CN105731551B - Adulterate cobalt carbonate, doped cobaltic-cobaltous oxide and preparation method thereof - Google Patents
Adulterate cobalt carbonate, doped cobaltic-cobaltous oxide and preparation method thereof Download PDFInfo
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Abstract
The invention provides one kind to adulterate cobalt carbonate preparation method, comprises the following steps：Prepare cobalt carbonate；The cobalt carbonate is added to the cobalt carbonate for being mixed to get in metal alkoxide solution and coating the metal alkoxide；The cobalt carbonate after cladding is dried to obtain doping cobalt carbonate.Present invention also offers a kind of doping cobalt carbonate prepared using above-mentioned doping cobalt carbonate preparation method, a kind of doped cobaltic-cobaltous oxide preparation method and a kind of doped cobaltic-cobaltous oxide prepared using above-mentioned doped cobaltic-cobaltous oxide preparation method.The doping cobalt carbonate and doped cobaltic-cobaltous oxide preparation method of the present invention, can prepare uniform particle diameter, be evenly coated, the doping cobalt carbonate and doped cobaltic-cobaltous oxide of big particle diameter.
Description
Technical field
The invention belongs to adulterate the preparing technical field of cobalt compound, and in particular to one kind doping cobalt carbonate, four oxygen of doping
Change three cobalts and preparation method thereof.
Background technology
Spherical cobaltous carbonate is that a kind of persursor material the most universal, cobalt are applied in lithium cobalt oxide cathode material for lithium ion battery
Sour lithium has that open-circuit voltage is high, bigger than energy and the advantages of be easily-synthesized for other positive electrodes, and can be quick
Discharge and recharge, but the cobalt acid lithium prepared with prior art has an overcharge resistant ability poor, the specific capacity under compared with high charge voltage
Rapid the shortcomings of reducing.In order to improve cobalt acid lithium performance, Mg, Al etc. will be adulterated in cobalt acid lithium material, existing doping method be
During cobalt carbonate precursor synthesis in the form of co-precipitation add, but Mg, Al etc. addition can influence cobalt carbonate balling-up and
Particle size growth.
The content of the invention
The above-mentioned deficiency for aiming to overcome that prior art of the embodiment of the present invention, there is provided one kind doping cobalt carbonate preparation side
Method, the doping cobalt carbonate being evenly coated can be prepared.
The another object of the embodiment of the present invention is the above-mentioned deficiency for overcoming prior art, there is provided one kind doping cobalt carbonate,
The doping cobalt carbonate is evenly coated.
A further object for the embodiment of the present invention is the above-mentioned deficiency for overcoming prior art, there is provided the oxidation three of one kind doping four
Cobalt preparation method, the doped cobaltic-cobaltous oxide being evenly coated can be prepared.
A further object of the embodiment of the present invention is the above-mentioned deficiency for overcoming prior art, there is provided the oxidation three of one kind doping four
Cobalt, the doped cobaltic-cobaltous oxide are evenly coated.
In order to realize foregoing invention purpose, the technical scheme of the embodiment of the present invention is as follows：
One kind doping cobalt carbonate preparation method, comprises the following steps：
Prepare cobalt carbonate；
The cobalt carbonate is added to the cobalt carbonate for being mixed to get in metal alkoxide solution and coating the metal alkoxide；
The cobalt carbonate after cladding is dried to obtain doping cobalt carbonate.
A kind of doping cobalt carbonate prepared using above-mentioned doping cobalt carbonate preparation method, the doping cobalt carbonate is with carbonic acid
Cobalt is core, and metal alkoxide is coated on the cobalt carbonate surface.
A kind of doped cobaltic-cobaltous oxide preparation method, by above-mentioned doping cobalt carbonate at 300~800 DEG C, oxygen or nitrogen
Under gas atmosphere, doped cobaltic-cobaltous oxide is prepared in 3~10h of roasting.
A kind of and doped cobaltic-cobaltous oxide prepared using above-mentioned doped cobaltic-cobaltous oxide preparation method.
The doping cobalt carbonate preparation method of above-described embodiment, the process for preparing cobalt carbonate and doping is separately carried out, is easy to
Control cobalt carbonate pattern and particle size growth so that the process of doping does not interfere with the growth of cobalt carbonate particle, can prepare particle diameter
It is homogeneous, be evenly coated, the doping cobalt carbonate of big particle diameter.
The doped cobaltic-cobaltous oxide preparation method of above-described embodiment, the decomposition temperature of metal alkoxide is low, is calcined in cobalt carbonate
Metal oxide is decomposed into during for cobaltosic oxide, is uniformly coated on cobaltosic oxide surface, uniformity is good.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is the scanning electron microscope (SEM) photograph of the doping cobalt carbonate of embodiments of the invention 3；
Fig. 2 is the scanning electron microscope (SEM) photograph of the doped cobaltic-cobaltous oxide of embodiments of the invention 6；
Fig. 3 is the scanning electron microscope (SEM) photograph of the doped cobaltic-cobaltous oxide of embodiments of the invention 8.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Present example provides a kind of doping cobalt carbonate preparation method, comprises the following steps：
Step S01：Prepare cobalt carbonate；
Step S02：Cobalt carbonate is added to the cobalt carbonate that cladding metal alkoxide is mixed to get in metal alkoxide, the process is
The process of physical absorption；
Step S03：Cobalt carbonate after cladding is dried to obtain doping cobalt carbonate.
