CN109319846A - The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide - Google Patents
The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide Download PDFInfo
- Publication number
- CN109319846A CN109319846A CN201811484455.XA CN201811484455A CN109319846A CN 109319846 A CN109319846 A CN 109319846A CN 201811484455 A CN201811484455 A CN 201811484455A CN 109319846 A CN109319846 A CN 109319846A
- Authority
- CN
- China
- Prior art keywords
- cobaltosic oxide
- preparation
- reaction vessel
- cobalt
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of cobalt carbonate and the preparation methods of cobaltosic oxide.The preparation method of the cobaltosic oxide includes the following steps: to prepare ammonium bicarbonate soln；It is configured to cobalt chloride solution；The deionized water of predetermined amount, heating deionized water to predetermined temperature are added in the reaction vessel；Part ammonium bicarbonate soln is added to reaction vessel, and adjust the pH value of solution in reaction vessel to pH be 7.1-7.6；Cobalt chloride solution and remaining ammonium bicarbonate soln are added in reaction vessel, are stirred to react, cobalt carbonate is generated；By in reaction vessel solution and cobalt carbonate be filtered, obtain cobalt carbonate；Wash cobalt carbonate；Cobalt carbonate is calcined, cobaltosic oxide powder is obtained.The preparation method of the cobaltosic oxide is low to the prices of raw materials, be easily achieved, degree of controllability is relatively high and the cobaltosic oxide particle size and pattern prepared are uniform.
Description
Technical field
The present invention relates to a kind of preparation method of cobalt carbonate and the preparation methods of cobaltosic oxide.
Background technique
Cobaltosic oxide is commonly applied to electrochemical field, is mainly used as the presoma-of production anode material for lithium-ion batteries
Cobalt acid lithium, it is also possible in the fields such as corrosion-resistant, high temperature resistant and magnetic material, in addition, in hard alloy, catalyst, pigment addition
It agent and prepares other materials etc. and is also widely used.The preparation of traditional cobaltosic oxide powder mainly uses cobalt oxalate
Thermal decomposition process, in recent years, oxalic acid rise in price are very fast, and the preparation cost of cobaltosic oxide is caused to be substantially increased, and tradition
Technique production cobaltosic oxide pattern be it is needle-shaped, cause the application range of cobaltosic oxide small.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method for the cobalt carbonate that prices of raw materials are low, degree of controllability is relatively high, also mention
It is low for a kind of prices of raw materials, degree of controllability is relatively high and the cobaltosic oxide particle size and cobaltosic oxide of uniform morphology prepared
Preparation method.
A kind of preparation method of cobalt carbonate, includes the following steps:
Prepare ammonium bicarbonate soln and cobalt chloride solution；
The deionized water of predetermined amount is added in the reaction vessel, heats the deionized water to predetermined temperature；
It is added in the ammonium bicarbonate soln to the reaction vessel of part, and adjusts solution in the reaction vessel
PH value to pH be 7.1-7.6；
It is added in the cobalt chloride solution and the remaining ammonium bicarbonate soln to the reaction vessel, is stirred to react,
Reaction generates cobalt carbonate.
A kind of preparation method of cobaltosic oxide, includes the following steps:
Prepare ammonium bicarbonate soln and cobalt chloride solution；
The deionized water of predetermined amount is added in the reaction vessel, heats the deionized water to predetermined temperature；
It is added in the ammonium bicarbonate soln to the reaction vessel of part, and adjusts solution in the reaction vessel
PH value to pH be 7.1-7.6；
It is added in the cobalt chloride solution and the remaining ammonium bicarbonate soln to the reaction vessel, is stirred to react,
Reaction generates cobalt carbonate；
The cobalt carbonate generated is collected, and carries out calcination processing, obtains the cobaltosic oxide.
The concentration of the ammonium bicarbonate soln is 230g/L-250g/L in one of the embodiments, and the cobalt chloride is molten
The concentration of liquid is 100g/L-120g/L.
The ammonium bicarbonate soln and the cobalt chloride solution are added by head tank respectively in one of the embodiments,
In to the reaction vessel.
In one of the embodiments, the ammonium bicarbonate soln in the head tank with it is described in the head tank
Cobalt chloride solution is added to the reaction vessel by way of cocurrent adding material.
