CN105731551A - Doped cobalt carbonate, doped tricobalt tetroxide and preparation methods thereof - Google Patents
Doped cobalt carbonate, doped tricobalt tetroxide and preparation methods thereof Download PDFInfo
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Abstract
The present invention provides a doped cobalt carbonate preparation method. The preparation method comprises the following steps: cobalt carbonate is prepared; the cobalt carbonate is added into a metal alkoxide solution to be mixed to obtain the cobalt carbonate wrapped by the metal alkoxide; and the wrapped cobalt carbonate is dried to obtain a doped cobalt carbonate. The present invention also provides the doped cobalt carbonate prepared by the doped cobalt carbonate preparation method, a doped tricobalt tetroxide preparation method, and a doped tricobalt tetroxide prepared by the doped tricobalt tetroxide preparation method. The doped cobalt carbonate preparation method and the doped tricobalt tetroxide preparation method can prepare the doped cobalt carbonate and the doped tricobalt tetroxide which are uniform in particle sizes, evenly coated, and large in particle sizes, respectively.
Description
Technical field
The invention belongs to the preparing technical field of cation doping compound, be specifically related to a kind of doping cobalt carbonate, doped cobaltic-cobaltous oxide and preparation method thereof.
Background technology
Spherical cobaltous carbonate is to apply a kind of persursor material the most general in lithium cobalt oxide cathode material for lithium ion battery, cobalt acid lithium is relative to having the advantage that open-circuit voltage height, specific energy are big and are easily-synthesized other positive electrode, and can fast charging and discharging, but it is poor to there is overcharge resistant ability in the cobalt acid lithium prepared with prior art, the shortcoming such as specific capacity reduction rapidly under relatively high charge voltage.In order to improve cobalt acid lithium performance, by adulterate in cobalt acid lithium material Mg, Al etc., existing doping method is that form with co-precipitation adds in cobalt carbonate precursor synthesis process, but the membership that adds of Mg, Al etc. affects balling-up and the particle size growth of cobalt carbonate.
Summary of the invention
The above-mentioned deficiency aiming to overcome that prior art of the embodiment of the present invention, it is provided that a kind of doping cobalt carbonate preparation method, it is possible to the doping cobalt carbonate that preparation is evenly coated.
The another object of the embodiment of the present invention is in that to overcome the above-mentioned deficiency of prior art, it is provided that a kind of doping cobalt carbonate, this doping cobalt carbonate is evenly coated.
The another above-mentioned deficiency aiming to overcome that prior art of the embodiment of the present invention, it is provided that a kind of doped cobaltic-cobaltous oxide preparation method, it is possible to the doped cobaltic-cobaltous oxide that preparation is evenly coated.
A further object of the embodiment of the present invention is in that to overcome the above-mentioned deficiency of prior art, it is provided that a kind of doped cobaltic-cobaltous oxide, this doped cobaltic-cobaltous oxide is evenly coated.
In order to realize foregoing invention purpose, the technical scheme of the embodiment of the present invention is as follows:
A kind of doping cobalt carbonate preparation method, comprises the steps:
Prepare cobalt carbonate；
Described cobalt carbonate is joined metal alkoxide solution is mixed to get the cobalt carbonate being coated with described metal alkoxide；
Described cobalt carbonate after cladding is dried and obtains doping cobalt carbonate.
A kind of doping cobalt carbonate adopting above-mentioned doping cobalt carbonate preparation method to prepare, described doping cobalt carbonate is with cobalt carbonate for core, and metal alkoxide is coated on described 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 under nitrogen atmosphere, roasting 3～10h prepares doped cobaltic-cobaltous oxide.
And, a kind of doped cobaltic-cobaltous oxide adopting above-mentioned doped cobaltic-cobaltous oxide preparation method to prepare.
The doping cobalt carbonate preparation method of above-described embodiment, by separately performed for the process of preparing cobalt carbonate and doping, easily controllable cobalt carbonate pattern and particle size growth so that the process of doping is without influence on the growth of cobalt carbonate particle, it is possible to preparation uniform particle diameter, 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 decomposed into metal-oxide, is uniformly coated on Cobalto-cobaltic oxide surface in the process that cobalt carbonate roasting is Cobalto-cobaltic oxide, and uniformity is good.
Accompanying drawing explanation
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.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Present example provides a kind of doping cobalt carbonate preparation method, comprises the steps:
Step S01: prepare cobalt carbonate；
Step S02: cobalt carbonate joins in metal alkoxide the cobalt carbonate being mixed to get cladding metal alkoxide, and this process is the process of physical absorption；
Step S03: the cobalt carbonate after cladding is dried and obtains doping cobalt carbonate.
