CN110040790A - A kind of high sphericity nickel-cobalt-manganese ternary presoma and preparation method thereof - Google Patents
A kind of high sphericity nickel-cobalt-manganese ternary presoma and preparation method thereof Download PDFInfo
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- CN110040790A CN110040790A CN201910353455.4A CN201910353455A CN110040790A CN 110040790 A CN110040790 A CN 110040790A CN 201910353455 A CN201910353455 A CN 201910353455A CN 110040790 A CN110040790 A CN 110040790A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- 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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- C01P2004/32—Spheres
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Abstract
A kind of high sphericity nickel-cobalt-manganese ternary presoma and preparation method thereof, it is characterized by: nickel cobalt manganese mixing salt solution, enveloping agent solution and hard microballoon suspension are added in reaction bottom liquid in a manner of at the uniform velocity cocurrent, keeping the slurry gross mass percentage that accounts for of hard microballoon is 2% ~ 25%.The present invention is in chemical coprecipitation reaction system, by adding hard microballoon, and under strong stirring action, to increase nickel-cobalt-manganese ternary presoma product collision frequency during the growth process and collision frequency, promote little particle nickel-cobalt-manganese ternary presoma in shorter growth time, just form higher sphericity, utilizes natural subsidence after reaction, by the hard microballoon suspension and pulp separation, high sphericity nickel-cobalt-manganese ternary presoma is obtained with this.Hard microballoon of the present invention is reusable, since the nickel-cobalt-manganese ternary presoma product sphericity prepared is high, increases the compacted density of product, is conducive to the volume energy density for promoting subsequent positive electrode.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high sphericity nickel-cobalt-manganese ternary presoma and its
Preparation method.
Background technique
Lithium ion battery is rapidly developed from latter stage in last century becomes research hotspot, obtains in telecommunications and Vehicular battery field
Extensive approval is arrived.The positive electrode of lithium ion battery not only occupies 25% or more of battery totle drilling cost, but also directly influences
The performances such as battery capacity, circulation and safety, therefore be the key that in battery technology one of with core.Lithium ion battery is occupied at present
The positive electrode in market mainly includes cobalt acid lithium, LiMn2O4, ternary material, LiFePO4.Cobalt acid lithium material is chiefly used in small-sized height
Electronic equipment is held, there is high cost, and overcharge security risk in the presence of certain.The specific capacity of LiMn2O4, high temperature circulation
It is poor with storge quality, also the development phase is being explored on how to promote the comprehensive performance of such material.LiFePO4 electric conductivity
Can be bad low with product repeatability, there has been no good solutions at present.
Ternary nickel cobalt manganese anode material is a kind of novel anode material occurred in recent years, will be far below tradition in cost
Lithium cobaltate cathode material, and energy density is higher than lithium iron phosphate positive material, just because of ternary nickel cobalt manganese anode material
Advantage of lower cost, comprehensive performance are good, therefore more and more enterprises have started the heat for studying the tertiary cathode material in recent years
Tide.To meet the needs of energy density and power density is continuously improved in automobile power cell, the appearance of material how is further promoted
Amount, it will be the important subject of the tertiary cathode material.
In ternary nickel cobalt manganese anode material, ternary precursor technology is even more core place.In tertiary cathode material forerunner
In many synthetic methods of body, coprecipitation method is strong to the controllability of product, can during the reaction to a variety of conditions (pH value,
Ammonia density, solid content, feed liquor flow, reaction atmosphere and temperature etc.) it is adjusted, to control the pattern and ruler of presoma product
It is very little.Wherein, the sphericity of presoma product directly influences the tap density of product, to influence the electrochemistry of positive electrode
Performance, therefore precursor spherical degree how is further increased as research hotspot in the prior art.
Chinese patent CN108615868A discloses one application No. is 201810473691.5, a kind of entitled " spherical shape
Degree is high and the nickel-cobalt-manganese ternary material precursor and its preparation method and application of the low impurity of surface compact " application for a patent for invention.
The invention is that the presoma product sphericity that granularity D50 is 10 ~ 15 μm is synthesized under the conditions of 62 ~ 78 DEG C by coprecipitation method
Well.Since growth time of the big granularity presoma product in reaction kettle is longer, often there is good sphericity, but it is small
The molding time of particle precursor body is shorter, and often sphericity is not good enough, therefore how to improve little particle precursor spherical degree is ability
The difficult point in domain.