Stirring rate when being stirred to react in one of the embodiments, is 80r/min-120r/min.
It in one of the embodiments, further include following steps: the carbonic acid cobalt button that interval predetermined time detection generates
The size of degree.
The calcination temperature for carrying out calcination processing to the cobalt carbonate in one of the embodiments, is 690 DEG C -780 DEG C.
The time calcined in one of the embodiments, is 2h-4h.
In one of the embodiments, the heating deionized water be to predetermined temperature will be in the reaction vessel
The deionized water is heated to 50 DEG C -60 DEG C.
The temperature of the deionized water in the reaction vessel is heated in one of the embodiments, to 54 DEG C.
Cobaltosic oxide made from the preparation method of above-mentioned cobaltosic oxide is pure cubic phase spinel structure, four oxidations three
Cobalt crystal grain is larger, and crystal structure is more complete, and tap density is high, and granularity is uniformly and consistent with pattern.Above-mentioned cobaltosic oxide
Preparation method has process route technology starting point low, and raw material cost is low, it is easy to accomplish and grasp, degree of controllability is relatively high etc. excellent
Point.
Detailed description of the invention
Fig. 1 is the XRD spectrum of cobaltosic oxide made from an embodiment, and wherein abscissa is the time to pass consumption, and ordinate is
Intensity value；
Fig. 2-Fig. 5 is granule-morphology figure of the cobaltosic oxide made from an embodiment in different amplification electron-microscope scanning；
Fig. 6 is the XRD spectrum of cobaltosic oxide made from another embodiment, and wherein abscissa is the time to pass consumption, ordinate
For intensity value；
Fig. 7-Figure 10 is granule-morphology of the cobaltosic oxide made from another embodiment in different amplification electron-microscope scanning
Figure.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.The present invention
It can realize in many different forms, however it is not limited to embodiment described herein.On the contrary, providing these embodiments
Purpose is to make the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The present invention provides a kind of preparation methods of cobaltosic oxide.
Experiment reagent needed for the present embodiment: ammonium hydrogen carbonate (NH is taken4HCO3) and cobalt chloride hexahydrate (CoCl2·6
(H2O)).Wherein, ammonium hydrogen carbonate, the production of the chemical inc Zhi Jiang, cobalt chloride hexahydrate, the limited public affairs of Guangxi hundred million shares of silver
Department's production.
Laboratory apparatus needed for the present embodiment includes: beaker, glass bar, thermostat water bath, reaction vessel, blender, temperature
Meter, thunder magnetic pH meter, Muffle furnace, (SHB-3) recirculated water multiplex vavuum pump (Suzhou Qi Le Electronic Science and Technology Co., Ltd.) and
Malvern2000 laser particle analyzer (Marl, Germany text Instrument Ltd.).
The preparation method of cobaltosic oxide includes the following steps:
Take ammonium hydrogen carbonate (NH4HCO3), it is dissolved with pure water, it is molten to be configured to the ammonium hydrogen carbonate that concentration is 230g/L-250g/L
Liquid is added to head tank, spare.
Take cobalt chloride hexahydrate (CoCl2·6(H2O)), dissolved with pure water, be configured to the chlorine that concentration is 100g/L-120g/L
Change cobalt liquor, is added to another head tank, it is spare.
The deionized water of predetermined amount is added in the reaction vessel, heating deionized water is to 50 DEG C -60 DEG C, and temperature is by thermometer
Measurement.
The valve of head tank is opened, is added in the ammonium bicarbonate soln to reaction vessel of part, and adjust in reaction vessel
The pH value of solution is 7.1-7.6 to pH, and the pH value of solution is measured by thunder magnetic pH meter.
The cobalt chloride solution in remaining ammonium bicarbonate soln and head tank in head tank is by way of cocurrent adding material
It is added to reaction vessel, is stirred by blender, reaction generates cobalt carbonate, when ammonium bicarbonate soln is reacted with cobalt chloride solution
Reaction equation are as follows: NH4HCO3+CoCl2=CoCO3+NH4Cl+HCl.Cobalt carbonate is a kind of compound of indissoluble, and solubility product is very
It is small, it is easy to reach degree of supersaturation.It mainly includes two stages, the nucleation process and nucleus of particle that cobalt carbonate, which precipitates forming process,
Growth course.In the presence of having NH4+ complexing agent, Co in reaction system2+With NH4 +It is initially formed cobalt ammonium complex ion, cobalt
Ammonium complex ion then again with CO3 2-Reaction generates cobalt carbonate.