The doping cobalt carbonate preparation method of above-described embodiment, by separately performed for the process of preparing cobalt carbonate and doping, make the process of doping without influence on the growth of cobalt carbonate particle, it is easy to control cobalt carbonate pattern and particle size growth, it is possible to preparation uniform particle diameter, be evenly coated, the doping cobalt carbonate of big particle diameter.
Specifically, metal alkoxide solution is at least one in Diethoxymagnesium solution, aluminum ethylate. solution and titanium ethanolate solution, then doping cobalt carbonate is mix at least one cobalt carbonate in Mg, Al and Ti.
Specifically, the process of step S01 comprises the following specific steps that:
Step S01-1: with pure water and ammonium hydrogen carbonate for end liquid, the carbonate concentration controlling to be hydrolyzed in the end liquid generation is 3～5g/L, and temperature is 30～65 DEG C；
Step S01-2: preparation cobalt salt concentration is the cobalt salt solution of 60～180g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 100～300g/L；
Step S01-3: according to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2～1:3, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring；
Step S01-4: washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate, and the moisture of the cobalt carbonate after dehydration is less than 5%.
Carbonate in step S01 is that bicarbonate ion hydrolysis produces.The process of step S01 can carry out in a kettle., is namely first added in reactor by end liquid, then cobalt salt solution and ammonium bicarbonate soln reaction mass are joined reaction kettle for reaction.
In step S01-1, the selection gist of temperature is: if lower than 30 DEG C, then grain growth is slow and intercrystalline is easily assembled；Higher than 65 DEG C, then grain growth is too fast, is unfavorable for size controlling.Additionally, ammonium hydrogen carbonate raises with temperature more easily decomposes (NH4HCO3=NH3+H2O+CO2), decompose the ammonia that produces easily with cobalt complexation, thus decreasing the generation quantity of nucleus, making cobalt source be prone on existing granule growth, affecting size controlling.Adding ammonium hydrogen carbonate in end liquid makes end liquid be alkalescence.When cobalt salt solution joins in end liquid, owing to end liquid having substantial amounts of ammonium hydrogen carbonate, easily generate substantial amounts of thin nucleus, be beneficial to the growth course controlling cobalt carbonate.
In step S01-3, by controlling the mol ratio of cobalt salt and ammonium hydrogen carbonate, it is possible to make cobalt salt molecule and ammonium hydrogen carbonate molecule in system be fully contacted reaction.
In step S01-4, adjusting follow-up saturated extent of adsorption by controlling the moisture of cobalt carbonate, thus controlling the cobalt carbonate ratio of adsorption to Mg, Al and Ti, drying steps saves time and the energy simultaneously.
Specifically, step S01-3 adopts the mode of control by stages technological parameter to carry out, it is simple to control pattern and the particle diameter of cobalt carbonate, 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 is 50～300L/h, the flow of ammonium bicarbonate soln is 100～800L/h, pH is 7.6～7.8, temperature is 30～65 DEG C, the rotating speed of stirring is 100～220r/min, it is preferred to 100～200r/min, and keeping solid content in course of reaction is 300～1000g/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 30～300L/h, the flow of ammonium bicarbonate soln is 50～800L/h, being preferably 50～700L/h, pH is 7.2～7.8, it is preferred to 7.2～7.6, temperature is 30～55 DEG C, the rotating speed of stirring is 100～250r/min, it is preferred to 110～250r/min, isolates mother solution, retaining solid continued growth, keeping solid content in course of reaction is 600～1200g/L.Generally, by flow-control, 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, it is preferred to 50～700L/h, pH is 7.0～7.8, being preferably 7.1～7.6, temperature is 30～50 DEG C, and the rotating speed of stirring is 100～300r/min, being preferably 120～300r/min, control solid content is 800～1400g/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 18 μm, the flow of cobalt salt solution is 10～300L/h, the flow of ammonium bicarbonate soln is 10～800L/h, pH is 6.8～7.8, temperature is 30～55 DEG C, and the rotating speed of stirring is 100～220r/min, and control solid content is 1000～1600g/L.Adding surfactant in reaction system, adding quality is 0.1～1% of the cobalt quality in cobalt carbonate.
The above-mentioned process preparing cobalt carbonate adopts the process conditions such as control by stages reactant flow, pH, temperature and/or solid content so that cobalt carbonate substep growth, it is easy to control pattern and the particle diameter of cobalt carbonate.
Reaction initial period, it is necessary to substantial amounts of granule growth substrate (nucleus), cobalt carbonate slowly grows at nucleating surface, just can obtain highdensity cobalt carbonate, at a high ph, ammonium hydrogen carbonate is significantly excessive, it is possible to accelerate the generation of cobalt carbonate, but pH value is higher than 7.8, nucleus can be assembled in a large number, affects its pattern and density, for preventing nucleus from assembling, within the scope of above-mentioned pH, need to adopt compared with strong mixing and relatively low solid content.
