CN102701292B - Preparation method of cobalt carbonate material with compact structure and spheroid shape - Google Patents

Preparation method of cobalt carbonate material with compact structure and spheroid shape Download PDF

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CN102701292B
CN102701292B CN201210173063.8A CN201210173063A CN102701292B CN 102701292 B CN102701292 B CN 102701292B CN 201210173063 A CN201210173063 A CN 201210173063A CN 102701292 B CN102701292 B CN 102701292B
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cobalt
carbonate material
solution
preparation
compact structure
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CN102701292A (en
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吉鸿安
朱来东
王同敏
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Northwest Research Institute of Mining and Metallurgy
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Abstract

The invention discloses a preparation method of a cobalt carbonate material with a compact structure and a spheroid shape, and aims to solve the problems of loose microstructure, disordered shape and poor uniformity of the cobalt carbonate material prepared by a conventional method. The preparation method comprises the following specific steps: placing a cobalt chloride solution with system temperature, pH value and cobalt concentration meeting the requirements into a reaction kettle, and keeping the cobalt chloride solution relatively constant; uniformly adding an ammonium bicarbonate solution into a cobalt solution system according to a certain flow, and taking a limited pH value as a reaction end point parameter of a control system; aging for a certain time, filtering, and repeatedly washing to obtain the required cobalt carbonate material. The cobalt carbonate material prepared by the method has the characteristics of spheroidal morphology, uniform particle size, compact structure and better particle size distribution, adopts standard conventional equipment, is easy to control process parameters, is simple to operate and is suitable for large-scale production.

