化学研究所 | Cobalt-coated nickel-containing hydroxide particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1794492A (en) * | 2005-11-11 | 2006-06-28 | 河南新飞科隆电源有限公司 | Method of cladding hydroxy cobalt oxide on spherical nickel hydroxide surface |
| CN101106193A (en) * | 2007-07-09 | 2008-01-16 | 金天能源材料有限公司 | Preparation method of nickel hydroxide with surface coated with gamma-hydroxy cobalt oxide |
| CN102142547A (en) * | 2011-01-29 | 2011-08-03 | 江门市长优实业有限公司 | Preparation method of spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide |
-
2013
- 2013-04-26 CN CN201310150593.5A patent/CN103204555B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1794492A (en) * | 2005-11-11 | 2006-06-28 | 河南新飞科隆电源有限公司 | Method of cladding hydroxy cobalt oxide on spherical nickel hydroxide surface |
| CN101106193A (en) * | 2007-07-09 | 2008-01-16 | 金天能源材料有限公司 | Preparation method of nickel hydroxide with surface coated with gamma-hydroxy cobalt oxide |
| CN102142547A (en) * | 2011-01-29 | 2011-08-03 | 江门市长优实业有限公司 | Preparation method of spherical nickel hydroxide anode material coated with gamma-hydroxy cobalt oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752688A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | Spherical nickel hydroxide coated with Co(OH)2 on surface and preparation method thereof |
| CN107452955A (en) * | 2016-06-01 | 2017-12-08 | 中国科学院大连化学物理研究所 | A kind of hexa-prism hydroxy cobalt oxide material with hollow structure and preparation method thereof |
| CN112136235A (en) * | 2018-05-21 | 2020-12-25 | 丰田自动车株式会社 | Positive electrode active material, positive electrode, alkaline storage battery, and method for producing positive electrode active material |
| EP3799166A4 (en) * | 2018-05-21 | 2022-03-09 | Toyota Jidosha Kabushiki Kaisha | Positive electrode active material, positive electrode, alkaline battery, and method for producing positive electrode active material |
| CN115697913A (en) * | 2020-06-18 | 2023-02-03 | 株式会社田中化学研究所 | Cobalt-coated nickel-containing hydroxide particles |
| CN115697913B (en) * | 2020-06-18 | 2024-04-26 | 株式会社田中化学研究所 | Cobalt-coated nickel-containing hydroxide particles |
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| CN103204555B (en) | 2015-08-19 |
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