CN101955234B - Method for preparing high purity nano cobalt hydroxide - Google Patents
Method for preparing high purity nano cobalt hydroxide Download PDFInfo
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- CN101955234B CN101955234B CN2009101646068A CN200910164606A CN101955234B CN 101955234 B CN101955234 B CN 101955234B CN 2009101646068 A CN2009101646068 A CN 2009101646068A CN 200910164606 A CN200910164606 A CN 200910164606A CN 101955234 B CN101955234 B CN 101955234B
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Abstract
The invention discloses a method for preparing high purity nano cobalt hydroxide, belonging to the technical field of battery energy material preparation. Homogeneous phase precipitation method is adopted to synthesize cobalt hydroxide, including that: cobaltous sulphate aqueous solution, sodium hydroxide aqueous solution, cobalt ion chelating agent aqueous solution and aqueous solution of reagent A which are in certain concentration are respectively, sequentially and continuously added into a reactor to be stirred according to flow ratio of 1: 0.68-0.74: 0.048-0.054: 0.058-0.064, reaction is taken place, appropriate amount of additive aqueous solution is added, and ageing, solid-liquid separation, washing and drying are carried out, thus obtaining the high purity nano cobalt hydroxide product. The product not only has high purity, regular shape, small grain size and uniform distribution, but also has high specific area, higher bulk density and good liquidity, dispersity and workability, thus being beneficial to separate processing or uniformly coating cobalt hydroxide on the surface of nickel hydroxide particle by adopting chemical plating, so that combination property of nickel-hydrogen battery is improved.
Description
Technical field
The invention belongs to the battery material preparing technical field, especially relate to a kind of preparation method of high-purity Nano-class cobaltous hydroxide.
Background technology
Along with the continuous development of China's economy, science and technology, to the also increase thereupon of use of the energy, especially industrial develops rapidly, and bigger to the consumption of battery power, the hazardous substance of generation causes the destruction of ecotope easily.Therefore, country proposes higher requirement to the use of the energy, not only requires to improve the service efficiency of the energy but also will reach energy-saving and emission-reduction, strengthens the natural ecological environment protection.Thus, improve the battery power device structure, particularly the preparation of high purity battery energy and material is very important.
The nickel-hydrogen cell that in daily industry, uses, nickel-cadmium cell positive electrode material are generally the ball-type nickel hydroxide, and it is the bad P-type semiconductor of a kind of electroconductibility.Existing bigger contact resistance between anodal nickel hydroxide particle and the particle and between particle and the nickel foam substrate.Because the transmission of electronics is affected Ni in process of charging
2+Fully oxidation; Ni in the discharge process
3+Can not fully reduce, active substance can not be made full use of, thereby be difficult to improve the quality of nickel hydroxide.Usually adopt the mode of co-precipitation to add additive such as cobalt and improve crystals proton (hydrogen ion) transmission situation; Improve loading capacity, voltage platform and cycle life, but still can not solve the conductivity problems that reaches between nickel hydroxide particle and the particle between particle and the nickel foam substrate.Thus, requisite needs directly add a kind of cobaltous hydroxide to solve between nickel hydroxide particle and the particle and the conductivity problems between particle and the nickel foam substrate.It is reported that this kind cobaltous hydroxide requires not only outside purity height, regular particles, the even particle size distribution, and specific surface area is big, has excellent flowability, dispersiveness and processability.
At present; Synthetic cobaltous hydroxide mainly closes the precipitin reaction method through ammino, promptly prepares certain density cobalt saline solution and adds certain amount of ammonia water, adds sodium hydroxide toward it again; Process control reaction end pH value can obtain the cobaltous hydroxide product through washing, oven dry then.The shortcoming that this method exists: the one, cobalt salt there is not clear and definite selection, the cobaltous hydroxide quality of different cobalt salt outputs is totally different, to the removal of soluble sodium salt, causes the product foreign matter content fluctuated when especially washing, and is extremely unstable; The 2nd, adopt step precipitator method and do not add any additives; Except can not effectively controlling crystalline particle diameter, pattern; Outside particle is random; Deterioration by oxidation very easily takes place in product in manufacturing procedures such as oven dry, fragmentation, screening, cause that product purity is impure, material phase analysis has dephasign to exist, and is difficult to satisfy the practical application of this material at battery industry.
In sum, preparation high-purity Nano-class cobaltous hydroxide is significant in the practicability of battery industry to cobaltous hydroxide.