Description

The preparation method of a kind of compact structure, globoid pattern cobaltous carbonate material
Technical field
The invention belongs to new forms of energy, field of new, relate to the preparation method who microscopic appearance and physicals is had to the cobaltous carbonate material of characteristic requirements, the cobaltous carbonate that this preparation method makes can be used for the precursor raw material of the cobalt oxide product of producing battery material, Wimet, electronic material etc.
Background technology
Flourish along with electronics, communications industry, various household electrical appliance, mobile phone, notebook computer are doubled and redoubled to the demand of lithium-ion secondary cell, and tricobalt tetroxide is also rapid progress as its production technology of important source material of lithium cell cobalt acid lithium material.Cobalt oxide (particularly tricobalt tetroxide) product appearance is grey black or black powder, a kind of important transition metal oxide, usually used as the catalyzer of producing in Wimet, battery material, the main raw material of electronic material and the tinting material of ceramic industry and chemical industry.In chemical industry, Co 3o 4it is a kind of efficient, lasting catalyzer.The production method of cobalt oxide cobaltous carbonate precursor used is more at present, routine joins carbonate solution and cobalt salt solution in reaction vessel, the cobaltous carbonate making as produce cobalt oxide when the precursor material because of its throw out particle aggregation bodily form looks invisible, loose frangible cobalt oxide that only can production common grade in a jumble, be more difficult to meet battery material etc. and produce the needs of required " the fine and close high-quality carbonic acid of globoid pattern cobalt precursor material ".
Summary of the invention
The object of this invention is to provide the preparation method of a kind of compact structure, globoid pattern cobaltous carbonate material, to solve, cobaltous carbonate material microstructure prepared by conventional production method is loose, pattern mixed and disorderly, the problem of lack of homogeneity.
Technical solution of the present invention is as follows:
A preparation method for compact structure, globoid pattern cobaltous carbonate material, is characterized in that concrete steps are as follows:
Figure 2012101730638100002DEST_PATH_IMAGE001
will be after filtration, cobalt concentration is that the cobalt chloride solution of 1～2 mol/L, pH value 4.75～5.20 is inserted in reactor;
Figure 440044DEST_PATH_IMAGE002
under agitation condition, heating steps
Figure 470317DEST_PATH_IMAGE001
solution, makes solution system temperature be controlled at 55～65 ℃, and keeps system temperature relatively stable;
Figure 2012101730638100002DEST_PATH_IMAGE003
to filter in advance and concentration is that the ammonium bicarbonate soln of 1.8～2.5 mol/L at the uniform velocity sprays to step with the flow of 250～800L/h
Figure 566449DEST_PATH_IMAGE002
system in;
Figure 278053DEST_PATH_IMAGE004
control step
Figure 205557DEST_PATH_IMAGE003
middle solution system pH value 7.0～7.5, as system reaction end, stops the interpolation of ammonium bicarbonate soln;
by step the ageing of gained solid-liquid system was filtered after 20～40 minutes, and repetitive scrubbing, obtains material requested.
The present invention adopts the conversion unit of standard normal just can produce " compact structure, globoid pattern cobaltous carbonate material ".The method is based on the most common, the most market-oriented cobalt chloride solution is as reaction system, utilize the effect of throw out particle spontaneous adsorbent solution medium ion in solution, the interfacial tension of adjustment system, simultaneously, in chemical precipitation process, nascent particulate is easy to the selective adsorption ion identical with its composition from solution, make throw out particle surface charged, produce double electrical layers at solid-liquid interface, be conducive to improve dispersion of particles, being reduced to nuclear energy builds, forming particle aggregation electricity builds, be conducive to dispersion of particles, prevent to a certain extent particle aggregation, in sedimentary process of growth, also comprise dispersion process and agglomeration in addition, in the time that two-phase mixing system reaches balance, system can change to making total surface free energy be tending towards minimum direction, result be have high surfaces free energy small-particle dissolve and macrobead is grown, make particle size distribution trend homogeneous, thereby control the pattern of particle.Agglomeration accounts for consequence in the process of growth of particle.In cobalt salt system, reunion is the major way of particle growth.In particle growth process, growth velocity reduces with the increase of particle radius, finally also can form the aggregates body that epigranular is consistent.After small-particle gathers on macroparticle, can " fusing " among macroparticle, form a larger integral particles by surface reaction, surface diffusion or volume diffusion; But also may only between particle, be in contact with one another place's local " fusing ", form a porous granule.If it is enough fast " to fuse " reaction, " fusing " time of reacting required is less than interval time of the adjacent secondary effective collision of particle, can form a larger integral particles cluster of grains by assembling, otherwise form porous granule aggregate, thereby control particle size.
The advantage that cobaltous carbonate material prepared by the inventive method has is:
Figure 927843DEST_PATH_IMAGE001
cobaltous carbonate material microscopic appearance be globoid, particle size evenly, compact structure and preferably characteristic of size-grade distribution.
Figure 239875DEST_PATH_IMAGE002
adopt standard normal equipment, processing parameter is easy to control, simple to operate, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the globoid pattern structure iron that the embodiment of the present invention 1 makes material;
Fig. 2 is the particle size distribution figure that the embodiment of the present invention 1 makes material;
Fig. 3 is the globoid pattern structure iron that the embodiment of the present invention 2 makes material;
Fig. 4 is the particle size distribution figure that the embodiment of the present invention 2 makes material;
Fig. 5 is the globoid pattern structure iron that the embodiment of the present invention 3 makes material;
Fig. 6 is the particle size distribution figure that the embodiment of the present invention 3 makes material;
Fig. 7 is the globoid pattern structure iron that the embodiment of the present invention 4 makes material;
Fig. 8 is the particle size distribution figure that the embodiment of the present invention 4 makes material.
Embodiment
The following examples can further illustrate structure and the physical index feature that present method is prepared cobaltous carbonate material, and example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Figure 225149DEST_PATH_IMAGE001
will be after filtration, the cobalt chloride solution of cobalt concentration 1.0 mol/L, pH value 4.75 is inserted in reactor;
under agitation condition, heating steps
Figure 605632DEST_PATH_IMAGE001
solution, makes solution system temperature be controlled at 55 ℃, and keeps system temperature relatively stable;
Figure 222820DEST_PATH_IMAGE003
to filter in advance and concentration is that the ammonium bicarbonate soln of 1.8 mol/L at the uniform velocity sprays to step with 800L/h flow system in;
Figure 605577DEST_PATH_IMAGE004
control step
Figure 898018DEST_PATH_IMAGE003
middle solution system pH value 7.5, as system reaction end, stops the interpolation of ammonium bicarbonate soln;
Figure 755116DEST_PATH_IMAGE005
by step
Figure 449402DEST_PATH_IMAGE004
the ageing of gained solid-liquid system was filtered after 20 minutes, and repetitive scrubbing, obtains material requested.
Embodiment 1 makes the globoid pattern structure of material and size-grade distribution as Fig. 1 and Fig. 2, and physical index " granularity and density measurement result " is as table 1.
Embodiment 2
Figure 163280DEST_PATH_IMAGE001
will be after filtration, the cobalt chloride solution of cobalt concentration 1.5 mol/L, pH value 4.80 is inserted in reactor;
Figure 208597DEST_PATH_IMAGE002
under agitation condition, heating steps
Figure 603806DEST_PATH_IMAGE001
solution, makes solution system temperature be controlled at 63 ℃, and keeps system temperature relatively stable;
Figure 214916DEST_PATH_IMAGE003
to filter in advance and concentration is that the ammonium bicarbonate soln of 2.0 mol/L at the uniform velocity sprays to step with 588L/h flow
Figure 302957DEST_PATH_IMAGE002
system in;
Figure 569991DEST_PATH_IMAGE004
control step
Figure 768891DEST_PATH_IMAGE003
middle solution system pH value 7.2, as system reaction end, stops the interpolation of ammonium bicarbonate soln;
by step
Figure 991985DEST_PATH_IMAGE004
the ageing of gained solid-liquid system was filtered after 30 minutes, and repetitive scrubbing, obtains material requested.
Embodiment 2 makes the globoid pattern structure of material and size-grade distribution as Fig. 3 and Fig. 4, and physical index " granularity and density measurement result " is as table 1.
Embodiment 3
Figure 746315DEST_PATH_IMAGE001
will be after filtration, the cobalt chloride solution of cobalt concentration 1.6 mol/L, pH value 5.09 is inserted in reactor;
under agitation condition, heating steps
Figure 69029DEST_PATH_IMAGE001
solution, makes solution system temperature be controlled at 60 ℃, and keeps system temperature relatively stable;
Figure 498873DEST_PATH_IMAGE003
to filter in advance and concentration is that the ammonium bicarbonate soln of 1.86 mol/L at the uniform velocity sprays to step with 280L/h flow
Figure 474919DEST_PATH_IMAGE002
system in;
Figure 15622DEST_PATH_IMAGE004
control step
Figure 659093DEST_PATH_IMAGE003
middle solution system pH value 7.2, as system reaction end, stops the interpolation of ammonium bicarbonate soln;
Figure 56576DEST_PATH_IMAGE005
by step the ageing of gained solid-liquid system was filtered after 30 minutes, and repetitive scrubbing, obtains material requested.
Embodiment 3 makes the globoid pattern structure of material and size-grade distribution as Fig. 5 and Fig. 6, and physical index " granularity and density measurement result " is as table 1.
Embodiment 4
Figure 864312DEST_PATH_IMAGE001
will be after filtration, the cobalt chloride solution of cobalt concentration 2.0 mol/L, pH value 5.20 is inserted in reactor;
Figure 362290DEST_PATH_IMAGE002
under agitation condition, heating steps
Figure 930674DEST_PATH_IMAGE001
solution, makes solution system temperature be controlled at 65 ℃, and keeps system temperature relatively stable;
to filter in advance and concentration is that the ammonium bicarbonate soln of 2.5 mol/L at the uniform velocity sprays to step with 250L/h flow
Figure 29397DEST_PATH_IMAGE002
system in;
Figure 381881DEST_PATH_IMAGE004
control step
Figure 888211DEST_PATH_IMAGE003
middle solution system pH value 7.0, as system reaction end, stops the interpolation of ammonium bicarbonate soln;
Figure 326146DEST_PATH_IMAGE005
by step the ageing of gained solid-liquid system was filtered after 40 minutes, and repetitive scrubbing, obtains material requested.
Embodiment 4 makes the globoid pattern structure of material and size-grade distribution as Fig. 7 and Fig. 8, and physical index " granularity and density measurement result " is as table 1.
The cobaltous carbonate granularity that table 1 embodiment makes and density measurement result
Figure 2012101730638100002DEST_PATH_IMAGE007

