CN109411749A - Mix Al bulky grain cobaltosic oxide with and preparation method thereof - Google Patents
Mix Al bulky grain cobaltosic oxide with and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to battery material field, in particular to one kind mix Al bulky grain cobaltosic oxide with and preparation method thereof.The preparation method of Al bulky grain cobaltosic oxide is mixed the following steps are included: stratum nucleare molten metal is mixed with precipitant solution and carries out multiple crystallization reaction formation nucleus；When the granularity of nucleus reaches preset granularity, shell metallic liquid is mixed with the nucleus for reaching nucleus granularity with the precipitant solution and carries out multiple encapsulation reaction makes nuclei growth；After nuclei growth to final preset granularity, the final slurry that encapsulation reaction obtains is sintered stage by stage.Using unique addition manner, so that shell Al encapsulation ratio is high, the secondary incorporation carried out when avoiding cobalt acid lithium calcining to maintain particle surface structure stability.The sufficiently balanced comprehensive performance and structural stability of material.It is simple that nucleocapsid converts preparation process, it is easy to accomplish.
Description
Technical field
The present invention relates to battery material fields, mix Al bulky grain cobaltosic oxide and its system in particular to one kind
Preparation Method.
Background technique
The fast development of lithium ion battery industry has driven the cobalts such as cobalt acid lithium, lithium nickel cobalt dioxide, nickle cobalt lithium manganate system anode material
The development of material, wherein cobalt acid lithium, discharge capacity and the stability of voltage etc. suffer from satisfactory performance, become
The crucial positive electrode of currently manufactured lithium ion chargeable battery, with the increasingly requirement that consumer is lightening to 3C Product,
The energy density of material needs to continue promotion, and the cobaltosic oxide as lithium cobaltate cathode material presoma, increasingly
As research emphasis.
In order to improve cobalt acid lithium performance, it will usually the additives such as Al are added in positive electrode, in high voltage charge and discharge
Play the role of stable lattice.Traditional lithium cobaltate cathode material generally use mix after cobalt carbonate synthesis Al cladding or
It is mixed when cobalt acid lithium is sintered with lithium carbonate, is then permeated by high-temperature calcination.The uneven distribution of Al is easily caused, no
Conducive to the stabilization of lattice structure.
Summary of the invention
The present invention provides a kind of preparation methods for mixing Al bulky grain cobaltosic oxide to be made using unique addition manner
Obtain the secondary incorporation that shell Al encapsulation ratio is high, carries out when avoiding cobalt acid lithium calcining to maintain particle surface structure stability.
The sufficiently balanced comprehensive performance and structural stability of material.It is simple that nucleocapsid converts preparation process, it is easy to accomplish.
The present invention also provides one kind to mix Al bulky grain cobaltosic oxide, which stablizes.
The present invention is implemented as follows:
A kind of preparation method for mixing Al bulky grain cobaltosic oxide, comprising the following steps:
Stratum nucleare molten metal is mixed with precipitant solution with the flow velocity of 800-1000L/h and repeatedly crystallize anti-
Nucleus should be formed；
When the granularity of nucleus reaches preset granularity, by shell metallic liquid and the precipitant solution with 400-700L/h
Flow velocity mixed with the nucleus for reaching nucleus granularity and carry out multiple encapsulation reaction and make nuclei growth；
After nuclei growth to final preset granularity, the final slurry that encapsulation reaction obtains is sintered stage by stage；
The quality of aluminium is 0.2-0.5g in every liter of stratum nucleare molten metal, and the quality of aluminium is in every liter of shell metallic liquid
0.5-1.0g。
One kind mixing Al bulky grain cobaltosic oxide, passes through the above-mentioned preparation method system for mixing Al bulky grain cobaltosic oxide
It is standby to obtain.