Summary of the invention
In view of the situation of the above-mentioned prior art, the present invention provides a kind of high sphericity nickel-cobalt-manganese ternary presoma and its preparation
Method, it is often spherical its purpose is to solve nickel-cobalt-manganese ternary precursor preparation small particles presoma since molding time is short
Not good enough problem is spent, to improve little particle precursor spherical degree.
In order to achieve the above objectives, the method for the present invention the technical solution adopted is that: a kind of high sphericity nickel-cobalt-manganese ternary forerunner
The preparation method of body, innovation are: the following steps are included:
Hard microballoon and the water of preprepared moulding are sufficiently mixed, hard microballoon are dispersed in water, is obtained by the first step
To hard microballoon suspension, wherein the quality of the hard microballoon accounts for the 2%-25% of hard microballoon suspension quality.
The hard microballoon is nonmetallic microballoon, and at least meets following condition:
(1) spheroidal, and average particle size (i.e. average grain diameter) is 10-30 μm；
(2) averag density is greater than or equal to 0.65 g/cm3, while being less than or equal to 1.00 g/cm3；
(3) surface hardness is shore hardness 50-90HD；
(4) not soluble in water, while not dissolving in alkali.
A part of hard microballoon suspension is put into chemical coprecipitation reaction unit, precipitating reagent is then added by second step
The PH that sodium hydroxide or/and potassium hydroxide solution adjust hard microballoon suspension in reaction unit is 11.5-13, obtains reaction bottom
Liquid.
Nickel cobalt manganese mixing salt solution and enveloping agent solution are added in the liquid of the reaction bottom by third step in a manner of cocurrent,
And be sufficiently stirred and carry out chemical coprecipitation reaction, reaction carries out under inert gas shielding state, and reaction temperature is at 35-80 DEG C；
During the reaction, the pH value that reaction system is maintained by being continuously added sodium hydroxide or/and potassium hydroxide solution is 11.5-
13, while during the reaction, hard is kept by being continuously added hard microballoon or another part hard microballoon suspension
Microballoon accounts for the 2%-25% of reaction system gross mass；The enveloping agent solution is ammonium salt solution.
4th step, after reaction, the hard microballoon of removal reacting rear material upper layer floating carried out remaining slurry
Filter cake is filtered or be centrifugally separating to obtain, then the filter cake is rinsed with water to pH value and is in neutrality, is finally dried, obtaining has high sphericity
Nickel-cobalt-manganese ternary presoma.
In order to achieve the above objectives, product of the present invention the technical solution adopted is that: a kind of high sphericity nickel-cobalt-manganese ternary forerunner
Body, innovation are: the high sphericity nickel-cobalt-manganese ternary presoma obtained according to the above-mentioned preparation method of the present invention.
The related content and change interpretation of above-mentioned technical proposal are as follows:
1. in above scheme, the hard microballoon is solid spherosome perhaps hollow spheres or for by external sheath inner core
Spherosome.
2. in above scheme, the hard microballoon is polymer microballoon.The polymer microballoon be polyethylene, polypropylene and
One of polystyrene is a variety of.
3. in above scheme, the hard microballoon averag density is in 0.65 ~ 1.00 g/cm3, preferably 0.85 ~ 1.00 g/
cm3。
4. in above scheme, being carried out in chemical coprecipitation reaction process in third step, it is desirable that hard microballoon is kept to account for reaction
The 2%-25% of system gross mass, preferably 3%-20%, most preferably 5%-15%.It is required that reaction temperature is at 35-80 DEG C, preferably 40-
60 DEG C, most preferably 45-55 DEG C.It is required that maintaining the pH value of reaction system for 11.5-13, preferably 11.7-12.9, most preferably
12.2-12.8.It is required that the speed of stirring is 600 ~ 1000rpm.
5. in above scheme, salt-mixture that the nickel cobalt manganese mixing salt solution is configured by nickel sulfate, cobaltous sulfate and manganese sulfate
Solution, the ammonium salt solution ammonium sulfate or ammonium hydroxide.
6. in above scheme, after four-step reaction, reacting rear material is stood 1-4 hours, allows nickel-cobalt-manganese ternary
After presoma sedimentation, then remove the hard microballoon of reacting rear material upper layer floating.