Claims (1)

1. a preparation method for compact structure, globoid pattern cobaltous carbonate material, is characterized in that concrete steps are as follows:
(1) will be after filtration, cobalt concentration is that the cobalt chloride solution of 1～2 mol/L, pH value 4.75～5.20 is inserted in reactor;
(2), under agitation condition, the solution in heating steps (1), makes solution system temperature be controlled at 55～65 ℃, and keeps system temperature relatively stable;
(3) will filter in advance and concentration is that the ammonium bicarbonate soln of 1.8～2.5 mol/L at the uniform velocity sprays to the system of step (2) with the flow of 250～800L/h;
(4) control solution system pH value 7.0～7.5 in step (3) and, as system reaction end, stop the interpolation of ammonium bicarbonate soln;
(5) ageing of step (4) gained solid-liquid system was filtered after 20～40 minutes, repetitive scrubbing, obtains material requested.
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CN102910686A (en) * 2011-08-04 2013-02-06 深圳市格林美高新技术股份有限公司 Cobalt carbonate preparation method and superfine cobalt powder preparation method
CN103351030A (en) * 2013-06-29 2013-10-16 西北矿冶研究院 Preparation method of low-anion residual basic cobalt carbonate
CN104944475B (en) * 2015-07-16 2017-03-08 南京寒锐钴业股份有限公司 A kind of preparation method of super coarse granule high-purity cobalt carbonate
CN106711449B (en) * 2017-01-06 2019-12-31 苏州宇量电池有限公司 Synthesis method of nano linear cobalt carbonate negative electrode material
CN114249355B (en) * 2021-12-20 2023-09-22 厦门厦钨新能源材料股份有限公司 Layered cobaltosic oxide material and preparation method and application thereof
CN115710022A (en) * 2022-11-17 2023-02-24 科立鑫(珠海)新能源有限公司 Preparation method of high-density cobalt carbonate

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