Stirring is realized by blender, and the stirring rate of blender is 80r/min-120r/min, makes cobalt carbonate
Grain is slowly equably grown up around nucleus.
Between at regular intervals by Malvern laser particle analyzer detection generate cobalt carbonate granularity size, to guarantee carbon
The granularity of sour cobalt is within control range.Meanwhile being increased with the pattern and granularity of optical microscopy observation cobalt carbonate crystalline particle
Variation, be monitored.
After qualified cobalt carbonate slurry is aged, by (SHB-3) recirculated water multiplex vavuum pump to reaction vessel
Interior solution and cobalt carbonate is filtered, and obtains cobalt carbonate.
Cobalt carbonate is washed by circulation vacuum pump.
Carbonic acid is calcined by Muffle furnace, obtains the cobaltosic oxide powder of black or grey black, the time of calcining is
2h-3h。
The equation that calcination reaction generates cobaltosic oxide is as follows: 6CoCO3+O2=2Co3O4+6CO2。
Cobaltosic oxide made from the preparation method of above-mentioned cobaltosic oxide is pure cubic phase spinel structure, four oxidations three
Cobalt crystal grain is larger, and crystal structure is more complete, and tap density is high, and granularity is uniformly and consistent with pattern.Above-mentioned cobaltosic oxide
Preparation method has process route technology starting point low, it is easy to accomplish and grasp, the advantages that degree of controllability is relatively high.
The present invention is using ammonium hydrogen carbonate as precipitating reagent, and pH value is more stable during the reaction, and ammonium hydrogen carbonate can
Buffer system is formed in the solution, ammonium hydrogen carbonate is easy to get, and it is cheap, it is pollution-free.Using ammonium hydrogen carbonate as precipitating reagent, it is made
Cobaltosic oxide have fine grain spherical shape surface topography, granularity is more uniform, high surface activity.
Embodiment 1
The present embodiment relates to a kind of preparation method of cobaltosic oxide comprising following steps:
Take NH4HCO3, dissolved with pure water, be configured to the ammonium bicarbonate soln that concentration is 240 ± 4g/L, be added to head tank
It is interior, it is spare.
Take CoCl2·6(H2O), dissolved with pure water, be configured to the cobalt chloride solution that concentration is 110 ± 3g/L, be added to another
It is spare in one head tank.
The deionized water of predetermined amount is added in the reaction vessel, heating deionized water is to 54 DEG C.
The valve for opening head tank, part ammonium bicarbonate soln is added to reaction vessel, and is adjusted in reaction vessel
Solution pH value to pH be 7.2 ± 0.05.
The cobalt chloride solution in ammonium bicarbonate soln and head tank in head tank be added by way of cocurrent adding material to
It in reaction vessel, is stirred to react by blender, the stirring rate of blender is 100r/min, reaction time 10h, generates carbonic acid
Cobalt makes cobalt carbonate particle slowly equably grow up around nucleus.Stirring has a major impact the crystallization process of cobalt carbonate, stirs
The reaction process of whole system can be made uniformly to carry out, to have prevented cobalt concentration local excessively high and generates a large amount of nucleus, so as to
To guarantee crystal growth process while progress.Reinforcement stirring appropriate is conducive to growing up for nucleus.In addition, reasonable stirring side
Formula can produce the formation that certain flow direction is conducive to spherical crystal.
Between at regular intervals by Malvern laser particle analyzer detection generate cobalt carbonate granularity size, to guarantee carbon
The granularity of sour cobalt is within control range.Meanwhile being increased with the pattern and granularity of optical microscopy observation cobalt carbonate crystalline particle
Variation, be monitored.
After qualified cobalt carbonate slurry is aged, by (SHB-3) recirculated water multiplex vavuum pump to reaction vessel
Interior solution and cobalt carbonate is filtered, and obtains cobalt carbonate.
Cobalt carbonate is washed by (SHB-3) recirculated water multiplex vavuum pump.