Design feature and beneficial effect of the invention is: in chemical coprecipitation reaction system, by adding sphericity
Higher hard microballoon, and under strong stirring action, Lai Zengjia nickel-cobalt-manganese ternary presoma product touching during the growth process
Frequency and collision frequency are hit, to promote little particle nickel-cobalt-manganese ternary presoma in shorter growth time, is just formed higher
Sphericity, then hard microballoon can be separated using natural sedimentation, and can be recycled.The present invention solves small
Particle nickel-cobalt-manganese ternary presoma is since growth time is short, and often the not good enough problem of molding sphericity, small due to what is prepared
Particle nickel-cobalt-manganese ternary presoma product sphericity is high, increases the compacted density of product, is conducive to promote subsequent positive electrode
Volume energy density.
Detailed description of the invention
Fig. 1 is the SEM(scanning electron microscope of comparative example nickel-cobalt-manganese ternary presoma of the present invention) picture；
Fig. 2 is the SEM(scanning electron microscope of 1 nickel-cobalt-manganese ternary presoma of the embodiment of the present invention) picture；
Fig. 3 is the SEM(scanning electron microscope of 2 nickel-cobalt-manganese ternary presoma of the embodiment of the present invention) picture；
Fig. 4 is the SEM(scanning electron microscope of 3 nickel-cobalt-manganese ternary presoma of the embodiment of the present invention) picture.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments:
A kind of comparative example 1: preparation method of nickel-cobalt-manganese ternary presoma
Step (1) in reaction kettle plus pure water 100L, opens stirring in 800rpm, 8mol/L sodium hydroxide solution tune is then added
The PH for saving solution in reaction kettle is 12.5, obtains reaction bottom liquid.
Step (2), the nickel cobalt manganese mixed sulfate solution of 2mol/L and 2mol/L ammonium sulfate is equal by metering pump
Speed be added reaction bottom liquid, wherein in raw material metal nickel cobalt manganese mole coefficient ratio for 8:1:1, ammonium ion and metal from
The molar ratio of son is 0.2；Supplying 8mol/L sodium hydroxide solution control process pH value simultaneously is 12.5 ± 0.1；In reaction unit
It is passed through nitrogen protection, is kept stirring speed in 800rpm and reaction unit temperature at 50 DEG C.
The slurry that the step (2) obtains after reacting 20h, is carried out centrifugal treating and obtains filter cake by step (3), then
It rinses through water to the filter cake and is in neutrality, be finally dried in vacuo 8 hours at 150 DEG C, obtain ternary precursor, be named as product
A1。
A kind of embodiment 1: preparation method of high sphericity nickel-cobalt-manganese ternary presoma
Ultrasonic disperse in 10L pure water is added in 6kg high ball-type degree polyethylene microballoon by step (1), wherein the polyethylene microballoon
Average particle size is 20 μm, density 0.9g/cm3；It opens stirring and adds pure water 90L in 800rpm, reaction kettle, be then added
The PH that 8mol/L sodium hydroxide solution adjusts suspension in reaction kettle is 12.5, obtains reaction bottom liquid.
Step (2), by the nickel cobalt manganese mixed sulfate solution of 2mol/L, 2mol/L ammonium sulfate and the high poly- second of ball-type degree
Reaction bottom liquid is added in alkene microballoon average rate, and wherein the mole coefficient ratio of metal nickel cobalt manganese is 8:1:1, ammonium ion in raw material
Molar ratio with metal ion is 0.2, and the mass percent that the microballoon accounts for slurry is 5% ~ 6%；8mol/L hydrogen-oxygen is supplied simultaneously
Changing sodium solution control process pH value is 12.5 ± 0.1；Nitrogen protection is passed through in reaction unit, be kept stirring speed in 800rpm and
Reaction unit temperature is at 50 DEG C.
Step (3), after reacting 20h, the slurry that the step (2) is obtained settles 1 ~ 4h, the floating of removal upper layer
After polyethylene microballoon, carries out centrifugal treating and obtain filter cake, then rinse through water to the filter cake and be in neutrality, it is finally true at 150 DEG C
Sky is 8 hours dry, obtains ternary precursor, is named as product B1.
A kind of embodiment 2: preparation method of high sphericity nickel-cobalt-manganese ternary presoma
Ultrasonic disperse in 10L pure water is added, wherein the polyethylene microballoon in 10kg high ball-type degree polyethylene microballoon by step (1)
Average particle size be 20 μm, density 0.9g/cm3；It opens stirring and adds pure water 90L in 800rpm, reaction kettle, be then added
The PH that 8mol/L sodium hydroxide solution adjusts suspension in reaction kettle is 12.5, obtains reaction bottom liquid.