The beneficial effects of the present invention are: the preparation method that the present invention mixes Al bulky grain cobaltosic oxide passes through wet process in front
Synthesis phase mixes aluminium, and adulterated al when rear end being avoided to be sintered ensure that the uniformity of aluminium doping, while be reacted using gradation, after
And realize and adulterate stage by stage, convenient for controlling the doping of aluminium, meanwhile, so that each layer adulterates the aluminium measured, further promoted
The homogeneity of aluminium doping, the secondary incorporation for avoiding cobalt acid lithium from carrying out when calcining to maintain particle surface structure stability.Sufficiently
The balanced comprehensive performance and structural stability of material.And the cobaltosic oxide aluminium doping being prepared is uniform, passes through four oxidations
The lithium cobaltate cathode material of three cobalts preparation, charge and discharge cycles number is high, capacity attenuation is low, improves the service life of battery.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described.
Fig. 1 is that the Al bulky grain cobaltosic oxide SEM that mixes of embodiment 1 schemes；
Fig. 2 is that the Al bulky grain cobaltosic oxide SEM that mixes of embodiment 2 schemes；
Fig. 3 is that the Al bulky grain cobaltosic oxide SEM that mixes of embodiment 3 schemes；
Fig. 4 is that the Al bulky grain cobaltosic oxide SEM that mixes of embodiment 4 schemes；
Fig. 5 is that the Al bulky grain cobaltosic oxide SEM that mixes of comparative example 1 schemes；
Fig. 6 is that the Al bulky grain cobaltosic oxide SEM that mixes of comparative example 2 schemes；
Fig. 7 is that the Al bulky grain cobaltosic oxide SEM that mixes of comparative example 3 schemes；
Fig. 8 is that the Al bulky grain cobaltosic oxide SEM that mixes of comparative example 4 schemes.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the embodiment of the present invention mix Al bulky grain cobaltosic oxide with and preparation method thereof be specifically described.
A kind of preparation method for mixing Al bulky grain cobaltosic oxide, comprising the following steps:
S1, metallic solution and precipitating reagent solvent are prepared respectively:
Respectively using water dissolution cobalt source and silicon source, cobalt source solution and various concentration silicon source solution are obtained then by silicon source and cobalt
Source carries out mixing and respectively obtains stratum nucleare molten metal and shell metallic liquid.
The quality of aluminium is 0.2-0.5g in every liter of stratum nucleare molten metal, and the content of cobalt is in every liter of stratum nucleare molten metal
50-150g, the quality of aluminium is 0.5-1.0g in every liter of shell metallic liquid, and the content of cobalt is in every liter of shell metallic liquid
50-150g,.Molten metal using different proportion is to being doped into aluminium more uniformly in cobalt carbonate lattice.
Cobalt source and silicon source are dissolved respectively, then mixed as a solution, more conducively the two is uniformly mixed,
Guarantee that aluminium can be more uniformly doped in cobaltosic oxide.
Further, cobalt source is cobalt salt, the cobalt salt in cobaltous sulfate, cobalt chloride and cobalt nitrate any one or extremely
It is two kinds few.
Silicon source is aluminium salt, the aluminium salt in aluminum nitrate, aluminum sulfate and aluminium chloride any one or at least two.
Precipitant solution is the solution obtained after mixing precipitating reagent with water, it is preferable that the precipitating reagent is carbonate, more excellent
Choosing, the carbonate be ammonium hydrogen carbonate, ammonium carbonate, sodium carbonate, in sodium bicarbonate any one or at least two.
The concentration of precipitant solution be 150-250g/L, using above-mentioned concentration can guarantee precipitating reagent well with cobalt, aluminium
Precipitating is formed, guarantees yield.
S2, crystallization reaction form nucleus；
The step is nucleus to be formed, and before being reacted, the conduct of 500-1000L precipitant solution is added into reactor
Bottom liquid.Bottom liquid is added, can quickly form precipitating, and wrap up aluminium.
It is then heated to 40-50 DEG C, stratum nucleare molten metal and precipitant solution are with the flow velocity of 800-1000L/h, and with simultaneously
The mode of stream is mixed, and liquid is stirred in mixed process.
