CN106784784A - A kind of nickel cobalt manganese presoma and preparation method thereof - Google Patents
A kind of nickel cobalt manganese presoma and preparation method thereof Download PDFInfo
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- CN106784784A CN106784784A CN201510815143.2A CN201510815143A CN106784784A CN 106784784 A CN106784784 A CN 106784784A CN 201510815143 A CN201510815143 A CN 201510815143A CN 106784784 A CN106784784 A CN 106784784A
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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
- H01M4/50—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
- 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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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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 invention provides a kind of nickel cobalt manganese presoma, the nickel cobalt manganese presoma be by formula be NixCoyMn1-x-yThe primary particle and formula of M are M '@NixCoyMn1-x-yThe second particle that the primary particle of M is piled up；Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.Compared with prior art, the nickel cobalt manganese presoma that the present invention is provided is optimized by coprecipitation reaction, pattern, particle diameter and the accumulation effect of primary particle are efficiently controlled, the second particle with tap density higher has been obtained, so as to be conducive to the lifting of lithium ion battery energy density.Test result indicate that, the tap density of the nickel cobalt manganese presoma that the present invention is provided is in 2.3g/cm3More than.
Description
Technical field
It is to be related to a kind of nickel cobalt manganese forerunner more specifically the present invention relates to technical field of lithium ion
Body and preparation method thereof.
Background technology
Lithium ion battery has been widely used for the two of the digital products such as mobile phone, notebook computer as a kind of
Primary cell, with discharge voltage it is high, security is good, discharge and recharge long lifespan and advantages of environment protection.Mesh
Before, the anode material for lithium-ion batteries of large-scale commercial production includes cobalt acid lithium, LiMn2O4, phosphorus
Sour iron lithium and ternary material.Wherein, but cobalt acid lithium specific discharge capacity is higher expensive and security performance
It is poor；LiFePO4 has a safety feature but material uniformity is poor；But ternary material is moderate pacifies
Full poor-performing；And LiMn2O4 has discharge voltage high, cheap, rich reserves, security performance high
The advantages of, the main development direction as anode material for lithium-ion batteries.But, manganate cathode material for lithium
High temperature cyclic performance is poor, limits application of the manganate cathode material for lithium in electrokinetic cell and energy storage field.And
Nickle cobalt lithium manganate has the advantages that specific capacity is high, heat endurance is good, as a kind of most potential lithium ion
Cell positive material, has good application prospect in dynamic fields such as electric automobiles.
At present, nickle cobalt lithium manganate (LiNi is preparedxCoyMn1-x-yO2) common method have high temperature solid-state method and
Co-precipitation-high temperature solid-state method.Wherein, high temperature solid-state method is by raw materials such as lithium source, nickel source, cobalt source and manganese sources
Ball milling mixing is uniform, then carries out high-temperature calcination, and the shortcoming of the method is to be difficult to mix three kinds of elements of nickel cobalt manganese
Close uniform, therefore the synergy of three cannot be given full play to, cause the specific capacity of material to be difficult to normally
Play, and material morphology prepared by this method is difficult to control to, and the powder body material granule-morphology for generally synthesizing is not
Rule, the bulk density of this kind of material is low, poor fluidity, is unfavorable for the making of positive electrode, and hindering should
The practical application of class material；And co-precipitation-high temperature solid-state method passes through to prepare nickel cobalt manganese presoma first, then will
Nickel cobalt manganese presoma carries out high-temperature calcination after mixing with lithium source, can effectively solve the problem that what high temperature solid-state method was present
Shortcoming.
But, the tap density of the nickel cobalt manganese presoma that prior art is prepared is not high, limit lithium from
The lifting of sub- battery energy density.
The content of the invention
In view of this, it is an object of the invention to provide a kind of nickel cobalt manganese presoma and preparation method thereof, this
Inventing the nickel cobalt manganese presoma for providing has tap density higher.
The invention provides a kind of nickel cobalt manganese presoma, the nickel cobalt manganese presoma be by formula be formula (I)
Primary particle and formula for formula (II) primary particle pile up second particle；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH) 22-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
Preferably, the nucleator of the nucleator including physical absorption, the nucleator of ionic adsorption and self solve
One or more in release nucleator.