React mid-term, when cobalt carbonate particle diameter grows to certain value, reduce pH value in reaction, and reduce inlet amount, it is prevented that generate new nucleus, make the material of follow-up addition only grow on the surface of existing cobalt carbonate, along with the carrying out of reaction, in reaction system, solid content increases, and stirring intensity can be made to reduce.In order to ensure its stirring intensity, speed of agitator can be increased.
In the reaction later stage, when particle diameter grows to certain limit, granule surface activity reduces, and hinders the continued growth of granule, it is easy to form new growing point, produces small grains.In order to suppress the generation of fine particle, in reaction system, add a certain amount of surfactant, reduce material charging rate simultaneously further.
Specifically, in step S02, in cobalt carbonate, in cobalt and metal alkoxide, the ratio of the mole of metal is 1:0.001～1:0.1.Such as, if being only doped with single metal Mg, Al or Ti, then in cobalt carbonate the mole of the Mg in cobalt and Diethoxymagnesium than for 1:0.001～1:0.1；And/or, in cobalt carbonate, the mole of the Al in cobalt and aluminum ethylate. is than for 1:0.001～1:0.1；And/or, in cobalt carbonate, the mole of the Ti in cobalt and titanium ethanolate is than for 1:0.001～1:0.1.
Specifically, in the process of the mixing of step S02, stirring cobalt carbonate and metal alkoxide solution 3～10 hours at normal temperatures.
Stirring can make metal alkoxide, and particularly Diethoxymagnesium, aluminum ethylate. and titanium ethanolate are evenly coated, and the length of mixing time affects cobalt carbonate cladding metal alkoxide, the particularly amount of Diethoxymagnesium, aluminum ethylate. and titanium ethanolate, thus affecting the effect of doping.If mixing time was less than 3 hours, then it is coated with insufficient；If mixing time is longer than 10 hours, then easily make local cladding too much.
Specifically, in the process of step S03, dry temperature is 60～200 DEG C.The alcohol, particularly ethanol that produce in dry run can reclaim use.
Under this baking temperature, metal alkoxide decomposition goes out alcohol, and metal is stayed on cobalt carbonate particle, for instance, Diethoxymagnesium, aluminum ethylate. and/or titanium ethanolate decomposite ethanol, and magnesium, aluminum and/or titanium are retained on cobalt carbonate particle；If higher than this temperature cobalt carbonate, easily decomposing.
The embodiment of the present invention adopts doping cobalt carbonate prepared by said method to be with cobalt carbonate for core, and metal alkoxide is coated on cobalt carbonate surface.This metal alkoxide can be at least one in Diethoxymagnesium, aluminum ethylate. and titanium ethanolate.
The embodiment of the present invention adopts the doping cobalt carbonate that said method prepares to be mix at least one cobalt carbonate in Mg, Al and Ti, and wherein, the gross mass of Mg, Al and/or Ti accounting in doping cobalt carbonate is 0.1%～10%.Such as, if being only doped with single metal, then the quality accounting of Mg is 0.1%～10%；And/or, the quality accounting of Al is 0.1%～10%；And/or, the quality accounting of Ti is 0.1%～10%.
Cobalt carbonate prepared by the present invention is mainly as the persursor material of lithium ion battery material cobalt acid lithium, and cobalt acid lithium has compacted density height, charging/discharging voltage advantages of higher, but there is the deficiencies such as poor heat stability；Foreign metal, particularly the addition of the element such as Mg, Al and Ti can improve the performance of cobalt acid lithium, when the addition of Mg, Al and Ti is respectively less than 0.1%, the lifting of performance is limited, but when the addition of Mg, Al and Ti is above 10%, the hydraulic performance decline such as density of cobalt acid lithium can be caused, therefore, select Mg, the addition of Al and Ti is 0.1%-10%.
The embodiment of the present invention additionally provides a kind of doped cobaltic-cobaltous oxide preparation method, by above-mentioned doping cobalt carbonate at 300～800 DEG C, and oxygen or under nitrogen atmosphere, roasting 3～10h prepares doped cobaltic-cobaltous oxide.Preferably this doping cobalt carbonate is mix at least one cobalt carbonate in Mg, Al and Ti, then doped cobaltic-cobaltous oxide is mix at least one Cobalto-cobaltic oxide in Mg, Al and Ti.
The embodiment of the present invention additionally provides a kind of doped cobaltic-cobaltous oxide adopting above-mentioned doped cobaltic-cobaltous oxide preparation method to prepare.Preferably this doped cobaltic-cobaltous oxide is mix at least one Cobalto-cobaltic oxide in Mg, Al and Ti.
