CN103204555B - Prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide - Google Patents
Prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide Download PDFInfo
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Abstract
The invention provides a kind of method preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, first the ball-shape nickel hydroxide of Surface coating cobaltous hydroxide is prepared, again in reactor, under agitation condition, pass into oxygen, in preoxidation to reactor, material color stops change, and it is 40 ~ 150 DEG C that reactor temperature controls; In reactor, add alkali hydroxide soln more afterwards, under agitation condition, continue to pass into oxygen, after oxidizing reaction certain hour, then will the product pure water obtained be oxidized---dry, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.Adopt preparation method of the present invention can the cobalt solubilizing reaction at inhibited oxidation initial stage, in preparation process, do not occur the generation of large water gaging, material screen overflow when sieving be less.
Description
Technical field
The present invention relates to a kind of preparation method of nickel-based battery material, particularly a kind of preparation method of ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide.
Background technology
The positive electrode active materials of nickel metal hydride battery uses conventional ball-shape nickel hydroxide at first.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 are at the coated one deck β of ball shape nickel hydroxide surface-Co (OH)
2, have developed the nickel hydroxide positive plate active substance of coated cobalt.This β-the Co (OH) being evenly coated on surface
2in charge and discharge process, oxidation generates β-CoOOH, can improve the homogeneity of conductive network, thus can improve the utilization of nickel hydroxide active material.But, when using the nickel-hydrogen secondary cell of this positive active material under the states such as heavy-current discharge, deep discharge, short circuit, often there is the irrecoverable problem of positive electrode capacity, major cause is wherein mainly 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, the complexing ion that divalent cobalt after its reduction can form cobalt in the electrolytic solution of battery causes the dissolving of cobalt, thus causes the imperfect of β-CoOOH conductive network.
Show through further studying, γ-the CoOOH of another kind of crystal formation can form the state 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 cobalt layers, patent CN101106193 refer to a kind of method of nickel hydroxide of coated gamma hydroxy cobalt oxide, under the condition of alkalescence, with the cobaltous hydroxide layer that oxygen is coated to nickel hydroxide surface, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
But, in preparation method described in above-mentioned patent, the direct oxidation reaction of cobaltous hydroxide can according to the concentration of the alkaline components around existed, particle trickle make moist and process time the temperature of particle self, humidity around and oxygen the difference of the condition such as concentration have a greater change, there is complicated reaction trajectory, cause the part cobalt covered in cobalt layers to be substantially oxidized.Generation water particularly in reaction process, can cause the cobalt ball nickel that covers in being oxidized to be easy to caking, in follow-up washing process, cover cobalt layers and occur breakage because of adhesion, lump simultaneously and also can cause screen overflow more when sieving.
Summary of the invention
The present invention aim to provide a kind of can reduce preparation technology to the dependence of environment, can the generation of water in inhibited reaction process, improve the method preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide of material integrity and conductive network electroconductibility.The present invention is realized by following scheme:
A kind of method preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, first by the method for the coated cobaltous hydroxide ball-shape nickel hydroxide of existing preparation, with the water-soluble salt of ball-shape nickel hydroxide, cobalt, alkali metal hydroxide, ammoniacal liquor and water for raw material, prepare the ball-shape nickel hydroxide of Surface coating cobaltous hydroxide; Afterwards, join in reactor by the ball-shape nickel hydroxide of the Surface coating cobaltous hydroxide obtained, under agitation, in reactor, add oxygenant, in preoxidation to reactor, material color stops change, and it is 40 ~ 150 DEG C that reactor temperature controls; In reactor, add alkali hydroxide soln more afterwards, under agitation condition, then add oxygenant, after continued oxidation reaction certain hour, then will the product pure water obtained be oxidized---dry, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
Generally in the application, described preoxidation and continued oxidation two benches adopt identical oxygenant.The preferred oxygen of oxygenant.The flow range of described oxygen can pass into the standard of 0.1 ~ 10L/ minute by material in every kilogram of reactor.
And in order to improve the electrical property of ball-shape nickel hydroxide, after described continued oxidation certain hour, the lithium hydroxide solution that concentration is 5 ~ 20g/L is added in products therefrom, under agitation, control temperature 30 ~ 100 DEG C, reaction times is 0.5 ~ 2.0 hour, then the product pure water that will be obtained by reacting---dry, the final product obtained is the nickel hydroxide of the coated gamma hydroxy cobalt oxide mixing lithium.
Compared with prior art, the present invention has following advantage:
1. adopt the cobalt solubilizing reaction of preparation method of the present invention to the inhibited oxidation initial stage to have positive effect, it shows as the generation not occurring large water gaging in preparation process, material screen overflow when sieving is less, the clustering phenomena of the material namely in preparation process is few, caking is few, thus the surperficial cobalt layers breakage of product is little.
2. adopt the product for preparing of the present invention, reduce its BET, and be 3.35 ± 0.1 by the cobalt average valence that iodometric determination goes out Surface coating cobalt.
Embodiment
embodiment 1
Prepare a method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide, according to the following steps:
(1) stock liquid preparation: 1mol/L cobalt sulfate solution, sodium hydroxide solution containing ammonia, wherein the concentration of sodium hydroxide is 5.0mol/L, and the concentration of ammonia is 0.5mol/L, 50% sodium hydroxide solution.