Preferably, the formula is that the particle diameter of the primary particle of formula (I) is 1 μm~7 μm；
The formula is for the particle diameter ratio of the primary particle that primary particle and the formula of formula (I) are formula (II)
(0.1~0.4)：1.
Present invention also offers a kind of preparation method of nickel cobalt manganese presoma, comprise the following steps：
A) nickel source, cobalt source, manganese source, precipitating reagent and complexing agent are mixed, carries out coprecipitation reaction, obtained
Formula is the primary particle of formula (I)；Precipitating reagent includes the salt containing carbonate, the salt containing bicarbonate radical and contains
One or more in salt hydroxy；
B) formula is carried out into secondary precipitation reaction for the primary particle of formula (I) mixes with nucleator, is obtained
Nickel cobalt manganese presoma；
The nickel cobalt manganese presoma is for the primary particle and formula of formula (I) are the one of formula (II) by formula
The second particle of secondary particle packing；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
Preferably, described complexing agent is the one kind in ammoniacal liquor, ammonium hydrogen carbonate, ammonium phosphate and phosphoric acid hydrogen ammonia
Or it is various.
Preferably, the process that coprecipitation reaction is carried out described in step a) is specially：
The mixed solution of nickel source, cobalt source and manganese source is mixed with precipitating reagent and complexing agent, is reacted, obtained
It is the primary particle of formula (I) to formula.
Preferably, nickel ion, cobalt ions and manganese ion total molal quantity and complexing agent in the mixed solution
The ratio between molal quantity be 2：(0.5~1.5).
Preferably, the pH value reacted described in step a) is 7.5~9.5, and the time is 1h~50h.
Preferably, formula described in step b) is 1 with the mol ratio of nucleator for the primary particle of formula (I)：
(0.001~0.5).
Preferably, the time of the reaction of secondary precipitation described in step b) is 8h~24h.
The invention provides a kind of nickel cobalt manganese presoma, the nickel cobalt manganese presoma is to be by formula
NixCoyMn1-x-yThe primary particle and formula of M are M '@NixCoyMn1-x-yThe primary particle of M pile up and
Into second particle；Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；
X+y ＜ 1；The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.Compared with prior art, this hair
The nickel cobalt manganese presoma of bright offer is optimized by coprecipitation reaction, has efficiently controlled primary particle
Pattern, particle diameter and pile up effect, the second particle with tap density higher has been obtained, so as to have
Beneficial to the lifting of lithium ion battery energy density.Test result indicate that, the nickel cobalt manganese forerunner that the present invention is provided
The tap density of body is in 2.3g/cm3More than.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to reality
The accompanying drawing to be used needed for example or description of the prior art is applied to be briefly described, it should be apparent that, below
Accompanying drawing in description is only embodiments of the invention, for those of ordinary skill in the art, not
On the premise of paying creative work, other accompanying drawings can also be obtained according to the accompanying drawing for providing.
Fig. 1 is the ESEM under the conditions of 4500 times of the nickel cobalt manganese presoma amplification that the embodiment of the present invention 1 is provided
Photo；
Fig. 2 is the ESEM under the conditions of 100 times of the nickel cobalt manganese presoma amplification that the embodiment of the present invention 1 is provided
Photo；
Fig. 3 is the nickel cobalt manganese presoma size distribution curve figure that the embodiment of the present invention 1 is provided；
Fig. 4 is the accumulation effect diagram of the nickel cobalt manganese presoma that the embodiment of the present invention 1 is provided；
ESEM under the conditions of 500 times of the nickel cobalt manganese presoma amplification that Fig. 5 is provided for comparative example of the present invention shines
Piece；
The nickel cobalt manganese presoma size distribution curve figure that Fig. 6 is provided for comparative example of the present invention；
The accumulation effect diagram of the nickel cobalt manganese presoma that Fig. 7 is provided for comparative example of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.
Based on the embodiment in the present invention, those of ordinary skill in the art are not under the premise of creative work is made
The every other embodiment for being obtained, belongs to the scope of protection of the invention.