Metallic solution is mixed by the way of cocurrent with precipitant solution, can be further ensured that in precipitant solution
Carbanion can be fully uniformly mixed with cobalt, the aluminium in metallic solution, then guarantee be prepared four oxidation three
Aluminium element is evenly distributed in cobalt.
Crystallization reaction for the first time is then carried out, is separated by solid-liquid separation after crystallization reaction 2.5-3.5 hours for the first time, it is preliminary in this time
Nucleus is formed, but nucleus granularity is smaller, is unfavorable for the doping of aluminium and the stabilization of cobaltosic oxide performance.
Separation of solid and liquid obtains the first slurry, then by first slurry again with the stratum nucleare molten metal and the precipitating reagent
Solution mixes and carries out circulation crystallization reaction, when relatively described first slurry of granularity for working as the nucleus that circulation crystallization reacts
When granularity increases 0.5-2 microns, it is separated by solid-liquid separation, obtains the second slurry；
Second slurry repeats the circulation crystallization reaction, until the granularity of the nucleus in isolated slurry reaches
Preset granularity；Aluminium is added using aforesaid way, can guarantee that the doping of each layer of aluminium is uniform, more conducively cobaltosic oxide
The performance of energy.
Meanwhile the growth of each nucleus granularity is controlled, and increase every time all the same, the doping of aluminium can be further controlled,
And guarantee the property of nucleus.
The reaction condition of reaction condition and crystallization reaction for the first time in circulation crystallization reaction process, by ceaselessly separating reaction
Liquid obtains slurry, and slurry is reacted with stratum nucleare molten metal with the precipitant solution, is conducive to the doping of aluminium, while preceding
Just adulterated al when face forms precipitating can guarantee the uniformity of aluminium doping, be also beneficial to the granularity for the nucleus that control is formed.
When carrying out crystallization reaction for the first time, the pH of reaction solution is 7.5-8.5, mixing speed 60-90r/min, and use is above-mentioned
Reaction condition can guarantee that nucleus is smoothly formed, and guarantee that aluminium equably adulterates.
S3, encapsulation reaction is carried out；
Form nucleus when carrying out multiple crystallization reaction, and the granularity of the nucleus reach wrap up after preset granularity it is anti-
It answers, nucleus is further grown up.
Specifically, the shell metallic liquid is reached with the flow velocity of 400-700L/h with described with the precipitant solution
The nucleus of nucleus granularity, which mixes and carries out multiple encapsulation reaction, makes nuclei growth.The step carries out outside molding nucleus
Not all rightly, it wraps up repeatedly, then expands the granularity of nucleus.
The quality of aluminium is 0.5-1.0g in every liter of shell metallic liquid.Using the aluminium of aforementioned proportion range, system can guarantee
The doping of aluminium is suitable in the shell of standby obtained cobaltosic oxide.
Multiple encapsulation reaction is that the nucleus for reaching presetting granularity that will be obtained after S2 and shell metallic liquid sink with described
Shallow lake agent solution mixes and carries out package crystallization reaction, when the granularity of nucleus that package crystallization reaction obtains is relative to reaching default grain
When the granularity of the nucleus of degree increases 0.5-2 microns, it is separated by solid-liquid separation, obtains the first package slurry；
Then the first package slurry and the shell metallic liquid and the precipitant solution repeat package crystallization reaction.
The first package slurry is mixed and carried out with the shell metallic liquid with the precipitant solution according to the condition of encapsulation reaction
Reaction is precipitated and is successively wrapped up so that shell metallic liquid reacts to be formed with precipitating reagent, and adulterated al in encapsulation process.
By controlling the batch of shell metallic liquid and the precipitant solution and slurry reaction, it can effectively control and to grow up
The granularity of nucleus, so that obtained nucleus granularity is more uniform.
Encapsulation reaction occurs for each slurry and shell metallic liquid and the precipitant solution, so that the grain of the nucleus in slurry
It is consistent to spend amount of increase, can guarantee that the structure for four cobalt oxides being prepared is more stable, and can be improved the encapsulation ratio of aluminium, also be promoted
The distributing homogeneity of aluminium.