The doping cobalt carbonate preparation method of above-described embodiment, the process for preparing cobalt carbonate and doping is separately carried out so that
The process of doping does not interfere with the growth of cobalt carbonate particle, easily controllable cobalt carbonate pattern and particle size growth, can prepare particle diameter
It is homogeneous, be evenly coated, the doping cobalt carbonate of big particle diameter.
Specifically, metal alkoxide solution is at least one of ethanol magnesium solution, ethanol aluminum solutions and ethanol titanium solution, then
It is the cobalt carbonate for mixing at least one of Mg, Al and Ti to adulterate cobalt carbonate.
Specifically, step S01 process comprises the following specific steps that：
Step S01-1：Using pure water and ammonium hydrogen carbonate as bottom liquid, control in the liquid of bottom carbonate concentration caused by hydrolysis be 3~
5g/L, temperature are 30~65 DEG C；
Step S01-2：The cobalt salt solution that cobalt salt concentration is 60~180g/L is prepared, ammonium bicarbonate concentration is 100~300g/
L ammonium bicarbonate soln；
Step S01-3：Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:2~1:
3, cobalt salt solution and ammonium bicarbonate soln cocurrent are added in the liquid of bottom the reaction under conditions of stirring and obtain cobalt carbonate wet feed；
Step S01-4：The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate, the moisture of the cobalt carbonate after dehydration is small
In 5%.
Carbonate in step S01 is caused by bicarbonate ion hydrolysis.Step S01 process can be in a kettle
Carry out, i.e., first add bottom liquid in reactor, then cobalt salt solution and ammonium bicarbonate soln reaction mass are added in reactor
Reaction.
In step S01-1, the selection gist of temperature is：If less than 30 DEG C, grain growth is slow and intercrystalline is easily poly-
Collection；Higher than 65 DEG C, then grain growth is too fast, is unfavorable for size controlling.In addition, ammonium hydrogen carbonate raises easier decomposition with temperature
(NH4HCO3=NH3+H2O+CO2), ammonia caused by decomposition is easily complexed with cobalt, so as to reduce the generation quantity of nucleus, makes cobalt source
It is easy to grow on existing particle, influences size controlling.Ammonium hydrogen carbonate is added in the liquid of bottom and make it that bottom liquid is in alkalescent.Work as cobalt salt
Solution is added in the liquid of bottom, due to having substantial amounts of ammonium hydrogen carbonate in the liquid of bottom, easily generates substantial amounts of fine grain core, beneficial to control cobalt carbonate
Growth course.
In step S01-3, by controlling the mol ratio of cobalt salt and ammonium hydrogen carbonate, cobalt salt molecule and carbon in system can be caused
The sour abundant haptoreaction of hydrogen ammonium molecule.
In step S01-4, follow-up saturated extent of adsorption is adjusted by controlling the moisture of cobalt carbonate, so as to control carbonic acid
Cobalt is to Mg, Al and Ti ratio of adsorption, while drying steps save time and the energy.
Specifically, step S01-3 is carried out by the way of control by stages technological parameter, is easy to control the pattern of cobalt carbonate
And particle diameter, it is specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 50~300L/h, carbon
The flow of sour hydrogen ammonium salt solution is 100~800L/h, and pH is 7.6~7.8, and temperature is 30~65 DEG C, the rotating speed of stirring for 100~
220r/min, preferably 100~200r/min, it is 300~1000g/L that solid content is kept in course of reaction.
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 30~300L/h, and the flow of ammonium bicarbonate soln is 50~800L/h, preferably 50~700L/h, pH
For 7.2~7.8, preferably 7.2~7.6, temperature is 30~55 DEG C, and the rotating speed of stirring is 100~250r/min, preferably 110
~250r/min, mother liquor is isolated, retain solid continued growth, it is 600~1200g/L that solid content is kept in course of reaction.One
As in the case of, controlled by flow, after material fills up reactor, the particle diameter of cobalt carbonate wet feed reaches 10 μm.
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 10~300L/h, and the flow of ammonium bicarbonate soln is 20~800L/h, preferably 50~700L/h, pH
For 7.0~7.8, preferably 7.1~7.6, temperature is 30~50 DEG C, and the rotating speed of stirring is 100~300r/min, preferably 120
~300r/min, it is 800~1400g/L to control solid content.
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 10~300L/h, and the flow of ammonium bicarbonate soln is 10~800L/h, and pH is 6.8~7.8, and temperature is
30~55 DEG C, the rotating speed of stirring is 100~220r/min, and it is 1000~1600g/L to control solid content.Added into reaction system
Surfactant, quality is added as 0.1~1% of the cobalt quality in cobalt carbonate.
It is above-mentioned to prepare during cobalt carbonate using control by stages reactant flow, pH, temperature and/or solid content etc.