Summary of the invention
In order to solve the deficiency that above technology exists; The present invention provides a kind of preparation method of high-purity Nano-class cobaltous hydroxide; Adopt cobaltous hydroxide product that this method prepares gained not only purity height, regular particles, specific surface area is big, size distribution is even, have bigger tap density; But also have excellent flowability, dispersiveness and processability, effectively solve the conductivity problems that reaches between nickel hydroxide particle and the particle between particle and the nickel foam substrate.
The present invention provides a kind of preparation method of high-purity Nano-class cobaltous hydroxide, adopts the synthetic cobaltous hydroxide of homogeneous precipitation method, it is characterized in that comprising following concrete process step:
1, a kind of preparation method of high-purity Nano-class cobaltous hydroxide adopts the synthetic cobaltous hydroxide of homogeneous precipitation method, it is characterized in that comprising following concrete process step:
(1) obtain solution
A, compound concentration are the cobalt sulfate solution of 0.2～2.5mol/l;
B, compound concentration are the aqueous sodium hydroxide solution of 3.0～12.0mol/l;
C, compound concentration are the cobalt ion complexing agent aqueous solution of 5.0～13.0mol/l;
D, compound concentration are the reagent A aqueous solution of 2.0～15.0mol/l, and reagent A is SEPIGEL 305, hydrazine hydrate or Peng Qinghuana;
E, an amount of additive aqueous solution of preparation, additive is pentanoic, xitix or double thioether;
(2) building-up reactions
With the cobalt sulfate solution that has prepared, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, the reagent A aqueous solution; Be 1: 0.68～0.74: 0.048～0.054: 0.058～0.064 to be input to continuously in the reactor drum that band stirs by its throughput ratio respectively; Take place to obtain the cobaltous hydroxide suspension liquid behind the chemical reaction, control reaction temperature is 20～60 ℃;
(3) ageing
Through reactor drum bottom valve input ageing tank, in cobaltous hydroxide suspension liquid weight ratio is 1: 80～120 ratio add ageing tank and stir ageing 2～6 hour with the additive aqueous solution simultaneously with the cobaltous hydroxide suspension liquid of gained, can obtain cobaltous hydroxide ageing liquid;
(4) solid-liquid separation, washing
Change gained cobaltous hydroxide ageing liquid over to solid-liquid separator and carry out solid-liquid separation, cobaltous hydroxide to the pH value of washing the solid-liquid separation gained with pure water is not more than till 7;
(5) oven dry finished product
The cobaltous hydroxide of solid-liquid separation, washing back gained is placed in the loft drier in 50～95 ℃ of oven dry 40～80 hours, can obtains the extremely low peach high-purity Nano-class cobaltous hydroxide product of oxidisability.
Described cobalt ion complexing agent is ammoniacal liquor, ammonium chloride or ammonium sulfate; The cobaltous hydroxide product average specific surface area that this method prepares gained is 18～30m
2/ g, median size is 230～300nm.
The invention has the beneficial effects as follows: cobaltous hydroxide product purity height of this method preparation, regular particles, size distribution evenly and also specific surface area greatly, have bigger tap density, also have excellent flowability, dispersiveness and processability.
Specific embodiment
Embodiment one
Obtain solution in advance: concentration is the cobalt sulfate solution of 0.2mol/l; Concentration is the 3.0mol/l aqueous sodium hydroxide solution; Concentration is the cobalt ion complexing agent aqueous solution of 5.0mol/l, and it is the polyacrylamide solution of 2.0mol/l that the reagent A aqueous solution is selected concentration for use, an amount of additive aqueous solution.Then with the cobalt sulfate solution for preparing, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, polyacrylamide solution, be 1: 0.68: 0.048 by its throughput ratio successively respectively: 0.058 is input in the reactor drum that has stirring continuously, and control reaction temperature is 20 ℃.Wherein, cobalt sulfate solution and aqueous sodium hydroxide solution can obtain the cobaltous hydroxide suspension liquid after reacting fully, and its reaction formula is CoSO
4+ 2NaOH=Co (OH)
2↓+Na
2SO
4Said cobalt ion complexing agent aqueous solution is an aqueous ammonium chloride solution; Can control speed and formation cobaltous hydroxide granule-morphology that cobalt sulfate solution and aqueous sodium hydroxide solution react effectively, said polyacrylamide solution plays effectively preliminary coating and forms the effect of cobaltous hydroxide particulate in reaction process.The cobaltous hydroxide suspension liquid of reaction being accomplished the back gained is through reactor drum bottom valve input ageing tank, is 1: 80 ratio adding ageing tank with the additive aqueous solution in cobaltous hydroxide suspension liquid weight ratio simultaneously and stirs ageing 2 hours, can obtain cobaltous hydroxide ageing liquid.The said additive aqueous solution is the pentanoic aqueous solution, plays coating cobaltous hydroxide particle antioxygenation once more.Change the cobaltous hydroxide ageing liquid of gained over to solid-liquid separator then and carry out solid-liquid separation, be not more than till 7 with cobaltous hydroxide to the pH value of pure water washing solid-liquid separation gained.The cobaltous hydroxide of washing back gained is placed in the loft drier in 50 ℃ of oven dry 80 hours, can obtain high-purity Nano-class cobaltous hydroxide product.