The invention provides a kind of nickel cobalt manganese presoma, the nickel cobalt manganese presoma be by formula be formula (I)
Primary particle and formula for formula (II) primary particle pile up second particle；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
In the present invention, the nickel cobalt manganese presoma be by formula be NixCoyMn1-x-yThe primary particle of M
It is M '@Ni with formulaxCoyMn1-x-yThe second particle that the primary particle of M is piled up.In the present invention,
M is CO3 2-Or (OH)2 2-, preferably CO3 2-。
In the present invention, M ' is nucleator；In the present invention, the nucleator preferably includes physical absorption
Nucleator, the nucleator of ionic adsorption and one or more from the nucleator of dissociative type.In this hair
In bright, the nucleator of the physical absorption can adsorb the little particle of suspension, form secondary crystallization core, after
It is continuous to carry out secondary precipitation reaction；In the present invention, the nucleator of the physical absorption be preferably activated carbon,
Silica gel, polymeric adsorbent, kaolin, montmorillonite, attapulgite, diatomite, molecular sieve, aluminum oxide,
Aluminium hydroxide, aluminium carbonate, magnesia, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, carbonic acid
One or more in calcium, more preferably activated carbon, kaolin, montmorillonite, attapulgite, diatom
One or more in soil, aluminum oxide, aluminium hydroxide, magnesia.The present invention is to the physical absorption
The source of nucleator is not particularly limited, using commercial goods well known to those skilled in the art.
In the present invention, the nucleator of the ionic adsorption has negative electrical charge in aqueous, can be by band
Have positive charge metal ion and metal ion compound aggregation it is agglomerating, formed secondary crystallization core, continue into
Row secondary precipitation is reacted；In the present invention, the nucleator of the ionic adsorption is preferably organising for alkyl
In compound, the organic compound containing aldehyde radical, the organic compound of hydroxyl and the organic compound containing phenolic group
One or more, more preferably methane, ethane, butane, hexane, formic acid, acetic acid, ascorbic acid,
Citric acid, methyl alcohol, ethanol, propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, n-undecane alcohol, ring ethanol,
One or more in the tert-butyl alcohol, triphenylcarbinol, phenol, cresols, amino phenols and nitrophenols, most preferably
It is methane, ethane, formic acid, acetic acid, ascorbic acid, citric acid, ethanol, phenol, cresols and amino
One or more in phenol.The present invention is not particularly limited to the source of the nucleator of the ionic adsorption,
Using commercial goods well known to those skilled in the art.
In the present invention, the nucleator from dissociative type can dissociate in reaction solution, with salt
Solution is mixed into new reaction solution, forms secondary crystallization core, proceeds secondary precipitation reaction；At this
In invention, it is described from the nucleator of dissociative type be preferably nickelous carbonate, manganese carbonate, cobalt carbonate, nickel hydroxide,
One or more in manganous hydroxide and cobalt hydroxide, more preferably manganese carbonate, nickel hydroxide, hydroxide
One or more in manganese or cobalt hydroxide.The present invention does not have to the source of the nucleator from dissociative type
It is specifically limited, using commercial goods well known to those skilled in the art.
In the present invention, 0 ＜ x ＜ 1,0 ＜ y ＜ 1, x+y ＜ 1, preferably 1/6≤x≤1/2,1/6≤y
≤1/3.In a preferred embodiment of the invention, M is CO3 2-, M ' be aluminium hydroxide, x=1/6,
Y=1/6, the nickel cobalt manganese presoma be by formula be Ni0.1665Co0.1665Mn0.667CO3Primary particle and
Formula is Al (OH)3@Ni0.1665Co0.1665Mn0.667CO3Primary particle pile up second particle；
In presently preferred embodiment, M is (OH)2 2-, M ' be aluminum oxide, x=0.4, y=0.2,
The nickel cobalt manganese presoma be by formula be Ni0.4Co0.2Mn04(OH)2Primary particle and formula be
Al2O3@Ni0.4Co0.2Mn0.4(OH)2Primary particle pile up second particle.