Carbonic acid is calcined by Muffle furnace, 720 DEG C ± 30 DEG C of calcination temperature, calcination time 2h obtains black or ash
The cobaltosic oxide powder of black.
Cobaltosic oxide obtained by the present embodiment is detected and analyzed, Malvern ParticleSizer is passed through
The D of cobaltosic oxide obtained is learnt in (Malvern2000 laser particle analyzer, Marl, Germany text Instrument Ltd.) detection50For
7.341 μm, crystal phase analysis is carried out by X- powder x ray diffractometer x.Spectral line shown in Figure 1, in the reference axis with number
The standard spectral line of cobaltosic oxide is represented, and each diffraction maximum in figure and the standard spectral line goodness of fit are high, without other impurity peaks,
Show that cobaltosic oxide obtained is pure cubic phase spinel structure；And each diffraction maximum is more sharp, shows in calcining and decomposing
When the cobaltosic oxide crystal grain that is formed it is larger, crystal structure is more complete.
Pattern and the energy spectrum analysis that observation particle is carried out by Zeiss SIGMA HD field emission scanning electron microscope, referring to
Shown in Fig. 2-Fig. 5, wherein Fig. 2, Fig. 3, Fig. 4, Fig. 5 are respectively institute under different amplification (multiple is sequentially increased) electron-microscope scanning
The granule-morphology for the cobaltosic oxide observed, as can be seen from Figure 2 the preparation method of cobaltosic oxide of the present invention is prepared
Cobaltosic oxide be spherical particle, sphericity is poor, and partial size difference is larger between variable grain, can be with from Fig. 3-Fig. 5
The particle surface that will become apparent from cobaltosic oxide is not round and smooth, and particle surface has many concave surfaces, indicates the crystal of cobaltosic oxide
Compactness extent is relatively poor.
Find that its cobalt content is lower than anticipation content by energy spectrum analysis, the energy spectrum analysis constituent content table of cobaltosic oxide
It see the table below shown in 1.
Table 1
| Element | Weight percent | Atomic percent |
| C | 9.86 | 18.17 |
| O | 47.61 | 65.86 |
| Co | 42.52 | 15.97 |
Embodiment 2
The present embodiment relates to a kind of preparation method of cobaltosic oxide comprising following steps:
Take NH4HCO3, dissolved with pure water, be configured to the ammonium bicarbonate soln that concentration is 240 ± 4g/L, be added to head tank
It is interior, it is spare.
Take CoCl2·6(H2O), dissolved with pure water, be configured to the cobalt chloride solution that concentration is 110 ± 3g/L, be added to another
It is spare in one head tank.
The deionized water of predetermined amount is added in the reaction vessel, heating deionized water is to 57 DEG C.
The valve for opening head tank, part ammonium bicarbonate soln is added to reaction vessel, and is adjusted in reaction vessel
Solution pH value to pH be 7.5 ± 0.05.
The cobalt chloride solution in ammonium bicarbonate soln and head tank in head tank be added by way of cocurrent adding material to
It in reaction vessel, is stirred to react by blender, the stirring rate of blender is 85r/min, reaction time 48h, generates carbonic acid
Cobalt makes cobalt carbonate particle slowly equably grow up around nucleus.
Between at regular intervals by Malvern laser particle analyzer detection generate cobalt carbonate granularity size, to guarantee carbon
The granularity of sour cobalt is within control range.Meanwhile being increased with the pattern and granularity of optical microscopy observation cobalt carbonate crystalline particle
Variation, be monitored.
After qualified cobalt carbonate slurry is aged, by (SHB-3) recirculated water multiplex vavuum pump to reaction vessel
Interior solution and cobalt carbonate is filtered, and obtains cobalt carbonate.
Cobalt carbonate is washed by (SHB-3) recirculated water multiplex vavuum pump.
Carbonic acid is calcined by Muffle furnace, 750 DEG C ± 30 DEG C of calcination temperature, calcination time 4h obtains black or ash
The cobaltosic oxide powder of black.