Process conditions so that cobalt carbonate substep grows, the pattern and particle diameter of easily controllable cobalt carbonate.
Initial period is reacted, it is necessary to substantial amounts of granular grows base (nucleus), cobalt carbonate slowly grow in nucleating surface, ability
Highdensity cobalt carbonate is obtained, at a high ph, ammonium hydrogen carbonate is significantly excessive, can accelerate the generation of cobalt carbonate, but pH value is high
In 7.8, nucleus can largely be assembled, and influence its pattern and density, to prevent nucleus from assembling, in the range of above-mentioned pH, need to use compared with
Strong mixing and relatively low solid content.
Mid-term is reacted, when cobalt carbonate particle diameter grows to certain value, reduces pH value in reaction, and reduces inlet amount, prevents that generation is new
Nucleus, the material for making subsequently to add only grows on the surface of existing cobalt carbonate, with the progress of reaction, in reaction system
Solid content increase, can reduce stirring intensity.In order to ensure its stirring intensity, speed of agitator can be increased.
The later stage is reacted, when particle diameter grows to certain limit, granule surface activity reduces, and hinders the continued growth of particle, holds
New growing point is easily formed, produces small grains.In order to suppress the generation of fine particle, added into reaction system a certain amount of
Surfactant, while further reduce material charging rate.
Specifically, in step S02, the ratio of the mole of metal is 1 in cobalt and metal alkoxide in cobalt carbonate:0.001~1:
0.1.If for example, were only doped with single metal Mg, Al or Ti, the mole of the Mg in cobalt carbonate in cobalt and magnesium ethylate
Than for 1:0.001~1:0.1；And/or the mole ratio of the Al in cobalt carbonate in cobalt and aluminium ethylate is 1:0.001~1:
0.1；And/or the mole ratio of the Ti in cobalt carbonate in cobalt and titanium ethanolate is 1:0.001~1:0.1.
Specifically, during step S02 mixing, cobalt carbonate and metal alkoxide solution 3~10 are stirred at normal temperatures
Hour.
Stirring can be evenly coated metal alkoxide, particularly magnesium ethylate, aluminium ethylate and titanium ethanolate, the length of mixing time
The amount of cobalt carbonate cladding metal alkoxide, particularly magnesium ethylate, aluminium ethylate and titanium ethanolate is influenceed, so as to influence the effect of doping.Such as
Fruit mixing time is less than 3 hours, then is coated insufficient；If mixing time is longer than 10 hours, easily make local cladding excessive.
Specifically, during step S03, dry temperature is 60~200 DEG C.Caused alcohol in drying process, especially
It is that ethanol can reclaim use.
Under the drying temperature, metal alkoxide decomposition goes out alcohol, and metal is stayed on cobalt carbonate particle, for example, magnesium ethylate, ethanol
Aluminium and/or titanium ethanolate decomposite ethanol, and magnesium, aluminium and/or titanium are retained on cobalt carbonate particle；If higher than if this temperature cobalt carbonate
Easily decompose.
The doping cobalt carbonate that the embodiment of the present invention uses the above method to prepare is using cobalt carbonate as core, and metal alkoxide is coated on
Cobalt carbonate surface.The metal alkoxide can be at least one of magnesium ethylate, aluminium ethylate and titanium ethanolate.
The embodiment of the present invention uses the doping cobalt carbonate that the above method is prepared to mix at least one of Mg, Al and Ti
Cobalt carbonate, wherein, the accounting of Mg, Al and/or Ti gross mass in cobalt carbonate is adulterated is 0.1%~10%.For example, such as
Fruit is only doped with single metal, then Mg quality accounting is 0.1%~10%；And/or Al quality accounting be 0.1%~
10%；And/or Ti quality accounting is 0.1%~10%.
Mainly as the persursor material of lithium ion battery material cobalt acid lithium, cobalt acid lithium has cobalt carbonate prepared by the present invention
The advantages that compacted density is high, and charging/discharging voltage is high, but the deficiencies of heat endurance difference be present；Foreign metal, particularly Mg, Al and Ti
Addition Deng element can improve the performance of cobalt acid lithium, when Mg, Al and Ti addition are respectively less than 0.1%, the lifting to performance
It is limited, but when Mg, Al and Ti addition are above 10%, the hydraulic performance declines such as the density of cobalt acid lithium can be caused, therefore, selection
Mg, Al and Ti addition are 0.1%-10%.
The embodiment of the present invention additionally provides a kind of doped cobaltic-cobaltous oxide preparation method, and above-mentioned doping cobalt carbonate is existed
300~800 DEG C, under oxygen or nitrogen atmosphere, doped cobaltic-cobaltous oxide is prepared in 3~10h of roasting.It is preferred that the doping carbonic acid
Cobalt is the cobalt carbonate for mixing at least one of Mg, Al and Ti, then doped cobaltic-cobaltous oxide is to mix at least one of Mg, Al and Ti
Cobaltosic oxide.