Embodiment two
Obtain solution in advance: concentration is the cobalt sulfate solution of 1.0mol/l; Concentration is the aqueous sodium hydroxide solution of 5.0mol/l; Concentration is the cobalt ion complexing agent aqueous solution of 7.5mol/l, and it is the hydrazine hydrate aqueous solution of 6.5mol/l that the reagent A aqueous solution is selected concentration for use, an amount of additive aqueous solution.With the cobalt sulfate solution for preparing, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, the hydrazine hydrate aqueous solution is 1: 0.70: 0.050 by its throughput ratio respectively successively: 0.060 is input in the reactor drum that has stirring continuously, and control reaction temperature is 35 ℃.Wherein, cobalt sulfate solution and aqueous sodium hydroxide solution can obtain the cobaltous hydroxide suspension liquid after reacting fully, and its reaction formula is CoSO
4+ 2NaOH=Co (OH)
2↓+Na
2SO
4Described cobalt ion complexing agent aqueous solution is an ammonia aqueous solution, can control speed and formation cobaltous hydroxide granule-morphology that cobalt sulfate solution and aqueous sodium hydroxide solution react effectively; The described hydrazine hydrate aqueous solution plays effectively preliminary coating cobaltous hydroxide particulate effect in reaction process.The cobaltous hydroxide suspension liquid of reaction being accomplished the back gained is through reactor drum bottom valve input ageing tank, is 1: 100 ratio adding ageing tank with the additive aqueous solution in cobaltous hydroxide suspension liquid weight ratio simultaneously and stirs ageing 3 hours, can obtain cobaltous hydroxide ageing liquid; The said additive aqueous solution is aqueous ascorbic acid, plays coating cobaltous hydroxide particle antioxygenation once more.Change the cobaltous hydroxide ageing liquid of gained over to solid-liquid separator then and carry out solid-liquid separation, be not more than till 7 with cobaltous hydroxide to the pH value of pure water washing solid-liquid separation gained.The cobaltous hydroxide of washing back gained is placed in the loft drier in 65 ℃ of oven dry 70 hours, can obtain high-purity Nano-class cobaltous hydroxide product.
Embodiment three
Obtain solution in advance: concentration is the cobalt sulfate solution of 1.5mol/l; Concentration is the aqueous sodium hydroxide solution of 8.0mol/l; Concentration is the cobalt ion complexing agent aqueous solution of 10.0mol/l, and it is the sodium borohydride aqueous solution of 11.0mol/l that the reagent A aqueous solution is selected concentration for use, an amount of additive aqueous solution.With the cobalt sulfate solution for preparing, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, sodium borohydride aqueous solution is 1: 0.72: 0.052 by its throughput ratio respectively successively: 0.062 is input to respectively in the reactor drum that has stirring continuously, and control reaction temperature is 50 ℃.Wherein, cobalt sulfate solution and aqueous sodium hydroxide solution can obtain the cobaltous hydroxide suspension liquid after reacting fully, and its reaction formula is CoSO
4+ 2NaOH=Co (OH)
2↓+Na
2SO
4Described cobalt ion complexing agent aqueous solution is an ammonium sulfate solution, can control speed and formation cobaltous hydroxide granule-morphology that cobalt sulfate solution and aqueous sodium hydroxide solution react effectively; Said sodium borohydride aqueous solution plays effectively preliminary coating cobaltous hydroxide particulate effect in reaction process.The cobaltous hydroxide suspension liquid of gained after the reaction completion is put into ageing tank through the reactor drum bottom valve; Be that 1: 110 ratio adds ageing tank and stirred ageing 5 hours with the additive aqueous solution in cobaltous hydroxide suspension liquid weight ratio simultaneously; Can obtain cobaltous hydroxide ageing liquid; The said additive aqueous solution is the double thioether aqueous solution, plays the oxidation resistant effect of coating cobaltous hydroxide particle once more.Change the cobaltous hydroxide ageing liquid of gained over to solid-liquid separator then and carry out solid-liquid separation, be not more than till 7 with cobaltous hydroxide to the pH value of pure water washing solid-liquid separation gained.The cobaltous hydroxide of washing back gained is placed in the loft drier in 80 ℃ of oven dry 55 hours, can obtain high-purity Nano-class cobaltous hydroxide product.