Further, the reaction condition of package crystallization reaction is all the same every time, and the pH of reaction solution is 7.0-7.5, reaction temperature
Degree is 50-60 DEG C, mixing speed 60-90r/min.
By the condition of control package crystallization reaction, shell metallic liquid and the precipitant solution are enabled to and containing crystalline substance
The slurry reaction of core constantly wraps up existing nucleus, then expands the granularity of nucleus, and guarantee the uniform of nucleus granularity
Property, avoid the secondary incorporation carried out when cobalt acid lithium calcining for maintenance particle surface structure stability.
If the condition of change package crystallization reaction, such as the consistent of the condition of crystallization and multiple crystallization reaction is wrapped up,
It will lead to and constantly form new nucleus, and only a small amount of substance wraps up existing nucleus, so that nucleus size distribution is uneven
One, meanwhile, influence the doping of aluminium.
Further, it whether carries out the multiple crystallization reaction of S2 or carries out the multiple encapsulation reaction of this step, anti-
The solid content in control reaction solution (mixed liquor of molten metal, precipitant solution and slurry) should be required in the process, work as reaction solution
In solid content when reaching 500-600g/L, the reaction solution of 1/3-1/2 volume is removed, remaining reaction solution then continues more
Secondary crystallization reaction or multiple encapsulation reaction.And the reaction solution of the 1/3-1/2 volume removed carries out repeatedly in empty reaction kettle
Crystallization reaction or multiple encapsulation reaction.Control the solid content in reaction solution, be because after solid content reaches 500-600g/L,
The long speed of crystal grain can be slower and slower, removes to reaction solution, " nucleus " of reservation can continue to grow, and guarantee the uniform of crystal grain
The speed of growth.
S4, calcining；
It obtains growing up to the nucleus of final preset granularity after multiple encapsulation reaction, then reaction solution is separated
Obtain final slurry, the solid matter in final slurry is the nucleus for meeting final preset granularity, then to final slurry into
Row washing and centrifugal treating, the water temperature of washing are 50-80 DEG C, can then guarantee treatment effect, can be by the salt of grain surface
Solution washes away.
It then carries out sublevel section calcining and the final slurry is specifically sintered 2.0- in the environment of 250-450 DEG C
4.0 hour；Then calcined 2.0-5.0 hours in the environment of 600-800 DEG C again.Since vapor can be generated in calcination process
With the gases such as carbon dioxide, the gas that vapor and decomposition obtain acts on simultaneously and solid, to the biggish impact force of crystal grain generation,
It is damaged to be easy to cause grain surface, or then aluminum oxide is unevenly precipitated.Therefore, it is calcined stage by stage, for the first time
Calcining removal vapor, calcines reaction of decomposing for the second time, excludes gas stage by stage, reduces impact of the gas to crystal grain, protects
The complete of the structure of crystal grain is demonstrate,proved, while the temperature of catabolic phase is unsuitable excessively high, temperature is excessively high to be easy to cause aluminum oxide uneven
Ground is precipitated, and then influences the doping of aluminium.
The embodiment of the present invention provides one kind and mixes Al bulky grain cobaltosic oxide, mixes the oxidation of Al bulky grain four three by above-mentioned
The preparation method of cobalt is prepared.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The Al bulky grain cobalt carbonate of design of the embodiment of the present invention --- the final preset granularity of nucleus is 21 microns, and pre-
If granularity be 17 microns.
The present embodiment provides a kind of preparation methods for mixing Al bulky grain cobaltosic oxide, comprising the following steps:
S1, metallic solution and precipitating reagent solvent are prepared respectively:
It is utilized respectively deionized water dissolving aluminum sulfate and cobalt chloride, then mixes aluminum sulfate solution and cobalt chloride solution,
Stratum nucleare molten metal and shell metallic liquid respectively.Wherein, the content of aluminium is 0.3g/L in stratum nucleare molten metal, and the content of cobalt is 90g/L；
The content of aluminium is 0.6g/L in shell metallic liquid, and the content of cobalt is 90g/L.In deionized water by ammonium bicarbonate solubility, so that
The concentration of precipitant solution is 220g/L.