Cobaltosic oxide made from the present embodiment 2 is detected and analyzed, Malvern ParticleSizer is passed through
The D of cobaltosic oxide obtained is learnt in (Malvern2000 laser particle analyzer, Marl, Germany text Instrument Ltd.) detection50For
17.108 μm, crystal phase analysis is carried out by X- powder x ray diffractometer x.XRD diagram shown in Figure 6 can be seen that is penetrated by X
The map diffraction maximum and standard spectral line that line diffractometer tests and analyzes are almost the same.And other impurity peaks are free of, show made
The product obtained is the cobaltosic oxide of pure cubic phase spinel structure；And each diffraction maximum is more sharp, shows that particle is larger, crystal grain
Structure is more complete.
Comparative example 1 and embodiment 2 are it is found that four oxidation obtained under embodiment 1 and 2 two kinds of process conditions of embodiment
The XRD diagram of three cobalts finds out that each diffraction maximum of the product of two batches has no significant difference, this is indicated that changes under preparation method of the same race
Become structure and purity that its process conditions has no effect on its crystal grain.
Pattern and the energy spectrum analysis of observation particle are carried out by Zeiss SIGMA HD field emission scanning electron microscope.Implement
The SEM of cobaltosic oxide obtained schemes as shown in Fig. 7-Figure 10 under the process conditions of example 2, and Fig. 7, Fig. 8, Fig. 9, Figure 10 are respectively not
The granule-morphology of cobaltosic oxide observed by under same amplification factor (multiple is sequentially increased) electron-microscope scanning, can be with from Fig. 7
Find out that the cobaltosic oxide that the preparation method of cobaltosic oxide of the present invention is prepared is spherical particle, sphericity is poor, different
Partial size difference is larger between particle, this it appears that the particle surface of cobaltosic oxide is not round and smooth from Fig. 8-Figure 10,
There are many concave surfaces on grain surface, indicates that the crystal compactness extent of cobaltosic oxide is relatively poor.
It can be seen that the product particle pattern of cobaltosic oxide is spherical shape or spherical from Fig. 7-Figure 10, pattern is more single
One, particle dispersion is good and particle is relatively uniform, and particle surface is relatively flat, but it is also seen that also has folder in bulky grain
Band little particle, and particle has the phenomenon that cracking.
It is obtained by comparing the SEM figure of the cobaltosic oxide under 2 two kinds of process conditions of embodiment 1 and embodiment, it is same
The change of its process conditions of preparation method can have an impact the pattern of the particle of cobaltosic oxide, can be the reason is that in preparation process
The change of technological parameter has an impact the nucleation rate of cobaltosic oxide particle and the coarsening rate of nucleus, changes its aggregation side
Formula causes finally formed cobaltosic oxide granule-morphology inconsistent；And change obtained cobaltosic oxide after technique
Grain has crackle, the reason is that the temperature of sintering is excessively high.
Find that its cobalt content is lower than anticipation content by energy spectrum analysis, the energy spectrum analysis constituent content table of cobaltosic oxide
It see the table below shown in 2.
Table 2
| Element | Weight percent | Atomic percent |
| C | 5.72 | 13.49 |
| O | 32.01 | 56.62 |
| Co | 62.26 | 29.89 |
Cobaltosic oxide energy spectrum analysis constituent content table obtained under 2 two kinds of process conditions of comparing embodiment 1 and embodiment,
Embodiment 1 gained four of the cobalt content of 2 gained cobaltosic oxide of embodiment after available technique change than technique before changing
The cobalt content of Co 3 O wants high, can be conducive to the cobalt content in cobaltosic oxide with the raising of Preliminary conclusion calcination temperature
Raising.But the cobaltosic oxide content prepared under 2 two kinds of process conditions of embodiment 1 and embodiment is all relatively low, so needing root
Calcination temperature and time are adjusted according to practical experience, to improve the cobalt content of final products.
The preparation method of cobaltosic oxide of the invention uses liquid-phase precipitation method of the ammonium hydrogen carbonate as precipitating reagent, this method tool
There is process route technology starting point low, it is easy to accomplish and grasp, degree of controllability is relatively high, can be adjusted according to actual production index
It is whole.Two batch cobaltosic oxides as made from the change of 2 technological parameter of embodiment 1 and embodiment are examined through XRD and are analysed, and find work
The change of skill parameter and have not been changed cobaltosic oxide each diffraction maximum feature, so obtain a conclusion, unified preparation method
Under, the change of technological parameter has no significant effect the structure of crystal grain.Two batches four as made from embodiment 1 and embodiment 2
The SEM of Co 3 O schemes, it can be deduced that, the change of technological parameter has a major impact the pattern of crystal grain.The change of technological parameter
Degree of supersaturation when cobalt carbonate precipitating is affected, and the variation of degree of supersaturation will affect the life of the nucleus in cobalt carbonate crystallization process
At speed and the coarsening rate of nucleus, the granularity pattern of cobalt carbonate determines the pattern of cobaltosic oxide to a certain extent.