The doped cobaltic-cobaltous oxide preparation method of above-described embodiment, metal alkoxide, particularly Diethoxymagnesium, aluminum ethylate., titanium ethanolate decomposition temperature are low, the roasting process of cobalt carbonate is decomposed into metal-oxide, such as magnesium oxide, aluminium oxide, titanium oxide can be uniformly coated on Cobalto-cobaltic oxide surface, and uniformity is good.
Illustrate below by way of multiple embodiments.
Embodiment 1
Step S01: prepare cobalt carbonate.The process of step S01 comprises the following specific steps that:
Step S01-1: preparation end liquid.
With pure water and ammonium hydrogen carbonate for end liquid, controlling carbonate concentration in end liquid is 3g/L, and temperature is 48 DEG C.
Step S01-2: preparation cobalt salt solution and ammonium bicarbonate soln.
Preparation cobalt salt concentration is the cobalt salt solution of 60g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 100g/L.
Step S01-3: prepare cobalt carbonate wet feed.
According to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring.
Step S01-4: washing, dehydration cobalt carbonate wet feed.
Washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate.The moisture of the cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 carries out stage by stage, specific as follows:
At the initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution is 300L/h, and the flow of ammonium bicarbonate soln is 100L/h, pH is 7.6, and temperature is 43 DEG C, and the rotating speed of stirring is 100r/min, and keeping solid content in course of reaction 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, the flow of ammonium bicarbonate soln is 100L/h, pH is 7.2, and temperature is 36 DEG C, the rotating speed of stirring is 110r/min, isolating mother solution, retain solid continued growth, keeping solid content in course of reaction is 900g/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 15 μm, the flow of cobalt salt solution is 50L/h, the flow of ammonium bicarbonate soln is 100L/h, pH is 7.1, and temperature is 36 DEG C, the rotating speed of stirring is 120r/min, and control solid content is 900g/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 18 μm, the flow of cobalt salt solution is 10L/h, the flow of ammonium bicarbonate soln is 10L/h, pH is 7.1, and temperature is 36 DEG C, the rotating speed of stirring is 100r/min, control solid content is 1100g/L, and adding surfactant PVP, PVP, to add quality be in cobalt carbonate the 0.1% of cobalt quality.
In step S01, the apparent density of the cobalt carbonate of preparation is more than 1.6g/cm3。
Step S02: cobalt carbonate is joined the cobalt carbonate being mixed to get cladding Diethoxymagnesium in Diethoxymagnesium solution.With stir process in the process of mixing, stirring cobalt carbonate and Diethoxymagnesium solution 3 hours at normal temperatures.Wherein, in cobalt carbonate the mole of the Mg in cobalt and Diethoxymagnesium than for 1:0.001.
Step S03: being dried at 100 DEG C by the cobalt carbonate after cladding and obtain mixing the cobalt carbonate of Mg, the quality of Mg accounting in doping cobalt carbonate is 0.1%.
Embodiment 2
Step S01: prepare cobalt carbonate.The process of step S01 comprises the following specific steps that:
Step S01-1: preparation end liquid.
With pure water and ammonium hydrogen carbonate for end liquid, controlling carbonate concentration in end liquid is 5g/L, and temperature is 36 DEG C.
Step S01-2: preparation cobalt salt solution and ammonium bicarbonate soln.
Preparation cobalt salt concentration is the cobalt salt solution of 180g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 300g/L.
Step S01-3: prepare cobalt carbonate wet feed.
According to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:3, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring.
Step S01-4: washing, dehydration cobalt carbonate wet feed.
Washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate.The moisture of the cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 carries out stage by stage, specific as follows:
At the initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution is 300L/h, and the flow of ammonium bicarbonate soln is 800L/h, pH is 7.8, and temperature is 43 DEG C, and the rotating speed of stirring is 200r/min, and keeping solid content in course of reaction 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, the flow of ammonium bicarbonate soln is 700L/h, pH is 7.6, and temperature is 55 DEG C, the rotating speed of stirring is 220r/min, isolating mother solution, retain solid continued growth, keeping solid content in course of reaction 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 15 μm, the flow of cobalt salt solution is 300L/h, the flow of ammonium bicarbonate soln is 600L/h, pH is 7.5, and temperature is 50 DEG C, the rotating speed of stirring is 220r/min, and control solid content is 1400g/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 18 μm, the flow of cobalt salt solution is 280L/h, the flow of ammonium bicarbonate soln is 500L/h, pH is 7.8, and temperature is 55 DEG C, the rotating speed of stirring is 220r/min, control solid content is 1600g/L, and adding surfactant PVP, PVP, to add quality be in cobalt carbonate the 1% of cobalt quality.