The embodiment of the present invention additionally provides a kind of doping four prepared using above-mentioned doped cobaltic-cobaltous oxide preparation method
Co 3 O.It is preferred that the doped cobaltic-cobaltous oxide is the cobaltosic oxide for mixing at least one of Mg, Al and Ti.
The doped cobaltic-cobaltous oxide preparation method of above-described embodiment, metal alkoxide, particularly magnesium ethylate, aluminium ethylate, ethanol
Titanium decomposition temperature is low, and metal oxide, such as magnesia, aluminum oxide, titanium oxide are decomposed into the roasting process of cobalt carbonate
Cobaltosic oxide surface can be uniformly coated on, uniformity is good.
Illustrated below by way of multiple embodiments.
Embodiment 1
Step S01：Prepare cobalt carbonate.Step S01 process comprises the following specific steps that：
Step S01-1：Prepare bottom liquid.
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 3g/L to control carbonate concentration in the liquid of bottom, and temperature is 48 DEG C.
Step S01-2：Prepare cobalt salt solution and ammonium bicarbonate soln.
The cobalt salt solution that cobalt salt concentration is 60g/L is prepared, ammonium bicarbonate concentration is 100g/L ammonium bicarbonate soln.
Step S01-3：Prepare cobalt carbonate wet feed.
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:2, by cobalt salt solution and
Ammonium bicarbonate soln cocurrent is added in the liquid of bottom the reaction under conditions of stirring and obtains cobalt carbonate wet feed.
Step S01-4：Washing, dehydration cobalt carbonate wet feed.
The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate.The moisture of cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 is carried out stage by stage, specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 300L/h, bicarbonate
The flow of ammonium salt solution is 100L/h, and pH 7.6, temperature is 43 DEG C, and the rotating speed of stirring is 100r/min, keeps solid in course of reaction
Content is 300g/L；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 180L/h, and the flow of ammonium bicarbonate soln is 100L/h, and pH 7.2, temperature is 36 DEG C, and stirring turns
Speed is 110r/min, isolates mother liquor, retains solid continued growth, it is 900g/L that solid content is kept in course of reaction；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 50L/h, and the flow of ammonium bicarbonate soln is 100L/h, and pH 7.1, temperature is 36 DEG C, and stirring turns
Speed is 120r/min, and it is 900g/L to control solid content；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 10L/h, and the flow of ammonium bicarbonate soln is 10L/h, and pH 7.1, temperature is 36 DEG C, the rotating speed of stirring
For 100r/min, it is 1100g/L to control solid content, adds surfactant PVP, it is cobalt quality in cobalt carbonate that PVP, which adds quality,
0.1%.
The apparent density of the cobalt carbonate prepared in step S01 is more than 1.6g/cm3。
Step S02：Cobalt carbonate is added to the cobalt carbonate that cladding magnesium ethylate is mixed to get in ethanol magnesium solution.The mistake of mixing
With stir process in journey, cobalt carbonate and ethanol magnesium solution 3 hours are stirred at normal temperatures.Wherein, cobalt and magnesium ethylate in cobalt carbonate
In Mg mole ratio be 1:0.001.
Step S03：Cobalt carbonate after cladding is dried to obtain to the cobalt carbonate for mixing Mg at 100 DEG C, Mg quality is in doped carbon
Accounting in sour cobalt is 0.1%.
Embodiment 2
Step S01：Prepare cobalt carbonate.Step S01 process comprises the following specific steps that：
Step S01-1：Prepare bottom liquid.
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 5g/L to control carbonate concentration in the liquid of bottom, and temperature is 36 DEG C.
Step S01-2：Prepare cobalt salt solution and ammonium bicarbonate soln.
The cobalt salt solution that cobalt salt concentration is 180g/L is prepared, ammonium bicarbonate concentration is 300g/L ammonium bicarbonate soln.
Step S01-3：Prepare cobalt carbonate wet feed.
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:3, by cobalt salt solution and
Ammonium bicarbonate soln cocurrent is added in the liquid of bottom the reaction under conditions of stirring and obtains cobalt carbonate wet feed.
Step S01-4：Washing, dehydration cobalt carbonate wet feed.
The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate.The moisture of cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 is carried out stage by stage, specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 300L/h, bicarbonate
The flow of ammonium salt solution is 800L/h, and pH 7.8, temperature is 43 DEG C, and the rotating speed of stirring is 200r/min, keeps solid in course of reaction
Content is 600g/L；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 300L/h, and the flow of ammonium bicarbonate soln is 700L/h, and pH 7.6, temperature is 55 DEG C, and stirring turns
Speed is 220r/min, isolates mother liquor, retains solid continued growth, it is 600g/L that solid content is kept in course of reaction；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 300L/h, and the flow of ammonium bicarbonate soln is 600L/h, and pH 7.5, temperature is 50 DEG C, and stirring turns
Speed is 220r/min, and it is 1400g/L to control solid content；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 280L/h, and the flow of ammonium bicarbonate soln is 500L/h, and pH 7.8, temperature is 55 DEG C, and stirring turns
Speed is 220r/min, and it is 1600g/L to control solid content, adds surfactant PVP, it is cobalt matter in cobalt carbonate that PVP, which adds quality,
The 1% of amount.