In the present invention, the particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm, preferably 12 μ
M~25 μm.In the present invention, the nickel cobalt manganese presoma be by formula be NixCoyMn1-x-yThe one of M
Secondary particle and formula are M '@NixCoyMn1-x-yThe second particle that the primary particle of M is piled up.At this
In invention, the formula is NixCoyMn1-x-yThe particle diameter of the primary particle of M is preferably 1 μm~7 μm,
More preferably 3.5 μm~5.5 μm；The formula M '@NixCoyMn1-x-yM is represented with M ' as nucleator
What is formed has the primary particle of different-grain diameter with formula (I), and nucleator M ' will can lead to a certain extent
Formula is NixCoyMn1-x-yThe primary particle of M is assembled, and forms the larger primary particle of particle diameter.At this
In invention, the formula is NixCoyMn1-x-yThe primary particle of M is M '@Ni with formulaxCoyMn1-x-yM
Primary particle particle diameter than be preferably (0.1~0.4)：1, more preferably (0.17~0.32)：1.
The nickel cobalt manganese presoma that the present invention is provided is by the primary particle accumulation of two kinds of different-shapes and particle diameter
Into with tap density higher, the nickel cobalt manganese presoma that the present invention is obtained uses people in the art
High temperature solid-state method known to member prepares positive electrode, and the lithium ion battery for further preparing has
Energy density higher.
Present invention also offers a kind of preparation method of nickel cobalt manganese presoma, comprise the following steps：
A) nickel source, cobalt source, manganese source, precipitating reagent and complexing agent are mixed, carries out coprecipitation reaction, obtained
Formula is the primary particle of formula (I)；Precipitating reagent includes the salt containing carbonate, the salt containing bicarbonate radical and contains
One or more in salt hydroxy；
B) formula is carried out into secondary precipitation reaction for the primary particle of formula (I) mixes with nucleator, is obtained
Nickel cobalt manganese presoma；
The nickel cobalt manganese presoma is for the primary particle and formula of formula (I) are the one of formula (II) by formula
The second particle of secondary particle packing；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x<1；0 ＜ y<1；x+y<1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
In the present invention, nickel source, cobalt source, manganese source, precipitating reagent and complexing agent are mixed, is co-precipitated
Reaction, obtains the primary particle that formula is formula (I).In the present invention, the nickel source preferably includes sulfuric acid
One or more in nickel, nickel nitrate and nickel chloride, more preferably nickel sulfate.The present invention is to the nickel source
Source be not particularly limited, using above-mentioned nickel sulfate well known to those skilled in the art, nickel nitrate and chlorine
Change the commercial goods of nickel.
In the present invention, the cobalt source preferably includes the one kind or many in cobaltous sulfate, cobalt nitrate and cobalt chloride
Plant, more preferably cobaltous sulfate.The present invention is not particularly limited to the source of the cobalt source, using this area
The commercial goods of above-mentioned cobaltous sulfate, cobalt nitrate and cobalt chloride known to technical staff.
In the present invention, the manganese source preferably includes the one kind or many in manganese sulfate, manganese nitrate and manganese chloride
Plant, more preferably manganese sulfate.The present invention is not particularly limited to the source of the manganese source, using this area
The commercial goods of above-mentioned manganese sulfate, manganese nitrate and manganese chloride known to technical staff.
The present invention first mixes nickel source, cobalt source and manganese source, obtains the mixed solution of nickel cobalt manganese, described mixed
The mol ratio for closing nickel, cobalt and manganese in solution is x：y：(1-x-y)；Wherein, the ＜ y ＜ 1 of 0 ＜ x ＜ 1,0,
X+y ＜ 1, preferably 1/6≤x≤1/2,1/6≤y≤1/3.The present invention is to the method for the mixing without spy
Different limitation, using mechanical agitation well known to those skilled in the art or artificial stirring.In the present invention,
The molar concentration of nickel ion, cobalt ions and manganese ion is preferably in the mixed solution of the nickel cobalt manganese
1.5mol/L~3.5mol/L, more preferably 2mol/L.
In the present invention, nickel source, cobalt source, manganese source, precipitating reagent and complexing agent are mixed, is co-precipitated
Reaction, obtains the primary particle that formula is formula (I)；The process for carrying out coprecipitation reaction is preferably specific
For：
The mixed solution of nickel source, cobalt source and manganese source is mixed with precipitating reagent and complexing agent, is reacted, obtained
It is the primary particle of formula (I) to formula.In the present invention, the precipitating reagent is preferably included containing carbonate
Salt, the salt containing bicarbonate radical and containing one or more in salt hydroxy, more preferably sodium carbonate, carbon
One or more in sour hydrogen sodium and NaOH.In the present invention, the precipitating reagent can be molten to mixing
The pH value of liquid is adjusted, and forms homogeneous precipitation；The present invention does not have special limit to the source of the precipitating reagent
System, using commercial goods well known to those skilled in the art.In the present invention, the precipitating reagent leads to
Cross the aqueous solution form be added to the mixed solution of nickel source, cobalt source and manganese source in mixed, the precipitation
The molar concentration of the aqueous solution of agent is preferably 2mol/L~6mol/L, more preferably 3mol/L~5mol/L.This
Invention is not particularly limited to the method for the mixing, using mechanical agitation well known to those skilled in the art
Or artificial stirring.