PH value control is prepared compared with one of high-tap density cobalt carbonate key factor in technological parameter.Because of the variation of pH value
It can change degree of supersaturation when cobalt carbonate precipitating generates, further will affect the nucleus formation speed in cobalt carbonate crystallization process
And the coarsening rate of crystal.It is shown experimentally that, in certain pH value range, pH raising is conducive to nucleus generation and goes forward side by side one
The biggish precipitation particles of step-length great achievement partial size.When pH value is more than this range, since the increase nucleus with degree of supersaturation is raw
It is bigger than nuclei growth speed amplitude at speed, therefore as pH value increases, it will cause nucleus formation speed in system and be significantly increased,
And nuclei growth speed is relatively slow, the tap density of the cobalt carbonate and cobaltosic oxide that finally obtain can all be lower than regulation model
It encloses.Learn that the optimum pH range for preparing cobaltosic oxide is 7.5 ± 0.05 by the Experimental comparison of embodiment 1 and embodiment 2.
Two batch cobaltosic oxides as made from the change of 2 technological parameter of embodiment 1 and embodiment are it is found that reaction temperature
Degree increases, and the degree of supersaturation of solution can decline therewith, and the height of degree of supersaturation determines the nucleation speed of cobalt carbonate crystallization process
Degree.Temperature increases, and reactant molecule kinetic energy will increase, it would be possible that will cause the reaction speed of each process can all accelerate.But
As reaction temperature increases, solution degree of supersaturation will be reduced, and the nucleation rate increasing degree of precipitating can be less than the growth of precipitating
Speed.So nuclei growth can be conducive to by improving temperature.But temperature is too high to be unfavorable for generating stable nucleus, temperature increases
The dissolution for being conducive to small crystal nucleus is reassembled in large particle surface, so, tap density higher four oxygen larger from generation granularity
Change the consideration of three cobalts, higher reaction temperature should be selected, but temperature is excessively high, reaction energy consumption can be made to increase, by technical study, so
50-60 DEG C of temperature range of selection, it is final to determine that optimal reactive temperature is 54 DEG C.
By embodiment 1 and the comparison of embodiment 2 it is found that stirring has a major impact the crystallization process of cobalt carbonate, stirring can
So that the reaction process of whole system uniformly carries out, to have prevented cobalt concentration local excessively high and generates a large amount of nucleus, so as to
Guarantee to carry out while crystal growth process.Reinforcement stirring appropriate is conducive to growing up for nucleus.In addition, reasonable agitating mode
It can produce the formation that certain flow direction is conducive to spherical crystal.
Influence of the calcination temperature to cobaltosic oxide: cobalt content and vibration density that calcination temperature is conducive to improve product are improved
Degree, but product specific surface area can reduce.
Influence of the reaction time to cobaltosic oxide: forming process, that is, nucleus generation of cobalt carbonate crystal and grow up be need
Certain time is wanted, the reaction time is inadequate, and with the variation in reaction time, the particle size and distribution of cobalt carbonate particle, pattern is all
Variation is occurring, the reaction time is short, and particle is smaller, pattern be it is spherical, particle size distribution range is wider, has a large amount of little particles to deposit
The compact crystallization degree of cobalt carbonate crystal is relatively poor at this time.As the reaction time is elongated, the partial size of cobalt carbonate particle is into one
Step increases, and bulky grain is opposite to be increased, and the gap accumulated between particle also accordingly becomes larger, and is likely to result in tap density decline at this time.