The apparent density of the cobalt carbonate prepared in step S01 is more than 1.6g/cm3。
Step S02：Cobalt carbonate is added in the solution of aluminium ethylate and titanium ethanolate and is mixed to get cladding aluminium ethylate and ethanol
The cobalt carbonate of titanium.With the solution 10 of stir process, at normal temperatures stirring cobalt carbonate, aluminium ethylate and titanium ethanolate during mixing
Hour.Wherein, the mole ratio of the aluminium in cobalt carbonate in cobalt and aluminium ethylate is 1:0.05, titanium in cobalt and titanium ethanolate in cobalt carbonate
Mole ratio is 1:0.05.
Step S03：Cobalt carbonate after cladding is dried to obtain to the cobalt carbonate for mixing Al and Ti at 120 DEG C, Al is in doping carbonic acid
The quality accounting that quality accounting in cobalt is 0.5%, Ti is 0.5%.
Embodiment 3
Step S01：Prepare cobalt carbonate.Step S01 process comprises the following specific steps that：
Step S01-1：Prepare bottom liquid.
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 4g/L to control carbonate concentration in the liquid of bottom, and temperature is 40 DEG C.
Step S01-2：Prepare cobalt salt solution and ammonium bicarbonate soln.
The cobalt salt solution that cobalt salt concentration is 100g/L is prepared, ammonium bicarbonate concentration is 200g/L ammonium bicarbonate soln.
Step S01-3：Prepare cobalt carbonate wet feed.
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:2.5, by cobalt salt solution
The reaction under conditions of stirring, which is added in the liquid of bottom, with ammonium bicarbonate soln cocurrent obtains cobalt carbonate wet feed.
Step S01-4：Washing, dehydration cobalt carbonate wet feed.
The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate.The moisture of cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 is carried out stage by stage, specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 300L/h, bicarbonate
The flow of ammonium salt solution is 500L/h, and pH 7.7, temperature is 43 DEG C, and the rotating speed of stirring is 150r/min, keeps solid in course of reaction
Content is 400g/L；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 180L/h, and the flow of ammonium bicarbonate soln is 400L/h, and pH 7.6, temperature is 43 DEG C, and stirring turns
Speed is 170r/min, isolates mother liquor, retains solid continued growth, it is 700g/L that solid content is kept in course of reaction；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 180L/h, and the flow of ammonium bicarbonate soln is 400L/h, and pH 7.6, temperature is 43 DEG C, and stirring turns
Speed is 170/min, and it is 1000g/L to control solid content；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 150L/h, and the flow of ammonium bicarbonate soln is 300L/h, and pH 7.6, temperature is 43 DEG C, and stirring turns
Speed is 180r/min, and it is 1200g/L to control solid content, adds surfactant PVP, it is cobalt matter in cobalt carbonate that PVP, which adds quality,
The 0.5% of amount.
The apparent density of the cobalt carbonate prepared in step S01 is more than 1.6g/cm3。
Step S02：Cobalt carbonate is added in the solution of magnesium ethylate, aluminium ethylate and titanium ethanolate and is mixed to get cladding ethanol
The cobalt carbonate of magnesium, aluminium ethylate and titanium ethanolate.With stir process during mixing, stir at normal temperatures cobalt carbonate, magnesium ethylate,
The solution of aluminium ethylate and titanium ethanolate 7 hours.The mole ratio of metal in cobalt carbonate in cobalt and metal alkoxide is 1:0.08, its
In, the mole ratio of the Mg in cobalt carbonate in cobalt and magnesium ethylate is 1:0.02nd, mole of the Al in cobalt carbonate in cobalt and aluminium ethylate
Amount is than being 1:0.02nd, the mole ratio of the Ti in cobalt carbonate in cobalt and titanium ethanolate is 1:0.04.
Step S03：Cobalt carbonate after cladding is dried to obtain to the cobalt carbonate for mixing Mg, Al and Ti, Mg, Al and Ti at 110 DEG C
Accounting of the gross mass in cobalt carbonate is adulterated be 9.9%, wherein, the Mg quality accounting in cobalt carbonate is adulterated is 2.4%, Al
Quality in accounting in adulterating cobalt carbonate be that 2.7%, Ti quality accounting in cobalt carbonate is adulterated is 4.8%.
As shown in figure 1, the scanning electron microscope (SEM) photograph of the doping cobalt carbonate for the embodiment of the present invention 3.It can be seen that prepare
The cobalt carbonate for mixing Mg, Al and Ti it is spherical in shape, shape and size are uniform.
Embodiment 4
Step S01：Prepare cobalt carbonate.Step S01 process comprises the following specific steps that：
Step S01-1：Prepare bottom liquid.
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 3.5g/L to control carbonate concentration in the liquid of bottom, and temperature is 30 DEG C.
Step S01-2：Prepare cobalt salt solution and ammonium bicarbonate soln.
The cobalt salt solution that cobalt salt concentration is 120g/L is prepared, ammonium bicarbonate concentration is 180g/L ammonium bicarbonate soln.