In the present invention, described complexing agent is preferably ammoniacal liquor, ammonium hydrogen carbonate, ammonium phosphate and phosphoric acid hydrogen ammonia
In one or more, more preferably ammoniacal liquor.The present invention is not particularly limited to the source of the complexing agent,
Using the commercially available of above-mentioned ammoniacal liquor well known to those skilled in the art, ammonium hydrogen carbonate, ammonium phosphate and phosphoric acid hydrogen ammonia
Commodity.In the present invention, the complexing agent by the form of the aqueous solution be added to nickel source, cobalt source and
Mixed in the mixed solution of manganese source, the molar concentration of the aqueous solution of the complexing agent is preferably
0.5mol/L~4.5mol/L, more preferably 1mol/L~4mol/L.The present invention does not have to the method for the mixing
It is specifically limited, using mechanical agitation well known to those skilled in the art or artificial stirring.
In the present invention, complexing agent can be complexed with nickel ion, cobalt ions and manganese ion；It is described mixed
The ratio between molal quantity of nickel ion, cobalt ions and the total molal quantity of manganese ion and complexing agent in solution is closed to be preferably
2：(0.5~1.5), more preferably 2：1.
In the present invention, the mixed solution of nickel source, cobalt source and manganese source is mixed with precipitating reagent and complexing agent,
Reacted, obtained the primary particle that formula is formula (I).In the present invention, the pH value of the reaction
Preferably 7.5~9.5, more preferably 8~9；The time of the reaction is preferably 1h~50h, more preferably
4h~20h.
After obtaining the primary particle that the formula is formula (I), the formula is the one of formula (I) by the present invention
Secondary particle mixes with nucleator, carries out secondary precipitation reaction, obtains nickel cobalt manganese presoma.In the present invention,
The nucleator preferably include the nucleator of physical absorption, the nucleator of ionic adsorption and from dissociative type into
One or more in core agent.In the present invention, the nucleator of the physical absorption can adsorb suspension
Little particle, forms secondary crystallization core, proceeds secondary precipitation reaction；In the present invention, the physics
The nucleator of absorption be preferably activated carbon, silica gel, polymeric adsorbent, kaolin, montmorillonite, attapulgite,
Diatomite, molecular sieve, aluminum oxide, aluminium hydroxide, aluminium carbonate, magnesia, magnesium hydroxide, magnesium carbonate,
One or more in calcium oxide, calcium hydroxide, calcium carbonate, more preferably activated carbon, kaolin,
One or more in montmorillonite, attapulgite, diatomite, aluminum oxide, aluminium hydroxide, magnesia.
The present invention is not particularly limited to the source of the nucleator of the physical absorption, using those skilled in the art
Well known commercial goods.
In the present invention, the nucleator of the ionic adsorption has negative electrical charge in aqueous, can be by band
Have positive charge metal ion and metal ion compound aggregation it is agglomerating, formed secondary crystallization core, continue into
Row secondary precipitation is reacted；In the present invention, the nucleator of the ionic adsorption is preferably organising for alkyl
In compound, the organic compound containing aldehyde radical, the organic compound of hydroxyl and the organic compound containing phenolic group
One or more, more preferably methane, ethane, butane, hexane, formic acid, acetic acid, ascorbic acid,
Citric acid, methyl alcohol, ethanol, propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, n-undecane alcohol, ring ethanol,
One or more in the tert-butyl alcohol, triphenylcarbinol, phenol, cresols, amino phenols and nitrophenols, most preferably
It is methane, ethane, formic acid, acetic acid, ascorbic acid, citric acid, ethanol, phenol, cresols and amino
One or more in phenol.The present invention is not particularly limited to the source of the nucleator of the ionic adsorption,
Using commercial goods well known to those skilled in the art.