The present invention can the property prepared by the change of process conditions using ammonium hydrogen carbonate as the liquid-phase precipitation method of precipitating reagent
The excellent cobaltosic oxide of energy.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of cobalt carbonate, which comprises the steps of:
Prepare ammonium bicarbonate soln and cobalt chloride solution；
The deionized water of predetermined amount is added in the reaction vessel, heats the deionized water to predetermined temperature；
It is added in the ammonium bicarbonate soln to the reaction vessel of part, and adjusts the soda acid of the solution in the reaction vessel
Spending to pH is 7.1-7.6；
It is added in the cobalt chloride solution and the remaining ammonium bicarbonate soln to the reaction vessel, is stirred to react, react
Generate cobalt carbonate.
2. a kind of preparation method of cobaltosic oxide, which comprises the steps of:
Prepare ammonium bicarbonate soln and cobalt chloride solution；
The deionized water of predetermined amount is added in the reaction vessel, heats the deionized water to predetermined temperature；
It is added in the ammonium bicarbonate soln to the reaction vessel of part, and adjusts the soda acid of the solution in the reaction vessel
Spending to pH is 7.1-7.6；
It is added in the cobalt chloride solution and the remaining ammonium bicarbonate soln to the reaction vessel, is stirred to react, react
Generate cobalt carbonate；
The cobalt carbonate generated is collected, and carries out calcination processing, obtains the cobaltosic oxide.
3. the preparation method of cobaltosic oxide according to claim 2, which is characterized in that the ammonium bicarbonate soln it is dense
Degree is 230g/L-250g/L, and the concentration of the cobalt chloride solution is 100g/L-120g/L.
4. the preparation method of cobaltosic oxide according to claim 2, which is characterized in that the ammonium bicarbonate soln and institute
It states cobalt chloride solution and passes through head tank respectively and be added to the reaction vessel.
5. the preparation method of cobaltosic oxide according to claim 4, which is characterized in that the carbon in the head tank
The cobalt chloride solution in sour hydrogen ammonium salt solution and the head tank is added to the reaction vessel by way of cocurrent adding material
It is interior.
6. according to the preparation method of cobaltosic oxide described in claim 2-5 any one, which is characterized in that when being stirred to react
Stirring rate be 80r/min-120r/min.
7. according to the preparation method of cobaltosic oxide described in claim 2-5 any one, which is characterized in that further include as follows
Step: the size for the cobalt carbonate granularity that interval predetermined time detection generates.
8. according to the preparation method of cobaltosic oxide described in claim 2-5 any one, which is characterized in that the carbonic acid
The calcination temperature that cobalt carries out calcination processing is 690 DEG C -780 DEG C.
9. the preparation method of cobaltosic oxide according to claim 8, which is characterized in that the time of calcining is 2h-4h.
10. according to the preparation method of cobaltosic oxide described in claim 2-5 any one, which is characterized in that the heating
The deionized water to predetermined temperature is that the deionized water in the reaction vessel is heated to 50 DEG C -60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484455.XA CN109319846A (en) | 2018-12-06 | 2018-12-06 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484455.XA CN109319846A (en) | 2018-12-06 | 2018-12-06 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109319846A true CN109319846A (en) | 2019-02-12 |
Family
ID=65256037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811484455.XA Pending CN109319846A (en) | 2018-12-06 | 2018-12-06 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109319846A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078134A (en) * | 2019-04-29 | 2019-08-02 | 合肥工业大学 | A kind of cobaltosic oxide and preparation method thereof for making lithium ion battery negative material |
| CN111874957A (en) * | 2020-06-30 | 2020-11-03 | 荆门市格林美新材料有限公司 | Production process of cobaltosic oxide precursor for superfine cobalt powder |
| CN112723424A (en) * | 2019-10-14 | 2021-04-30 | 荆门市格林美新材料有限公司 | Rod-shaped composite basic cobalt carbonate precursor and preparation method thereof |
| CN113200573A (en) * | 2021-05-28 | 2021-08-03 | 金川集团股份有限公司 | Preparation method of hollow shell ball cobaltosic oxide |
| CN113292108A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Preparation process of low-chlorine cobalt carbonate for superfine cobalt powder |