In step S01, the apparent density of the cobalt carbonate of preparation is more than 1.6g/cm3。
Step S02: cobalt carbonate is joined the cobalt carbonate being mixed to get cladding aluminum ethylate. and titanium ethanolate in the solution of aluminum ethylate. and titanium ethanolate.With stir process in the process of mixing, stir the solution 10 hours of cobalt carbonate, aluminum ethylate. and titanium ethanolate at normal temperatures.Wherein, in cobalt carbonate, the mole of the aluminum in cobalt and aluminum ethylate. is than for 1:0.05, in cobalt carbonate in cobalt and titanium ethanolate the mole of titanium than for 1:0.05.
Step S03: the cobalt carbonate after cladding dry is obtained mixing the cobalt carbonate of Al and Ti at 120 DEG C, Al in doping cobalt carbonate quality accounting be 0.5%, the quality accounting of Ti is 0.5%.
Embodiment 3
Step S01: prepare cobalt carbonate.The process of step S01 comprises the following specific steps that:
Step S01-1: preparation end liquid.
With pure water and ammonium hydrogen carbonate for end liquid, controlling carbonate concentration in end liquid is 4g/L, and temperature is 40 DEG C.
Step S01-2: preparation cobalt salt solution and ammonium bicarbonate soln.
Preparation cobalt salt concentration is the cobalt salt solution of 100g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 200g/L.
Step S01-3: prepare cobalt carbonate wet feed.
According to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2.5, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring.
Step S01-4: washing, dehydration cobalt carbonate wet feed.
Washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate.The moisture of the cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 carries out stage by stage, specific as follows:
At the initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution is 300L/h, and the flow of ammonium bicarbonate soln is 500L/h, pH is 7.7, and temperature is 43 DEG C, and the rotating speed of stirring is 150r/min, and keeping solid content in course of reaction 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, the flow of ammonium bicarbonate soln is 400L/h, pH is 7.6, and temperature is 43 DEG C, the rotating speed of stirring is 170r/min, isolating mother solution, retain solid continued growth, keeping solid content in course of reaction is 700g/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 15 μm, the flow of cobalt salt solution is 180L/h, the flow of ammonium bicarbonate soln is 400L/h, pH is 7.6, and temperature is 43 DEG C, the rotating speed of stirring is 170/min, and control solid 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 18 μm, the flow of cobalt salt solution is 150L/h, the flow of ammonium bicarbonate soln is 300L/h, pH is 7.6, and temperature is 43 DEG C, the rotating speed of stirring is 180r/min, control solid content is 1200g/L, and adding surfactant PVP, PVP, to add quality be in cobalt carbonate the 0.5% of cobalt quality.
In step S01, the apparent density of the cobalt carbonate of preparation is more than 1.6g/cm3。
Step S02: cobalt carbonate is joined the cobalt carbonate being mixed to get cladding Diethoxymagnesium, aluminum ethylate. and titanium ethanolate in the solution of Diethoxymagnesium, aluminum ethylate. and titanium ethanolate.With stir process in the process of mixing, stir the solution 7 hours of cobalt carbonate, Diethoxymagnesium, aluminum ethylate. and titanium ethanolate at normal temperatures.In cobalt carbonate, the mole of the metal in cobalt and metal alkoxide is than for 1:0.08, wherein, in cobalt carbonate the mole of the Mg in cobalt and Diethoxymagnesium than the mole for cobalt in 1:0.02, cobalt carbonate and the Al in aluminum ethylate. than the mole for cobalt in 1:0.02, cobalt carbonate and the Ti in titanium ethanolate than for 1:0.04.
Step S03: the cobalt carbonate after cladding is dried at 110 DEG C and obtains mixing the cobalt carbonate of Mg, Al and Ti, Mg, Al and Ti gross mass doping cobalt carbonate in accounting be 9.9%, wherein, the quality of Mg accounting in doping cobalt carbonate is 2.4%, the quality of Al accounting in doping cobalt carbonate is 2.7%, and the quality of Ti accounting in doping cobalt carbonate is 4.8%.
As it is shown in figure 1, be the scanning electron microscope (SEM) photograph of the doping cobalt carbonate of the embodiment of the present invention 3.It can be seen that preparation mix Mg, Al and Ti cobalt carbonate spherical in shape, shape and size are uniform.
Embodiment 4
Step S01: prepare cobalt carbonate.The process of step S01 comprises the following specific steps that:
Step S01-1: preparation end liquid.
With pure water and ammonium hydrogen carbonate for end liquid, controlling carbonate concentration in end liquid is 3.5g/L, and temperature is 30 DEG C.