Step S01-3：Prepare cobalt carbonate wet feed.
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:2.5, by cobalt salt solution
The reaction under conditions of stirring, which is added in the liquid of bottom, with ammonium bicarbonate soln cocurrent obtains cobalt carbonate wet feed.
Step S01-4：Washing, dehydration cobalt carbonate wet feed.
The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate.The moisture of cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 is carried out stage by stage, specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 50L/h, ammonium hydrogen carbonate
The flow of solution is 300L/h, and pH 7.7, temperature is 30 DEG C, and the rotating speed of stirring is 120r/min, keeps containing admittedly in course of reaction
Measure as 500g/L；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 30L/h, and the flow of ammonium bicarbonate soln is 50L/h, and pH 7.5, temperature is 30 DEG C, the rotating speed of stirring
For 140r/min, mother liquor is isolated, retains solid continued growth, it is 800g/L that solid content is kept in course of reaction；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 10L/h, and the flow of ammonium bicarbonate soln is 20L/h, and pH 7.0, temperature is 30 DEG C, the rotating speed of stirring
For 140r/min, it is 800g/L to control solid content；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 10L/h, and the flow of ammonium bicarbonate soln is 10L/h, and pH 6.8, temperature is 30 DEG C, the rotating speed of stirring
For 150r/min, it is 1000g/L to control solid content, adds surfactant PVP, it is cobalt quality in cobalt carbonate that PVP, which adds quality,
0.3%.
The apparent density of the cobalt carbonate prepared in step S01 is more than 1.6g/cm3。
Step S02：Cobalt carbonate is added in the solution of magnesium ethylate, aluminium ethylate and titanium ethanolate and is mixed to get cladding ethanol
The cobalt carbonate of magnesium, aluminium ethylate and titanium ethanolate.With stir process during mixing, stir at normal temperatures cobalt carbonate, magnesium ethylate,
The solution of aluminium ethylate and titanium ethanolate 3 hours.The mole ratio of metal in cobalt carbonate in cobalt and metal alkoxide is 1:0.08, its
In, the mole ratio of the Mg in cobalt carbonate in cobalt and magnesium ethylate is 1:0.02nd, mole of the Al in cobalt carbonate in cobalt and aluminium ethylate
Amount is than being 1:0.02nd, the mole ratio of the Ti in cobalt carbonate in cobalt and titanium ethanolate is 1:0.04.
Step S03：Cobalt carbonate after cladding is dried to obtain to the cobalt carbonate for mixing Mg, Al and Ti at 60 DEG C, Mg, Al and Ti's
Accounting of the gross mass in cobalt carbonate is adulterated is 8.25%, wherein, the Mg quality accounting in cobalt carbonate is adulterated is 2.0%, Al
Quality in accounting in adulterating cobalt carbonate be that 2.25%, Ti quality accounting in cobalt carbonate is adulterated is 4.0%.
Embodiment 5
Step S01：Prepare cobalt carbonate.Step S01 process comprises the following specific steps that：
Step S01-1：Prepare bottom liquid.
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 4.5g/L to control carbonate concentration in the liquid of bottom, and temperature is 65 DEG C.
Step S01-2：Prepare cobalt salt solution and ammonium bicarbonate soln.
The cobalt salt solution that cobalt salt concentration is 160g/L is prepared, ammonium bicarbonate concentration is 280g/L ammonium bicarbonate soln.
Step S01-3：Prepare cobalt carbonate wet feed.
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in cobalt salt solution and ammonium bicarbonate soln is 1:2, by cobalt salt solution and
Ammonium bicarbonate soln cocurrent is added in the liquid of bottom the reaction under conditions of stirring and obtains cobalt carbonate wet feed.
Step S01-4：Washing, dehydration cobalt carbonate wet feed.
The washing of cobalt carbonate wet feed, dehydration are obtained into cobalt carbonate.The moisture of cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 is carried out stage by stage, specific as follows：
The initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution are 280L/h, bicarbonate
The flow of ammonium salt solution is 700L/h, and pH 7.8, temperature is 65 DEG C, and the rotating speed of stirring is 200r/min, keeps solid in course of reaction
Content is 1000g/L；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 10 μm,
The flow of cobalt salt solution is 250L/h, and the flow of ammonium bicarbonate soln is 680L/h, and pH 7.6, temperature is 50 DEG C, and stirring turns
Speed is 250r/min, isolates mother liquor, retains solid continued growth, it is 1200g/L that solid content is kept in course of reaction；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 15 μm,
The flow of cobalt salt solution is 240L/h, and the flow of ammonium bicarbonate soln is 650L/h, and pH 7.5, temperature is 45 DEG C, and stirring turns
Speed is 300r/min, and it is 1300g/L to control solid content；
In the course of reaction of cobalt salt solution and ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is 18 μm,
The flow of cobalt salt solution is 220L/h, and the flow of ammonium bicarbonate soln is 600L/h, and pH 7.5, temperature is 50 DEG C, and stirring turns
Speed is 220r/min, and it is 1500g/L to control solid content, adds surfactant PVP, it is cobalt gold in cobalt carbonate that PVP, which adds quality,
Belong to the 0.8% of quality.