Step (2), by the nickel cobalt manganese mixed sulfate solution of 2mol/L, 2mol/L ammonium sulfate and the high poly- second of ball-type degree
Reaction bottom liquid is added in alkene microballoon average rate, and wherein the mole coefficient ratio of metal nickel cobalt manganese is 8:1:1, ammonium ion in raw material
Molar ratio with metal ion is 0.2, and the mass percent that the microballoon accounts for slurry is 9% ~ 10%；8mol/L hydrogen-oxygen is supplied simultaneously
Changing sodium solution control process pH value is 12.5 ± 0.1；Nitrogen protection is passed through in reaction unit, be kept stirring speed in 800rpm and
Reaction unit temperature is at 50 DEG C.
Step (3), after reacting 20h, the slurry that the step (2) is obtained settles 1 ~ 4h, the floating of removal upper layer
After polyethylene microballoon, carries out centrifugal treating and obtain filter cake, then rinse through water to the filter cake and be in neutrality, it is finally true at 150 DEG C
Sky is 8 hours dry, obtains ternary precursor, is named as product B2.
A kind of embodiment 3: preparation method of high sphericity nickel-cobalt-manganese ternary presoma
Ultrasonic disperse in 10L pure water is added, wherein the polyethylene microballoon in 15kg high ball-type degree polyethylene microballoon by step (1)
Average particle size be 20 μm, density 0.9g/cm3；It opens stirring and adds pure water 90L in 800rpm, reaction kettle, be then added
The PH that 8mol/L sodium hydroxide solution adjusts suspension in reaction kettle is 12.5, obtains reaction bottom liquid.
Step (2), by the nickel cobalt manganese mixed sulfate solution of 2mol/L, 2mol/L ammonium sulfate and the high poly- second of ball-type degree
Reaction bottom liquid is added in alkene microballoon average rate, and wherein the mole coefficient ratio of metal nickel cobalt manganese is 8:1:1, ammonium ion in raw material
Molar ratio with metal ion is 0.2, and the mass percent that the microballoon accounts for slurry is 13% ~ 14%；8mol/L hydrogen is supplied simultaneously
Sodium hydroxide solution control process pH value is 12.5 ± 0.1；It is passed through nitrogen protection in reaction unit, is kept stirring speed in 800rpm
With reaction unit temperature at 50 DEG C.
Step (3), after reacting 20h, the slurry that the step (2) is obtained settles 1 ~ 4h, the floating of removal upper layer
After polyethylene microballoon, carries out centrifugal treating and obtain filter cake, then rinse through water to the filter cake and be in neutrality, it is finally true at 150 DEG C
Sky is 8 hours dry, obtains ternary precursor, is named as product B3.
Properties of sample parameter in 1 comparative example of table and embodiment 1-3:
In conjunction with table 1 and Fig. 1-4 as can be seen that addition polyethylene microballoon can be obvious in the preparation process of nickel-cobalt-manganese ternary presoma
Improvement product sphericity, and in reaction process polyethylene microballoon content improve products obtained therefrom sphericity get over
Good, the improvement of presoma product sphericity helps to improve the tap density of product.
It is explained as follows below for other performances of the invention and variation:
1. in above embodiments 1-3, the hard microballoon uses polythene material using high ball-type degree polyethylene microballoon
Made solid spherosome.But the present invention is not limited to this, and from the point of view of structure and construction, hard microballoon of the present invention is in addition to reality
Heart spherosome and it is outer, can be hollow spheres, for example be hollow corrosion-resistant nonmetallic bead, hollow glass pellet etc.
Deng.It is also possible to by the spherosome of external sheath inner core, than the inner core if any a lightweight, surface is covered with corrosion-resistant nonmetallic
Shell etc..
From the point of view of material, hard microballoon of the present invention in addition to using polyethylene and other than, polypropylene, polyphenyl can also be used
The other polymeric materials such as ethylene, polyamide (nylon), ethylene-vinyl alcohol copolymer (EVOH), polymethyl methacrylate.When
When the density of the polymer material of use is greater than 1.00 g/cm3, it can be mixed by the modification to the material or with other materials
It closes to meet upper density limit for the requirement less than or equal to 1.00 g/cm3, can also be reduced by the way of hollow structure hard
The averag density of matter microballoon is met the requirements.In addition, hard microballoon can also use other Erosion-Resisting Non-metallic Materials, such as glue
Wood etc..