S2, crystallization reaction form nucleus；
In 10m3500L ammonium bicarbonate soln is added in reaction kettle, by stratum nucleare metallic solution and heavy after being then warming up to 40 DEG C
Shallow lake agent solution mixes in manner of cocurrent flow and carries out crystallization reaction for the first time.Wherein, reaction condition are as follows: the flow of stratum nucleare metallic solution
For 800L/h, precipitant solution flow is 900L/h, mixing speed 60r/min, pH 7.5.After reaction 2.5-3.5 hours,
Reaction solution is separated by solid-liquid separation, the first slurry is obtained；
Then the first slurry mixes with stratum nucleare metallic solution with precipitant solution again and carries out circulation crystallization and reacts, when first
The granularity of crystal grain in slurry carries out reaction solution after increasing 0.5-2 microns to be separated by solid-liquid separation the second slurry；
Second slurry is mixed and is reacted with stratum nucleare metallic solution with precipitant solution again, the crystal grain in the first slurry
Granularity increase 0.5-2 micron after reaction solution is separated by solid-liquid separation, the second slurry repetitive cycling crystallization reaction, so constantly instead
It is multiple, until the granularity of the crystal grain in slurry reaches 17 microns.The condition that crystallization reaction and circulation crystallization react for the first time is identical.
When carrying out circulation crystallization reaction, when the solid content in reaction solution reaches 500g/L, by the reaction solution of 1/3 volume
It removes, remaining reaction solution then continues circulation crystallization reaction.
S3, encapsulation reaction is carried out；
By shell metallic liquid with 600L/h, precipitant solution is mixed with the flow velocity cocurrent of 700L/h, is added to crystalline substance
The granularity of core has reached in 17 microns of slurry and carries out package crystallization reaction, after the granularity of nucleus increases 0.5-2 microns, into
Row is separated by solid-liquid separation and obtains the first package slurry；
First package slurry is mixed with the shell metallic liquid with the precipitant solution and carries out package crystallization reaction again,
After the nucleus granularity in the first package slurry increases 0.5-2 microns, it is separated by solid-liquid separation, the slurry being separated by solid-liquid separation repeats
Crystallization reaction is wrapped up, until reaction obtains the nucleocapsid difference that partial size is 21um and mixes Al bulky grain cobalt carbonate, be separated by solid-liquid separation
To final slurry.
Wrap up the condition of crystallization reaction are as follows: the pH of reaction solution is 7.3, and reaction temperature is 55 DEG C, mixing speed 60r/
Min, the reaction time 2.5 hours.
When carrying out package crystallization reaction, when the solid content in reaction solution reaches 500g/L, by the reaction solution of 1/3 volume
It removes, remaining reaction solution then continues to wrap up crystallization reaction.
S4, sublevel section calcining；
Firstly, final slurry is washed and is centrifuged, the water temperature of washing is 50 DEG C, and the water content of slurry is little after centrifugation
In 10.0%.It then at a temperature of 250 DEG C, is sintered 2 hours, then at a temperature of 700 DEG C, is sintered 2 hours.
The present embodiment provides one kind to mix Al bulky grain cobaltosic oxide, passes through the above-mentioned Al bulky grain cobaltosic oxide mixed
Preparation method is prepared.
Embodiment 2-4
The intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide and embodiment 1 that embodiment 2-4 is provided provide
The intermittent preparation method basic operation for mixing aluminium little particle spherical cobaltic-cobaltous oxide it is consistent, difference is, concrete operations condition
It changes.
Embodiment 2
Cobalt source is cobalt nitrate, and silicon source is aluminium chloride, in stratum nucleare metallic solution cobalt ions and aluminium ion be respectively 100g/L with
0.2g/L, cobalt ions and aluminium ion are respectively 100g/L and 1.0g/L in shell metallic solution, and precipitating reagent is sodium carbonate, precipitating reagent
Solution concentration is 150g/L.