(2) cobaltous hydroxide is coated:
Ball-shape nickel hydroxide matrix puts into reactor, add pure water, use the sodium hydroxide solution adjust ph to 10.5 containing ammonia, under the agitation condition of 200 revs/min, continuous print adds cobalt sulfate solution and the sodium hydroxide solution containing ammonia, control temperature is 60 DEG C, in 4 hours reaction times, the cobalt liquor amount added in reaction accounts for 5% of nickel hydroxide matrix by coated cobaltous hydroxide amount.By the material filtering after coated, wash to pH to be 7.0, then at 60 DEG C, to dry the nickel hydroxide namely obtaining Surface coating cobaltous hydroxide.
(3) preoxidation:
The ball-shape nickel hydroxide of coated cobaltous hydroxide is added in reactor, under agitation, pass into oxygen and carry out preoxidation, control temperature is 75 DEG C, oxygen flow is material minute in 5.0L/kg reactor, in reaction process, in reactor, material color successively experiences white---yellow-white---yellow-green colour, 4 hours time.
(4) be oxidized:
In reactor, material color becomes after yellow-green colour no longer changes, and in reactor, slowly add 50% sodium hydroxide solution that temperature is 80 DEG C, add-on is 4.0% of ball-shape nickel hydroxide material total mass in reactor; Under agitation condition, continue to pass into oxygen, oxygen flow is: material minute in 5.0L/kg reactor, keeps reactor temperature 80 DEG C, reacts after 20 minutes and stops.
(5) dry:
To be oxidized products therefrom pure water to neutral, dry at 110 DEG C, 200 orders sieve, and namely obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
In reaction process, the phenomenon that in reactor, material does not have the occurrence of wetness to lump, when product sieves, screen overflow is little.
After testing, the powder impedance of the above-mentioned nickel hydroxide active material prepared is 3.0 Ω cm, BET is 9.75m
2/ g, the cobalt average valence being gone out Surface coating cobalt by iodometric determination is 3.35.
Embodiment 2:
Oxidation products embodiment 1 obtained does doping further, and step is:
Gained material after oxidizing reaction is joined in the lithium hydroxide solution of 10g/L, nickel hydroxide active material solids concn is in the solution made to be 200g/L, maintain temperature of reaction system 60 DEG C under agitation, reaction times is 30min, again the material processed is carried out filtering, washing to neutral with pure water, then at 110 DEG C, dry the nickel hydroxide of the coated gamma hydroxy cobalt oxide namely obtaining elements doped lithium.
The product powder impedance that embodiment 2 obtains is 1.5 Ω cm, BET is 9.79m
2/ g, the cobalt average valence being gone out Surface coating cobalt by iodometric determination is 3.35; The content of the Li in nickel hydroxide active material is 0.30%.
Claims (5)
1. prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide for one kind, first with the water-soluble salt of ball-shape nickel hydroxide, cobalt, alkali metal hydroxide, ammoniacal liquor and water for raw material, prepare the ball-shape nickel hydroxide of Surface coating cobaltous hydroxide, it is characterized in that: afterwards, the ball-shape nickel hydroxide of the Surface coating cobaltous hydroxide obtained is joined in reactor, under agitation, oxygenant is added in reactor, in preoxidation to reactor, material color stops change, and it is 40 ~ 150 DEG C that reactor temperature controls; In reactor, add alkali hydroxide soln more afterwards, under agitation condition, then add oxygenant, after continued oxidation reaction certain hour, then will the product pure water obtained be oxidized---dry, obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
2. prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide as claimed in claim 1, it is characterized in that: described preoxidation and continued oxidation two benches adopt identical oxygenant.
3. prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide as claimed in claim 2, it is characterized in that: the preferred oxygen of described oxygenant.
4. prepare the method for the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide as claimed in claim 3, it is characterized in that: the standard that the flow of described oxygen passes into 0.1 ~ 10L/ minute by material in every kilogram of reactor passes into.
5. the method preparing the ball-shape nickel hydroxide of coated gamma hydroxy cobalt oxide as described in one of Claims 1 to 4, it is characterized in that: after described continued oxidation certain hour, the lithium hydroxide solution that concentration is 5 ~ 20g/L is added in products therefrom, under agitation, control temperature 30 ~ 100 DEG C, reaction times is 0.5 ~ 2.0 hour, then the product pure water that will be obtained by reacting---dry.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN107452955B (en) * | 2016-06-01 | 2020-05-19 | 中国科学院大连化学物理研究所 | Hexagonal-prism-shaped cobalt oxyhydroxide material with hollow structure and preparation method thereof |
| JP7057271B2 (en) * | 2018-05-21 | 2022-04-19 | トヨタ自動車株式会社 | Method for manufacturing positive electrode active material, positive electrode, alkaline storage battery and positive electrode active material |
| WO2019225461A1 (en) * | 2018-05-21 | 2019-11-28 | トヨタ自動車株式会社 | Positive electrode active material, positive electrode, alkaline battery, and method for producing positive electrode active material |
| JP6806943B1 (en) * | 2020-06-18 | 2021-01-06 | 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 | Making method of nickel hydroxide with coated 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 |
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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 | Making method of nickel hydroxide with coated 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 |
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