Step S01-2: preparation cobalt salt solution and ammonium bicarbonate soln.
Preparation cobalt salt concentration is the cobalt salt solution of 120g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 180g/L.
Step S01-3: prepare cobalt carbonate wet feed.
According to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2.5, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring.
Step S01-4: washing, dehydration cobalt carbonate wet feed.
Washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate.The moisture of the cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 carries out stage by stage, specific as follows:
At the initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution is 50L/h, and the flow of ammonium bicarbonate soln is 300L/h, pH is 7.7, and temperature is 30 DEG C, and the rotating speed of stirring is 120r/min, and keeping solid content in course of reaction is 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, the flow of ammonium bicarbonate soln is 50L/h, pH is 7.5, and temperature is 30 DEG C, the rotating speed of stirring is 140r/min, isolating mother solution, retain solid continued growth, keeping solid content in course of reaction is 800g/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 15 μm, the flow of cobalt salt solution is 10L/h, the flow of ammonium bicarbonate soln is 20L/h, pH is 7.0, and temperature is 30 DEG C, the rotating speed of stirring is 140r/min, and control solid content is 800g/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 18 μm, the flow of cobalt salt solution is 10L/h, the flow of ammonium bicarbonate soln is 10L/h, pH is 6.8, and temperature is 30 DEG C, the rotating speed of stirring is 150r/min, control solid content is 1000g/L, and adding surfactant PVP, PVP, to add quality be in cobalt carbonate the 0.3% of cobalt quality.
In step S01, the apparent density of the cobalt carbonate of preparation is more than 1.6g/cm3。
Step S02: cobalt carbonate is joined the cobalt carbonate being mixed to get cladding Diethoxymagnesium, aluminum ethylate. and titanium ethanolate in the solution of Diethoxymagnesium, aluminum ethylate. and titanium ethanolate.With stir process in the process of mixing, stir the solution 3 hours of cobalt carbonate, Diethoxymagnesium, aluminum ethylate. and titanium ethanolate at normal temperatures.In cobalt carbonate, the mole of the metal in cobalt and metal alkoxide is than for 1:0.08, wherein, in cobalt carbonate the mole of the Mg in cobalt and Diethoxymagnesium than the mole for cobalt in 1:0.02, cobalt carbonate and the Al in aluminum ethylate. than the mole for cobalt in 1:0.02, cobalt carbonate and the Ti in titanium ethanolate than for 1:0.04.
Step S03: the cobalt carbonate after cladding is dried at 60 DEG C and obtains mixing the cobalt carbonate of Mg, Al and Ti, Mg, Al and Ti gross mass doping cobalt carbonate in accounting be 8.25%, wherein, the quality of Mg accounting in doping cobalt carbonate is 2.0%, the quality of Al accounting in doping cobalt carbonate is 2.25%, and the quality of Ti accounting in doping cobalt carbonate is 4.0%.
Embodiment 5
Step S01: prepare cobalt carbonate.The process of step S01 comprises the following specific steps that:
Step S01-1: preparation end liquid.
With pure water and ammonium hydrogen carbonate for end liquid, controlling carbonate concentration in end liquid is 4.5g/L, and temperature is 65 DEG C.
Step S01-2: preparation cobalt salt solution and ammonium bicarbonate soln.
Preparation cobalt salt concentration is the cobalt salt solution of 160g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 280g/L.
Step S01-3: prepare cobalt carbonate wet feed.
According to cobalt salt in cobalt salt solution and in ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2, cobalt salt solution and ammonium bicarbonate soln stream are joined in end liquid and are obtained by reacting cobalt carbonate wet feed when stirring.
Step S01-4: washing, dehydration cobalt carbonate wet feed.
Washed by cobalt carbonate wet feed, dehydration obtains cobalt carbonate.The moisture of the cobalt carbonate after dehydration is less than 5%.
Wherein, step S01-3 carries out stage by stage, specific as follows:
At the initial stage of the course of reaction of cobalt salt solution and ammonium bicarbonate soln, the flow of cobalt salt solution is 280L/h, and the flow of ammonium bicarbonate soln is 700L/h, pH is 7.8, and temperature is 65 DEG C, and the rotating speed of stirring is 200r/min, and keeping solid content in course of reaction 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, the flow of ammonium bicarbonate soln is 680L/h, pH is 7.6, and temperature is 50 DEG C, the rotating speed of stirring is 250r/min, isolating mother solution, retain solid continued growth, keeping solid content in course of reaction is 1200g/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 15 μm, the flow of cobalt salt solution is 240L/h, the flow of ammonium bicarbonate soln is 650L/h, pH is 7.5, and temperature is 45 DEG C, the rotating speed of stirring is 300r/min, and control solid content is 1300g/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 18 μm, the flow of cobalt salt solution is 220L/h, the flow of ammonium bicarbonate soln is 600L/h, pH is 7.5, and temperature is 50 DEG C, the rotating speed of stirring is 220r/min, control solid content is 1500g/L, and adding surfactant PVP, PVP, to add quality be in cobalt carbonate the 0.8% of cobalt metal quality.