The amount of the precipitant solution of bottom liquid is 800L, forms the crystallization reaction for the first time of nucleus and the temperature of circulation crystallization reaction
It is 46 DEG C, the flow velocity of stratum nucleare metallic solution is 900L/h, and precipitant solution flow velocity is 850L/h, mixing speed 90r/min,
PH is 8, is separated by solid-liquid separation after crystallization reaction 3-3.5 hours for the first time, and the amount of increase that circulation crystallization reacts each granularity is 1-2 micro-
Rice/time.
When the solid content of reaction solution reaches 600g/L, the reaction solution of 1/2 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
The condition of encapsulation reaction are as follows: the flow velocity of shell metallic solution is 500L/h, and precipitant solution flow velocity is 650L/h, is stirred
Mixing speed is 90r/min, and pH 7.3, temperature is 60 DEG C, and the package each granularity amount of increase of crystallization reaction is 1-2 micron/time.
When the solid content of reaction solution reaches 600g/L, the reaction solution of 1/2 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
Be sintered stage by stage: wash temperature is 60 DEG C, at a temperature of 300 DEG C, is sintered 3 hours, then at a temperature of 600 DEG C,
Sintering 4 hours.
Embodiment 3
Cobalt source is cobalt chloride, and silicon source is aluminum sulfate, in stratum nucleare metallic solution cobalt ions and aluminium ion be respectively 150g/L with
0.4g/L, cobalt ions and aluminium ion are respectively 150g/L and 0.9g/L in shell metallic solution, and precipitating reagent is sodium bicarbonate, precipitating
Agent solution concentration is 250g/L.
The amount of the precipitant solution of bottom liquid is 600L, forms the crystallization reaction for the first time of nucleus and the temperature of circulation crystallization reaction
It is 50 DEG C, the flow velocity of stratum nucleare metallic solution is 1000L/h, and precipitant solution flow velocity is 1000L/h, mixing speed 80r/
Min, pH 8.5 is separated by solid-liquid separation after crystallization reaction 2.5-3 hours for the first time, and the amount of increase that circulation crystallization reacts each granularity is
0.5-1.5 micron/time.
When the solid content of reaction solution reaches 550g/L, the reaction solution of 1/2 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
The condition of encapsulation reaction are as follows: the flow velocity of shell metallic solution is 400L/h, and precipitant solution flow velocity is 400L/h, is stirred
Mixing speed is 70r/min, and pH 7.2, temperature is 58 DEG C, the package each granularity amount of increase of crystallization reaction is 0.5-1.5 microns/
It is secondary.
When the solid content of reaction solution reaches 550g/L, the reaction solution of 1/2 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
Be sintered stage by stage: wash temperature is 80 DEG C, at a temperature of 450 DEG C, is sintered 2.5 hours, then in 800 DEG C of temperature
Under, it is sintered 3 hours.
Embodiment 4
Cobalt source is cobaltous sulfate, and silicon source is aluminum nitrate, in stratum nucleare metallic solution cobalt ions and aluminium ion be respectively 120g/L with
0.5g/L, cobalt ions and aluminium ion are respectively 120g/L and 0.5g/L in shell metallic solution, and precipitating reagent is ammonium carbonate, precipitating reagent
Solution concentration is 200g/L.
The amount of the precipitant solution of bottom liquid is 1000L, forms the crystallization reaction for the first time of nucleus and the temperature of circulation crystallization reaction
Degree is 42 DEG C, and the flow velocity of stratum nucleare metallic solution is 900L/h, and precipitant solution flow velocity is 800L/h, mixing speed 70r/
Min, pH 7.8 is separated by solid-liquid separation after crystallization reaction 2.7-3.2 hours for the first time, and the amount of increase that circulation crystallization reacts each granularity is equal
For 0.8-1.3 micron/time.