Embodiment four
Obtain solution in advance: concentration is the cobalt sulfate solution of 2.5mol/l; Concentration is the aqueous sodium hydroxide solution of 12.0mol/l, and concentration is the cobalt ion complexing agent aqueous solution of 13.0mol/l, and it is the polyacrylamide solution of 15.0mol/l that the reagent A aqueous solution is selected concentration for use, an amount of additive aqueous solution.With the cobalt sulfate solution for preparing, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, polyacrylamide solution is 1: 0.74: 0.054 by its throughput ratio respectively successively: 0.064 is input to respectively in the reactor drum that has stirring continuously, and control reaction temperature is 60 ℃.Wherein, cobalt sulfate solution and aqueous sodium hydroxide solution can obtain the cobaltous hydroxide suspension liquid after reacting fully, and its reaction formula is CoSO
4+ 2NaOH=Co (OH)
2↓+Na
2SO
4Described cobalt ion complexing agent aqueous solution is an aqueous ammonium chloride solution, can control speed and formation cobaltous hydroxide granule-morphology that cobalt sulfate solution and aqueous sodium hydroxide solution react effectively; Said polyacrylamide solution effectively plays the effect of preliminary coating cobaltous hydroxide in reaction process.The cobaltous hydroxide suspension liquid of gained after the reaction completion is put into ageing tank through the reactor drum bottom valve; Be that 1: 120 ratio adds ageing tank and stirred ageing 6 hours with the additive aqueous solution in cobaltous hydroxide suspension liquid weight ratio simultaneously; Can obtain cobaltous hydroxide ageing liquid; The said additive aqueous solution is the pentanoic aqueous solution, plays the oxidation resistant effect of coating cobaltous hydroxide particle once more.Change the cobaltous hydroxide ageing liquid of gained over to solid-liquid separator then and carry out solid-liquid separation, be not more than till 7 with cobaltous hydroxide to the pH value of pure water washing solid-liquid separation gained.The cobaltous hydroxide of washing back gained is placed in the loft drier in 95 ℃ of oven dry 40 hours, can obtain high-purity Nano-class cobaltous hydroxide product.
Above embodiment gained cobaltous hydroxide product check and analysis result is following:
Through check and analysis instance cobaltous hydroxide product, its average specific surface area is 18～30m
2/ g, median size is 230～300nm, is evenly distributed, it is few to reunite, good dispersivity.This its preparation process obtains the high-purity Nano-class cobaltous hydroxide product of the granulometric composition of purity height, specific storage height, even particle size distribution.