In addition, the hard microballoon of different materials can also be used simultaneously in the present invention is implemented.
In short, in the present invention, as long as the nonmetallic microballoon of hard microballoon, and meet following condition and can answer
For the present invention, and obtains identical and similar technical effect (this is that those skilled in the art hold upon reading this disclosure
It is readily understood and know):
(1) spheroidal, and average particle size (i.e. average grain diameter) is 10-30 μm；
(2) averag density is greater than or equal to 0.65 g/cm3, while being less than or equal to 1.00 g/cm3；
(3) surface hardness is shore hardness 50-90HD；
(4) not soluble in water, while not dissolving in alkali.
2. in above embodiments 1-3, hard microballoon is using high ball-type degree polyethylene microballoon, and average particle size is 20 μ
M, density 0.9g/cm3.But the present invention is not limited to this, and actually the average particle size of the hard microballoon is (flat in the present invention
Equal partial size) in 10-30 μ m, same or similar technology may be implemented in 0.65 ~ 1.00 g/cm3 range in averag density
Effect, preferably 0.85 ~ 1.00 g/cm3.This be those skilled in the art according to the present invention content it will be appreciated that and cognition feelings
Condition.
3. in above embodiments 1-3, it is different that hard microballoon accounts for reaction system total mass ratio, wherein embodiment 1 is 5-
6%, embodiment 2 is 9-10%, and embodiment 3 is 13-14%.In conjunction with table 1 and Fig. 1-4 as can be seen that with polyethylene in reaction process
The sphericity that the content of microballoon improves products obtained therefrom is better.According to conclusions it can be concluded that, it is anti-in chemical coprecipitation of the present invention
During answering, the 2%-25% for keeping hard microballoon to account for reaction system gross mass can obtain same or similar technical effect,
This is the situation of change skilled addressee readily understands that with cognition.For the present invention, hard microballoon is accounted for instead
The system total mass ratio of answering is preferably 3%-20%, most preferably 5%-15%.
4. in above embodiments 1-3, the reaction temperature of chemical coprecipitation reaction of the present invention is 50 DEG C.But the present invention does not limit to
In this, actually reaction temperature, which can control, can obtain same or similar technical effect at 35-80 DEG C, this is this field
Technical staff it will be appreciated that and cognition the case where.In the present invention, reaction temperature is preferably 40-60 DEG C, and most preferably 45-55 DEG C.
5. in above embodiments 1-3, it is 12.5 ± 0.1 that the pH value of reaction system is maintained in chemical coprecipitation reaction.But this
Invent not limited to this, the pH value of actually maintenance reaction system is that 11.5-13 can obtain same or similar technology effect
Fruit, this be skilled artisans appreciate that and cognition the case where.In the present invention, the pH value for maintaining reaction system is preferably
11.7-12.9, most preferably 12.2-12.8.
6. in above embodiments 1-3, the mixing speed that chemical coprecipitation reaction process uses is in 800rpm.But the present invention is not
It is confined to this, actually 600 ~ 1000rpm of mixing speed can obtain same or similar technical effect, this is this field skill
Art personnel it will be appreciated that and cognition the case where.
7. in above embodiments 1-3, salt-mixture that nickel cobalt manganese mixing salt solution is configured by nickel sulfate, cobaltous sulfate and manganese sulfate
Solution, wherein the mole coefficient ratio of metal nickel cobalt manganese is 8:1:1 type in raw material.But the present invention is not limited to this, 6:2:2 type,
5:2:3 type, 4:2:4 type etc. can be applied to the present invention, and obtain same or similar technical effect, this is art technology
Personnel it will be appreciated that and cognition the case where.And the nickel cobalt manganese mixing salt solution is chlorate, sulfate, the nitrate of nickel cobalt manganese
The mixing salt solutions prepared according to a certain percentage of one or more.
8. in above embodiments 1-3, the ammonium salt solution uses ammonium sulfate, ammonium hydroxide etc. also can be used.
9. in above embodiments 1-3, chemical coprecipitation reaction carries out under nitrogen protection state, can also be in argon gas or helium
It is carried out under the inert gas shieldings state such as gas.This be skilled artisans appreciate that and cognition the case where.