In step S01, the apparent density of the cobalt carbonate of preparation is more than 1.6g/cm3。
Step S02: cobalt carbonate is joined the cobalt carbonate being mixed to get cladding Diethoxymagnesium, aluminum ethylate. and titanium ethanolate in the solution of Diethoxymagnesium, aluminum ethylate. and titanium ethanolate.With stir process in the process of mixing, stir the solution 3 hours of cobalt carbonate, Diethoxymagnesium, aluminum ethylate. and titanium ethanolate at normal temperatures.In cobalt carbonate, the mole of the metal in cobalt and metal alkoxide is than for 1:0.045, wherein, in cobalt carbonate the mole of the Mg in cobalt and Diethoxymagnesium than the mole for cobalt in 1:0.01, cobalt carbonate and the Al in aluminum ethylate. than the mole for cobalt in 1:0.015, cobalt carbonate and the Ti in titanium ethanolate than for 1:0.02.
Step S03: the cobalt carbonate after cladding is dried at 200 DEG C and obtains mixing the cobalt carbonate of Mg, Al and Ti, Mg, Al and Ti gross mass doping cobalt carbonate in accounting be 9.375%, wherein, the quality of Mg accounting in doping cobalt carbonate is 2%, the quality of Al accounting in doping cobalt carbonate is 3.375%, and the quality of Ti accounting in doping cobalt carbonate is 4%.
Embodiment 6
The cobalt carbonate mixing Mg embodiment 1 prepared is at 480 DEG C, and in oxygen atmosphere, roasting 10h obtains mixing the Cobalto-cobaltic oxide of Mg.As in figure 2 it is shown, be the scanning electron microscope (SEM) photograph of the doped cobaltic-cobaltous oxide of embodiments of the invention 6.It can be seen that preparation to mix Mg Cobalto-cobaltic oxide spherical in shape, shape and size are uniform.
Embodiment 7
The cobalt carbonate mixing Al and Ti embodiment 2 prepared is at 530 DEG C, and in oxygen atmosphere, roasting 3h obtains mixing the Cobalto-cobaltic oxide of Al and Ti.
Embodiment 8
Embodiment 3 is prepared mix Mg, Al and Ti cobalt carbonate at 500 DEG C, in oxygen atmosphere, roasting 5h obtains mixing the Cobalto-cobaltic oxide of Mg, Al and Ti.As it is shown on figure 3, be the scanning electron microscope (SEM) photograph of the doped cobaltic-cobaltous oxide of embodiments of the invention 8.It can be seen that preparation mix Mg, Al and Ti Cobalto-cobaltic oxide spherical in shape, shape and size are uniform.
Embodiment 9
Embodiment 4 is prepared mix Mg, Al and Ti cobalt carbonate at 300 DEG C, in oxygen atmosphere, roasting 8h obtains mixing the Cobalto-cobaltic oxide of Mg, Al and Ti.
Embodiment 10
Embodiment 5 is prepared mix Mg, Al and Ti cobalt carbonate at 800 DEG C, in oxygen atmosphere, roasting 4h obtains mixing the Cobalto-cobaltic oxide of Mg, Al and Ti.
In sum, in the preparation method of the doping cobalt carbonate of the embodiment of the present invention, cobalt carbonate preparation is separately performed with metal-doped process, it is easy to control cobalt carbonate pattern and particle size growth.Additionally, the substep growth of cobalt carbonate particle diameter, it is also easy to control pattern and the size of cobalt carbonate.Employing metallorganic adsorbs, and primary sorption amount is big, and simple to operate, cost is low.In the preparation method of the doped cobaltic-cobaltous oxide of the embodiment of the present invention, the decomposition temperature of metal alkoxide is low, is decomposed into metal-oxide and is coated on Cobalto-cobaltic oxide surface in cobalt carbonate roasting process, and the uniformity of cladding is good.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, all should include within protection scope of the present invention.
Claims (10)
1. a doping cobalt carbonate preparation method, it is characterised in that comprise the steps:
Prepare cobalt carbonate；
Described cobalt carbonate is joined metal alkoxide solution is mixed to get the cobalt carbonate being coated with described metal alkoxide；
Described cobalt carbonate after cladding is dried and obtains doping cobalt carbonate.