The apparent density of the cobalt carbonate prepared in step S01 is more than 1.6g/cm3。
Step S02：Cobalt carbonate is added in the solution of magnesium ethylate, aluminium ethylate and titanium ethanolate and is mixed to get cladding ethanol
The cobalt carbonate of magnesium, aluminium ethylate and titanium ethanolate.With stir process during mixing, stir at normal temperatures cobalt carbonate, magnesium ethylate,
The solution of aluminium ethylate and titanium ethanolate 3 hours.The mole ratio of metal in cobalt carbonate in cobalt and metal alkoxide is 1:0.045, its
In, the mole ratio of the Mg in cobalt carbonate in cobalt and magnesium ethylate is 1:0.01st, mole of the Al in cobalt carbonate in cobalt and aluminium ethylate
Amount is than being 1:0.015th, the mole ratio of the Ti in cobalt carbonate in cobalt and titanium ethanolate is 1:0.02.
Step S03：Cobalt carbonate after cladding is dried to obtain to the cobalt carbonate for mixing Mg, Al and Ti, Mg, Al and Ti at 200 DEG C
Accounting of the gross mass in cobalt carbonate is adulterated be 9.375%, wherein, the Mg quality accounting in cobalt carbonate is adulterated is 2%, Al
Quality in accounting in adulterating cobalt carbonate be that 3.375%, Ti quality accounting in cobalt carbonate is adulterated is 4%.
Embodiment 6
10h, which is calcined, by the cobalt carbonate for mixing Mg that embodiment 1 is prepared at 480 DEG C, in oxygen atmosphere obtains mixing the four of Mg
Co 3 O.As shown in Fig. 2 the scanning electron microscope (SEM) photograph of the doped cobaltic-cobaltous oxide for embodiments of the invention 6.Can from figure
Go out, preparation mixes that Mg cobaltosic oxides are spherical in shape, and shape and size are uniform.
Embodiment 7
Be calcined by the cobalt carbonate for mixing Al and Ti that embodiment 2 is prepared at 530 DEG C, in oxygen atmosphere 3h obtain mixing Al and
Ti cobaltosic oxide.
Embodiment 8
5h is calcined by the cobalt carbonate for mixing Mg, Al and Ti that embodiment 3 is prepared at 500 DEG C, in oxygen atmosphere to be mixed
Mg, Al and Ti cobaltosic oxide.As shown in figure 3, the ESEM of the doped cobaltic-cobaltous oxide for embodiments of the invention 8
Figure.It can be seen that the cobaltosic oxide for mixing Mg, Al and Ti prepared is spherical in shape, shape and size are uniform.
Embodiment 9
8h is calcined by the cobalt carbonate for mixing Mg, Al and Ti that embodiment 4 is prepared at 300 DEG C, in oxygen atmosphere to be mixed
Mg, Al and Ti cobaltosic oxide.
Embodiment 10
4h is calcined by the cobalt carbonate for mixing Mg, Al and Ti that embodiment 5 is prepared at 800 DEG C, in oxygen atmosphere to be mixed
Mg, Al and Ti cobaltosic oxide.
In summary, the embodiment of the present invention doping cobalt carbonate preparation method in, cobalt carbonate prepare with it is metal-doped
Process is separately carried out, easily controllable cobalt carbonate pattern and particle size growth.In addition, cobalt carbonate particle diameter substep grows, it is also easy to control
The pattern and size of cobalt carbonate.Adsorbed using metallorganic, one time adsorbance is big, and simple to operate, cost is low.The present invention is implemented
In the preparation method of the doped cobaltic-cobaltous oxide of example, the decomposition temperature of metal alkoxide is low, the decomposable asymmetric choice net in cobalt carbonate roasting process
Cobaltosic oxide surface is coated on into metal oxide, the uniformity of cladding is good.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., all should be included within protection scope of the present invention.
Claims (5)
1. one kind doping cobalt carbonate preparation method, it is characterised in that comprise the following steps：
Using pure water and ammonium hydrogen carbonate as bottom liquid, it is 3~5g/L to control carbonate concentration caused by hydrolysis in the bottom liquid, and temperature is
30~65 DEG C；
The cobalt salt solution that cobalt salt concentration is 60~180g/L is prepared, ammonium bicarbonate concentration is that 100~300g/L ammonium hydrogen carbonate is molten
Liquid；
Mol ratio according to ammonium hydrogen carbonate in cobalt salt in the cobalt salt solution and the ammonium bicarbonate soln is 1:2~1:3, by institute
State cobalt salt solution and the ammonium bicarbonate soln cocurrent is added in the bottom liquid, reacted under conditions of stirring and obtain cobalt carbonate
Wet feed；
Cobalt carbonate wet feed washing, dehydration are obtained into the cobalt carbonate, the moisture of the cobalt carbonate is less than 5%；
The cobalt carbonate is added to the cobalt carbonate for being mixed to get in metal alkoxide solution and coating the metal alkoxide；
The cobalt carbonate after cladding is dried to obtain doping cobalt carbonate.