10. in above embodiments 1-3, high ball-type degree polyethylene microballoon being added in pure water and is dispersed using ultrasonic wave.
But the present invention is not limited to this, wherein pure water is readily modified as deionized water or distilled water.And ultrasonic wave dispersion is readily modified as stirring
Dispersion.This be skilled artisans appreciate that and cognition the case where.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high sphericity nickel-cobalt-manganese ternary presoma, it is characterised in that: the following steps are included:
Hard microballoon and the water of preprepared moulding are sufficiently mixed, hard microballoon are dispersed in water, is obtained by the first step
To hard microballoon suspension, wherein the quality of the hard microballoon accounts for the 2%-25% of hard microballoon suspension quality；
The hard microballoon is nonmetallic microballoon, and at least meets following condition:
(1) spheroidal, and average particle size is 10-30 μm；
(2) averag density is greater than or equal to 0.65 g/cm3, while being less than or equal to 1.00 g/cm3；
(3) surface hardness is shore hardness 50-90HD；
(4) not soluble in water, while not dissolving in alkali；
Second step puts into a part of hard microballoon suspension in chemical coprecipitation reaction unit, and precipitating reagent hydrogen-oxygen is then added
Change sodium or/and potassium hydroxide solution adjusts the PH of hard microballoon suspension in reaction unit as 11.5-13, obtains reaction bottom liquid；
Nickel cobalt manganese mixing salt solution and enveloping agent solution are added in the liquid of the reaction bottom in a manner of cocurrent, and filled by third step
Stirring is divided to carry out chemical coprecipitation reaction, reaction carries out under inert gas shielding state, and reaction temperature is at 35-80 DEG C；Anti-
During answering, it is 11.5-13 that the pH value of reaction system is maintained by being continuously added sodium hydroxide or/and potassium hydroxide solution,
Simultaneously during the reaction, hard microballoon is kept by being continuously added hard microballoon or another part hard microballoon suspension
Account for the 2%-25% of reaction system gross mass；The enveloping agent solution is ammonium salt solution；
4th step, after reaction, removal reacting rear material upper layer floating hard microballoon, remaining slurry is filtered or
It is centrifugally separating to obtain filter cake, then the filter cake is rinsed with water to pH value and is in neutrality, is finally dried, the nickel with high sphericity is obtained
Cobalt-manganese ternary presoma.
2. preparation method according to claim 1, it is characterised in that: the hard microballoon is solid spherosome or hollow
Spherosome, or for by the spherosome of external sheath inner core.
3. preparation method according to claim 1 or 2, it is characterised in that: the hard microballoon is polymer microballoon.
4. preparation method according to claim 3, it is characterised in that: the polymer microballoon be polyethylene, polypropylene and
One of polystyrene is a variety of.
5. preparation method according to claim 1, it is characterised in that: the averag density is greater than or equal to 0.85 g/
Cm3, while being less than or equal to 1.00 g/cm3.
6. preparation method according to claim 1, it is characterised in that: carry out chemical coprecipitation reaction process in third step
In, keep hard microballoon to account for the 3%-20% of reaction system gross mass, reaction temperature maintains the pH value of reaction system at 40-60 DEG C
For 11.7-12.9.
7. preparation method according to claim 6, it is characterised in that: carry out chemical coprecipitation reaction process in third step
In, keep hard microballoon to account for the 5%-15% of reaction system gross mass, reaction temperature maintains the pH value of reaction system at 45-55 DEG C
For 12.2-12.8, the speed of stirring is 600 ~ 1000rpm.
8. preparation method according to claim 1, it is characterised in that: the nickel cobalt manganese mixing salt solution is by nickel sulfate, sulphur
The mixing salt solution of sour cobalt and manganese sulfate configuration, the ammonium salt solution ammonium sulfate or ammonium hydroxide.
9. preparation method according to claim 1, it is characterised in that: after four-step reaction, by reacting rear material
1-4 hours are stood, after allowing nickel-cobalt-manganese ternary presoma to settle, then removes the hard microballoon of reacting rear material upper layer floating.
10. a kind of high sphericity nickel-cobalt-manganese ternary presoma, it is characterised in that: obtained according to preparation method described in claim 1
High sphericity nickel-cobalt-manganese ternary presoma.
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