When the solid content of reaction solution reaches 570g/L, the reaction solution of 1/3 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
The condition of encapsulation reaction are as follows: the flow velocity of shell metallic solution is 450L/h, and precipitant solution flow velocity is 600L/h, is stirred
Mixing speed is 80r/min, and pH 7.1, temperature is 56 DEG C, and the package each granularity amount of increase of crystallization reaction is 0.8-1.3 micron/time.
When the solid content of reaction solution reaches 570g/L, the reaction solution of 1/3 volume is removed, remaining reaction solution then continue into
The reaction of row circulation crystallization.
Be sintered stage by stage: wash temperature is 70 DEG C, at a temperature of 400 DEG C, is sintered 4 hours, then at a temperature of 750 DEG C,
Sintering 5 hours.
Comparative example 1: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is at a temperature of 250 DEG C, burns
Knot 4 hours.
Comparative example 2: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is at a temperature of 700 DEG C, burns
Knot 4 hours.
Comparative example 3: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is when the crystal grain in slurry
Granularity reach 17 microns after, still allow and circulation crystallization reaction carried out to slurry, the condition of circular response is stratum nucleare metallic solution
Flow is 1000L/h, and precipitant solution flow is 900L/h, mixing speed 60r/min, pH 7.0, reaction time and implementation
The time for the encapsulation reaction that example 1 provides is identical.
Comparative example 4: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is in every liter of stratum nucleare gold
The quality for belonging to aluminium in liquid is 1.0g.
Comparative example 5: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is in every liter of shell gold
The quality for belonging to aluminium in liquid is 0.1g.
D10, D50, D90, D100 of the cobaltosic oxide that measurement embodiment 1-4 and comparative example 1-5 is prepared and vibration
Real density, specific testing result is referring to table 1.
1 testing result of table
According to table 1, sublevel section calcining is not used, and sintering degree is unstable, obtained cobaltosic oxide TD fluctuation
Greatly.The reaction condition of the embodiment of the present invention is changed, the cobalt carbonate particle of preparation is excessively fine and close, and TD is higher.The change present invention is implemented
The content of aluminium, TD are remarkably decreased in the metallic solution of example.
(SEM) detection is carried out to embodiment 1-4 and comparative example 1-5, testing result is respectively referring to Fig. 1-Fig. 8, figure-Fig. 8
Embodiment 1- embodiment 4 and comparative example 1-4's mixes Al bulky grain cobaltosic oxide SEM detection figure.
According to Fig. 1-Fig. 8 it is found that 1. after solid content increase, reaction system is also easy to produce new " nucleus ", with the small of free state
Particle form exists；2. with core, shell aluminium content raising, the cobalt carbonate of formation and sintered cobalt oxide particle surface
Al distributing homogeneity have certain reduction.
It is utilized respectively the cobaltosic oxide preparation cobalt acid lithium of embodiment 1-4 and comparative example 1-5, preparation cobalt acid lithium is using existing
Prepared by technology, then can be carried out detection to the electrochemistry of cobalt acid lithium, testing result is referring to table 2.
2 chemical property of table
By improving the additive amount of Al known to table 3, be conducive to the capacity and cycle life that improve material to a certain extent.