| CN113617346A (en) * | 2021-08-18 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Preparation method of small-particle cobaltosic oxide |
| WO2022127129A1 (en) * | 2020-12-18 | 2022-06-23 | 巴斯夫杉杉电池材料有限公司 | Doped cobaltosic oxide and preparation method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540024A (en) * | 2017-09-14 | 2018-01-05 | 湖南雅城新材料有限公司 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
-
2018
- 2018-12-06 CN CN201811484455.XA patent/CN109319846A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540024A (en) * | 2017-09-14 | 2018-01-05 | 湖南雅城新材料有限公司 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078134A (en) * | 2019-04-29 | 2019-08-02 | 合肥工业大学 | A kind of cobaltosic oxide and preparation method thereof for making lithium ion battery negative material |
| CN110078134B (en) * | 2019-04-29 | 2021-08-03 | 合肥工业大学 | Preparation method of cobaltosic oxide for preparing lithium ion battery cathode material |
| CN112723424A (en) * | 2019-10-14 | 2021-04-30 | 荆门市格林美新材料有限公司 | Rod-shaped composite basic cobalt carbonate precursor and preparation method thereof |
| CN113292108A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Preparation process of low-chlorine cobalt carbonate for superfine cobalt powder |
| CN111874957A (en) * | 2020-06-30 | 2020-11-03 | 荆门市格林美新材料有限公司 | Production process of cobaltosic oxide precursor for superfine cobalt powder |
| WO2022127129A1 (en) * | 2020-12-18 | 2022-06-23 | 巴斯夫杉杉电池材料有限公司 | Doped cobaltosic oxide and preparation method therefor |
| CN113200573A (en) * | 2021-05-28 | 2021-08-03 | 金川集团股份有限公司 | Preparation method of hollow shell ball cobaltosic oxide |
| CN113617346A (en) * | 2021-08-18 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Preparation method of small-particle cobaltosic oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109319846A (en) | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide | |
| CN105417507B (en) | A kind of preparation method and products obtained therefrom of azotized carbon nano particle | |
| JP2011057518A (en) | High-density nickel-cobalt-manganese coprecipitation hydroxide and method for producing the same | |
| CN104671245B (en) | Preparation method of hafnium carbide nano-powder | |
| CN105322154B (en) | Electrode active substance precursor nickel manganese oxide with special morphology | |
| Chen et al. | Microstructure evolution and advanced performance of Mn 3 O 4 nanomorphologies | |
| CN101434418A (en) | Method for preparing Co3O4 nano material by hydrothermal method under magnetic field effect | |
| CN102049527A (en) | Nanocrystal with core-shell structure and preparation method thereof | |
| CN108328665A (en) | A kind of preparation method of battery grade spherical cobaltosic oxide particle | |
| Pudukudy et al. | Facile synthesis of mesoporous α-Mn2O3 microspheres via morphology conserved thermal decomposition of MnCO3 microspheres | |
| Wang et al. | Controllable synthesis of metastable γ-Bi2O3 architectures and optical properties | |
| Inderan et al. | Synthesis and characterisations of SnO2 nanorods via low temperature hydrothermal method | |
| CN106558695A (en) | A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof | |
| CN105127441A (en) | Preparation method of platinum nanocrystalline dispersion system | |
| Li et al. | Growth of cubic anhydrous magnesium carbonate single crystal in deep eutectic solvent | |
| Payam et al. | Synthesis and Characterization of MOF‐Derived Structures: Recent Advances and Future Perspectives | |
| CN106430330A (en) | Preparation method of cobalt oxide powder | |
| CN105964260A (en) | Preparation method for metal catalyst and preparation method for carbon nano tube prepared by metal catalyst | |
| CN106673046B (en) | Setting conversion method prepares basic carbonate cerium precursor and fine cerium oxide | |
| Wang et al. | Electrolytic approach towards the controllable synthesis of symmetric, hierarchical, and highly ordered nickel dendritic crystals | |
| CN113798504A (en) | Preparation method of rare earth oxide dispersion-enhanced tungsten powder for 3D printing | |
| Dong et al. | Apparent activation energy of multicomponent transition metal oxalates to probe synthesis of battery precursor materials | |
| KR20150142755A (en) | Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby | |
| ZHANG et al. | Preparation of ultra-fine fibrous Fe–Ni alloy powder by coordinated co-precipitation–direct reduction process | |
| CN110697776A (en) | Preparation method of spherical nano chromium sesquioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190212 |
|
| RJ01 | Rejection of invention patent application after publication |