2. the preparation method of the cobalt carbonate that adulterates as claimed in claim 1, it is characterized in that: described metal alkoxide solution is at least one in Diethoxymagnesium solution, aluminum ethylate. solution and titanium ethanolate solution, described doping cobalt carbonate is mix at least one cobalt carbonate in Mg, Al and Ti.
3. doping cobalt carbonate preparation method as claimed in claim 1 or 2, it is characterised in that the described process preparing cobalt carbonate comprises the steps:
With pure water and ammonium hydrogen carbonate for end liquid, the carbonate concentration controlling to be hydrolyzed in liquid of the described end generation is 3～5g/L, and temperature is 30～65 DEG C；
Preparation cobalt salt concentration is the cobalt salt solution of 60～180g/L, and ammonium bicarbonate concentration is the ammonium bicarbonate soln of 100～300g/L；
According to cobalt salt in described cobalt salt solution and in described ammonium bicarbonate soln the mol ratio of ammonium hydrogen carbonate be 1:2～1:3, described cobalt salt solution and described ammonium bicarbonate soln stream are joined in liquid of the described end, are obtained by reacting cobalt carbonate wet feed when stirring；
Washed by described cobalt carbonate wet feed, dehydration obtains described cobalt carbonate, and the moisture of described cobalt carbonate is less than 5%.
4. doping cobalt carbonate preparation method as claimed in claim 3, it is characterised in that:
The initial stage of described cobalt salt solution and described ammonium bicarbonate soln course of reaction, the flow of described cobalt salt solution is 50～300L/h, the flow of described ammonium bicarbonate soln is 100～800L/h, pH is 7.6～7.8, temperature is 30～65 DEG C, the rotating speed of described stirring is 100～220r/min, and keeping solid content in described course of reaction is 300～1000g/L；
In the course of reaction of described cobalt salt solution and described ammonium bicarbonate soln, when the particle diameter of the described cobalt carbonate wet feed of preparation is 10 μm, the flow of described cobalt salt solution is 30～300L/h, the flow of described ammonium bicarbonate soln is 50～800L/h, pH is 7.2～7.8, and temperature is 30～55 DEG C, the rotating speed of described stirring is 100～250r/min, isolating mother solution, retain solid continued growth, keeping solid content in described course of reaction is 600～1200g/L；
In the course of reaction of described cobalt salt solution and described ammonium bicarbonate soln, when the particle diameter of the described cobalt carbonate wet feed of preparation is 15 μm, the flow of described cobalt salt solution is 10～300L/h, the flow of described ammonium bicarbonate soln is 20～800L/h, pH is 7.0～7.8, temperature is 30～50 DEG C, and the rotating speed of described stirring is 100～300r/min, and controlling described solid content is 800～1400g/L；
In the course of reaction of described cobalt salt solution and described ammonium bicarbonate soln, when the particle diameter of the described cobalt carbonate wet feed of preparation is 18 μm, the flow of described cobalt salt solution is 10～300L/h, the flow of described ammonium bicarbonate soln is 10～800L/h, pH is 6.8～7.8, temperature is 30～55 DEG C, the rotating speed of described stirring is 100～220r/min, controlling described solid content is 1000～1600g/L, and adding surfactant, the addition quality of described surfactant is the 0.1～1% of the quality of the cobalt in described cobalt carbonate.
5. doping cobalt carbonate preparation method as claimed in claim 2, it is characterised in that: in described cobalt carbonate, in cobalt and described metal alkoxide, the ratio of the mole of metal is 1:0.001～1:0.1.
6. doping cobalt carbonate preparation method as claimed in claim 1 or 2, it is characterised in that: with stir process in the process of described mixing, stir described cobalt carbonate and described metal alkoxide solution 3～10 hours at normal temperatures；And/or, described dry temperature is 60～200 DEG C.
7. doping cobalt carbonate prepared by the doping cobalt carbonate preparation method that a kind adopts as described in any one of claim 1～6, it is characterised in that: described doping cobalt carbonate is with cobalt carbonate for core, and metal alkoxide is coated on described cobalt carbonate surface.
8. adulterate cobalt carbonate as claimed in claim 7, it is characterised in that: described doping cobalt carbonate is mix at least one cobalt carbonate in Mg, Al and Ti, and wherein, the gross mass of described Mg, Al and/or Ti accounting in described doping cobalt carbonate is 0.1%～10%.
9. a doped cobaltic-cobaltous oxide preparation method, it is characterised in that: by the doping cobalt carbonate described in claim 7 or 8 at 300～800 DEG C, oxygen or under nitrogen atmosphere, roasting 3～10h prepares doped cobaltic-cobaltous oxide.
10. one kind adopts doped cobaltic-cobaltous oxide prepared by doped cobaltic-cobaltous oxide preparation method as claimed in claim 9.
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