In conclusion the preparation method that the present invention mixes Al bulky grain cobaltosic oxide is mixed by the Moist chemical synthesis stage in front
Enter aluminium, adulterated al when rear end being avoided to be sintered ensure that the uniformity of aluminium doping, while using reacting by several times, then realize sublevel
Section doping, convenient for controlling the doping of aluminium, meanwhile, so that each layer adulterates the aluminium measured, further promote the equal of aluminium doping
One property, the secondary incorporation for avoiding cobalt acid lithium from carrying out when calcining to maintain particle surface structure stability.Sufficiently balanced material
Comprehensive performance and structural stability.And the cobaltosic oxide aluminium doping being prepared is uniform, is prepared by cobaltosic oxide
Lithium cobaltate cathode material, charge and discharge cycles number is high, capacity attenuation is low, improves the service life of battery.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for mixing Al bulky grain cobaltosic oxide, which comprises the following steps:
Stratum nucleare molten metal is mixed with precipitant solution with the flow velocity of 800-1000L/h and carries out multiple crystallization reaction shape
At nucleus；
When the granularity of nucleus reaches preset granularity, by shell metallic liquid and the precipitant solution with the stream of 400-700L/h
Speed, which mixes with the nucleus for reaching nucleus granularity and carries out multiple encapsulation reaction, makes nuclei growth；
After nuclei growth to final preset granularity, the final slurry that encapsulation reaction obtains is sintered stage by stage；
The quality of aluminium is 0.2-0.5g in every liter of stratum nucleare molten metal, and the quality of aluminium is 0.5- in every liter of shell metallic liquid
1.0g。
2. the preparation method according to claim 1 for mixing Al bulky grain cobaltosic oxide, which is characterized in that repeatedly crystallization is anti-
Should the stratum nucleare molten metal be mixed with the precipitant solution with the flow velocity of 800-1000L/h and is crystallized for the first time instead
It answers, is separated by solid-liquid separation after crystallization reaction 2.5-3.5 hours for the first time, obtain the first slurry；
First slurry is mixed with the stratum nucleare molten metal with the precipitant solution again then and to carry out circulation crystallization anti-
It answers, when the granularity of relatively described first slurry of the granularity for the nucleus that circulation crystallization reacts increases 0.5-2 microns, consolidate
Liquid separation, obtains the second slurry；
Second slurry repeats the circulation crystallization reaction, until the granularity of the nucleus in isolated slurry reaches default
Granularity after carry out encapsulation reaction.
3. the preparation method according to claim 1 for mixing Al bulky grain cobaltosic oxide, which is characterized in that repeatedly package is anti-
Should form multiple crystallization reaction to reach the nucleus of presetting granularity and mix and go forward side by side with the precipitant solution with shell metallic liquid
Row package crystallization reaction, when the granularity for the nucleus that package crystallization reaction obtains increases relative to the granularity for the nucleus for reaching presetting granularity
It when 0.5-2 microns long, is separated by solid-liquid separation, obtains the first package slurry；
Then the first package slurry and the shell metallic liquid and the precipitant solution repeat the package crystallization reaction.
4. the preparation method according to claim 2 for mixing Al bulky grain cobaltosic oxide, which is characterized in that tied for the first time
Before crystalline substance reaction, to reactor addition 500-1000L precipitant solution as bottom liquid.
5. the preparation method according to claim 1 for mixing Al bulky grain cobaltosic oxide, which is characterized in that carrying out repeatedly
During crystallization reaction or the multiple encapsulation reaction of progress, when the solid content in reaction solution reaches 500-600g/L, by 1/
The reaction solution of volume removes, and remaining reaction solution then continues to react.
6. the preparation method according to claim 1 for mixing Al bulky grain cobaltosic oxide, which is characterized in that repeatedly crystallization is anti-
At once, the pH of reaction solution is 7.5-8.5, and reaction temperature is 40-50 DEG C, mixing speed 60-90r/min.
7. the preparation method according to claim 6 for mixing Al bulky grain cobaltosic oxide, which is characterized in that repeatedly package is anti-
At once, the pH of reaction solution is 7.0-7.5, and reaction temperature is 50-60 DEG C, mixing speed 60-90r/min.
8. the preparation method according to claim 1 for mixing Al bulky grain cobaltosic oxide, which is characterized in that be sintered stage by stage
It is to be sintered the final slurry 2.0-4.0 hours in the environment of 250-450 DEG C；Then again in the environment of 600-800 DEG C
Calcining 2.0-5.0 hours.
9. the preparation method according to claim 8 for mixing Al bulky grain cobaltosic oxide, which is characterized in that carry out stage by stage
The final slurry is washed and is centrifuged before sintering.
10. one kind mixes Al bulky grain cobaltosic oxide, which is characterized in that it is mixed by described in any one of claim 1-9
The preparation method of Al bulky grain cobaltosic oxide is prepared.
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