2. the preparation method of doping cobalt carbonate as claimed in claim 1, it is characterised in that：The metal alkoxide solution is ethanol
At least one of magnesium solution, ethanol aluminum solutions and ethanol titanium solution, the doping cobalt carbonate is to mix in Mg, Al and Ti at least
A kind of cobalt carbonate.
3. doping cobalt carbonate preparation method as claimed in claim 1, it is characterised in that：
The initial stage of the cobalt salt solution and the ammonium bicarbonate soln course of reaction, the flow of the cobalt salt solution for 50~
300L/h, the flow of the ammonium bicarbonate soln is 100~800L/h, and pH is 7.6~7.8, and temperature is 30~65 DEG C, described to stir
The rotating speed mixed is 100~220r/min, and it is 300~1000g/L that solid content is kept in the course of reaction；
In the course of reaction of the cobalt salt solution and the ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is
At 10 μm, the flow of the cobalt salt solution is 30~300L/h, and the flow of the ammonium bicarbonate soln is 50~800L/h, and pH is
7.2~7.8, temperature is 30~55 DEG C, and the rotating speed of the stirring is 100~250r/min, isolates mother liquor, retains solid and continues
Grow, it is 600~1200g/L that solid content is kept in the course of reaction；
In the course of reaction of the cobalt salt solution and the ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is
At 15 μm, the flow of the cobalt salt solution is 10~300L/h, and the flow of the ammonium bicarbonate soln is 20~800L/h, and pH is
7.0~7.8, temperature be 30~50 DEG C, the rotating speed of the stirring be 100~300r/min, control the solid content be 800~
1400g/L；
In the course of reaction of the cobalt salt solution and the ammonium bicarbonate soln, when the particle diameter of the cobalt carbonate wet feed of preparation is
At 18 μm, the flow of the cobalt salt solution is 10~300L/h, and the flow of the ammonium bicarbonate soln is 10~800L/h, and pH is
6.8~7.8, temperature be 30~55 DEG C, the rotating speed of the stirring be 100~220r/min, control the solid content be 1000~
1600g/L, and surfactant is added, the addition quality of the surfactant is the quality of the cobalt in the cobalt carbonate
0.1~1%.
4. doping cobalt carbonate preparation method as claimed in claim 2, it is characterised in that：Cobalt and the metal in the cobalt carbonate
The ratio of the mole of metal is 1 in alkoxide:0.001~1:0.1.
5. doping cobalt carbonate preparation method as claimed in claim 1 or 2, it is characterised in that：It is adjoint during the mixing
Stir process, the cobalt carbonate and the metal alkoxide solution 3~10 hours are stirred at normal temperatures；And/or the drying
Temperature is 60~200 DEG C.
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| CN106629870B (en) * | 2016-11-28 | 2018-11-06 | 荆门市格林美新材料有限公司 | A kind of preparation method of small particle spherical cobaltous carbonate |
| CN106825597A (en) * | 2016-12-23 | 2017-06-13 | 荆门市格林美新材料有限公司 | A kind of preparation method of cobalt powder |
| HUE063153T2 (en) | 2017-03-08 | 2024-01-28 | Umicore Nv | Precursors of cathode materials for a rechargeable lithium ion battery |
| CN108011101B (en) * | 2017-11-28 | 2020-04-03 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size uniformly-aluminum-doped cobaltosic oxide |
| CN108649219B (en) * | 2018-05-14 | 2021-09-24 | 荆门市格林美新材料有限公司 | Preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN108807881A (en) * | 2018-05-21 | 2018-11-13 | 兰州金川新材料科技股份有限公司 | A kind of body mutually mixes the preparation method of aluminium cobaltosic oxide |
| CN110540249A (en) * | 2018-05-28 | 2019-12-06 | 荆门市格林美新材料有限公司 | Preparation method of high-tap-density aluminum-doped cobaltosic oxide |
| KR20190142067A (en) | 2018-06-15 | 2019-12-26 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, and rechargeable lithium battery including same |
| CN110071275A (en) * | 2019-04-23 | 2019-07-30 | 金川集团股份有限公司 | A kind of preparation method coating metal cobaltosic oxide |
| CN113651366A (en) * | 2020-05-12 | 2021-11-16 | 荆门市格林美新材料有限公司 | Secondary calcination preparation method of small-particle-size aluminum-doped cobaltosic oxide |
| CN111646519A (en) * | 2020-07-17 | 2020-09-11 | 衢州华友钴新材料有限公司 | Preparation method of aluminum-doped cobaltosic oxide |
| CN114684865B (en) * | 2020-12-30 | 2023-08-08 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of aluminum-doped cobalt carbonate particles |
| CN113087024B (en) * | 2021-05-12 | 2022-11-11 | 浙江格派钴业新材料有限公司 | Preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide |
| CN115394993A (en) * | 2022-09-16 | 2022-11-25 | 广东邦普循环科技有限公司 | Surface-coated modified cobaltosic oxide and preparation method and application thereof |
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