Claims (2)
1. the preparation method of a high-purity Nano-class cobaltous hydroxide adopts the synthetic cobaltous hydroxide of homogeneous precipitation method, it is characterized in that comprising following concrete process step:
(1) obtain solution
A, compound concentration are the cobalt sulfate solution of 0.2～2.5mol/l;
B, compound concentration are the aqueous sodium hydroxide solution of 3.0～12.0mol/l;
C, compound concentration are the cobalt ion complexing agent aqueous solution of 5.0～13.0mol/l;
D, compound concentration are the reagent A aqueous solution of 2.0～15.0mol/l, and reagent A is SEPIGEL 305, hydrazine hydrate or Peng Qinghuana;
E, an amount of additive aqueous solution of preparation, additive is pentanoic, xitix or double thioether;
(2) building-up reactions
With the cobalt sulfate solution that has prepared, aqueous sodium hydroxide solution, cobalt ion complexing agent aqueous solution, the reagent A aqueous solution; Be 1: 0.68～0.74: 0.048～0.054: 0.058～0.064 to be input to continuously in the reactor drum that band stirs by its throughput ratio respectively; Take place to obtain the cobaltous hydroxide suspension liquid behind the chemical reaction, control reaction temperature is 20～60 ℃;
(3) ageing
Through reactor drum bottom valve input ageing tank, in cobaltous hydroxide suspension liquid weight ratio is 1: 80～120 ratio add ageing tank and stir ageing 2～6 hour with the additive aqueous solution simultaneously with the cobaltous hydroxide suspension liquid of gained, can obtain cobaltous hydroxide ageing liquid;
(4) solid-liquid separation, washing
Change gained cobaltous hydroxide ageing liquid over to solid-liquid separator and carry out solid-liquid separation, cobaltous hydroxide to the pH value of washing the solid-liquid separation gained with pure water is not more than till 7;
(5) oven dry finished product
The cobaltous hydroxide of solid-liquid separation, washing back gained is placed in the loft drier in 50～95 ℃ of oven dry 40～80 hours; Can obtain the extremely low peach high-purity Nano-class cobaltous hydroxide product of oxidisability, described cobaltous hydroxide product average specific surface area is 18～30m
2/ g, median size is 230～300nm.
2. the preparation method of a kind of high-purity Nano-class cobaltous hydroxide according to claim 1 is characterized in that described cobalt ion complexing agent is ammonium chloride, ammoniacal liquor or ammonium sulfate.
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Families Citing this family (12)
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| CN102390873A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for removing sulfate radicals in cobalt hydroxide |
| CN103342394B (en) * | 2013-07-10 | 2015-03-25 | 浙江华友钴业股份有限公司 | Method for continuously preparing cobalt hydroxide with high bulk density |
| CN104261489B (en) * | 2014-09-25 | 2016-06-01 | 安徽师范大学 | Hexagon beta cobaltous hydroxide nanometer sheet and its preparation method, ultracapacitor and electrode thereof |
| CN105152230B (en) * | 2015-09-07 | 2017-01-18 | 无锡中经金属粉末有限公司 | Process and equipment of preparing high-power-type cobalt oxide |
| CN105271443B (en) * | 2015-11-16 | 2017-02-01 | 江西省钨与稀土产品质量监督检验中心（江西省钨与稀土研究院） | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating |
| CN105463215B (en) * | 2015-11-27 | 2018-02-06 | 江苏理工学院 | The method that cobalt product is prepared by cobalt ammonia complex |
| CN108654640B (en) * | 2018-03-15 | 2021-01-01 | 安徽师范大学 | Silver-doped cobalt hydroxide material and preparation method and application thereof |
| CN110233263A (en) * | 2019-05-20 | 2019-09-13 | 湖南雅城新材料有限公司 | A kind of preparation method of doping type cobalt hydroxide |
| CN110676063A (en) * | 2019-08-19 | 2020-01-10 | 深圳职业技术学院 | High-conductivity cobalt hydroxide electrode material, preparation method thereof, electrode and capacitor |
| CN112320854A (en) * | 2020-10-26 | 2021-02-05 | 合肥融捷金属科技有限公司 | Method for improving production rate of cobaltosic oxide |
| CN114105216B (en) * | 2021-10-27 | 2024-03-29 | 厦门厦钨新能源材料股份有限公司 | Cobalt hydroxide with micro-crack structure, and preparation method and application thereof |
| CN115849459A (en) * | 2022-12-29 | 2023-03-28 | 贵州雅友新材料有限公司 | Preparation method and application of cobalt hydroxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1207576A2 (en) * | 2000-11-15 | 2002-05-22 | Matsushita Electric Industrial Co., Ltd. | Cobalt compound for use in alkaline storage battery, method for manufacturing the same, and positive electrode plate of alkaline storage battery employing the same |
| CN1359353A (en) * | 1999-06-29 | 2002-07-17 | Omg芬兰公司 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
-
2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359353A (en) * | 1999-06-29 | 2002-07-17 | Omg芬兰公司 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
| EP1207576A2 (en) * | 2000-11-15 | 2002-05-22 | Matsushita Electric Industrial Co., Ltd. | Cobalt compound for use in alkaline storage battery, method for manufacturing the same, and positive electrode plate of alkaline storage battery employing the same |
Non-Patent Citations (1)
| Title |
|---|
| 贾殿赠等.氢氧化钴纳米棒的室温固相化学合成及其表征.《无机化学学报》.2005,第21卷(第4期),第536页第1.2节. * |
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