In the present invention, the nucleator from dissociative type can dissociate in reaction solution, with salt
Solution is mixed into new reaction solution, forms secondary crystallization core, proceeds secondary precipitation reaction；At this
In invention, it is described from the nucleator of dissociative type be preferably nickelous carbonate, manganese carbonate, cobalt carbonate, nickel hydroxide,
One or more in manganous hydroxide and cobalt hydroxide, more preferably manganese carbonate, nickel hydroxide, hydroxide
One or more in manganese or cobalt hydroxide.The present invention does not have to the source of the nucleator from dissociative type
It is specifically limited, using commercial goods well known to those skilled in the art.
In the present invention, by formula for the primary particle of formula (I) mixes with nucleator, the formula is formula
(I) primary particle is preferably 1 with the mol ratio of nucleator：(0.001~0.5), more preferably 1：
(0.01~0.1).In the present invention, the solution or suspension obtained after the nucleator with water by mixing
Form and the formula mixed for the primary particle of formula (I), the aqueous solution of the nucleator or outstanding
The molar concentration of turbid liquid is preferably 0.001mol/L~0.5mol/L.
In the present invention, the time that the secondary precipitation is reacted is preferably 8h~24h, more preferably 10h~20h.
In the present invention, a small amount of nucleator can form secondary crystallization core, proceed secondary precipitation reaction, obtain
To formula for formula (II) primary particle, the formula for formula (II) primary particle with do not react
Formula second particle is formed by accumulation for the primary particle of formula (I), that is, obtain nickel cobalt manganese presoma.
The invention provides a kind of nickel cobalt manganese presoma, the nickel cobalt manganese presoma is to be by formula
NixCoyMn1-x-yThe primary particle and formula of M are M '@NixCoyMn1-x-yThe primary particle of M pile up and
Into second particle；Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；
X+y ＜ 1；The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.Compared with prior art, this hair
The nickel cobalt manganese presoma of bright offer is optimized by coprecipitation reaction, has efficiently controlled primary particle
Pattern, particle diameter and pile up effect, the second particle with tap density higher has been obtained, so as to have
Beneficial to the lifting of lithium ion battery energy density.Test result indicate that, the nickel cobalt manganese forerunner that the present invention is provided
The tap density of body is in 2.3g/cm3More than.
Additionally, the preparation method production efficiency that the present invention is provided is high, continuous prodution can be realized, had
Economic benefit higher, and the discharge of the heavy metal ion in production process is reduced, it is environment-friendly.
In order to further illustrate the present invention, it is described in detail below by following examples.The present invention with
The source of medicine used is shown in Table 1 in lower embodiment.
The source of medicine used in the embodiment of the present invention of table 1
| Nomenclature of drug | Manufacturer | Specification |
| Nickel sulfate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 98.5% |
| Cobaltous sulfate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.5% |
| Manganese sulfate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.0% |
| Sodium carbonate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.0% |
| Ammoniacal liquor | Chemical Reagent Co., Ltd., Sinopharm Group | 25%~28% |
| Aluminum nitrate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99% |
| Aluminium hydroxide | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99% |
| Manganese carbonate | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 98.5% |
| Nickel hydroxide | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.0% |
| Cobalt hydroxide | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.0% |
| NaOH | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 99.0% |
| Aluminum oxide | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 98.0% |
| Ascorbic acid | Chemical Reagent Co., Ltd., Sinopharm Group | Analyze pure 98.0% |
| Activated carbon | Chemical Reagent Co., Ltd., Sinopharm Group | 98.0% |
| Citric acid | Chemical Reagent Co., Ltd., Sinopharm Group | 99.5% |
Embodiment 1
(1) it is 1/6 first by mol ratio：1/6：2/3 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 4mol/L are the ammonia spirit of 2mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonia spirit is added in the reactor with stirring, is reacted, control nickel sulfate, cobaltous sulfate and sulfuric acid
The mixed solution of manganese is 2 with the volume ratio of ammonia spirit：1, by the addition control for adjusting sodium carbonate liquor
The pH value for making reaction is 8.1, carries out coprecipitation reaction 10h, and obtaining formula is
Ni0.1665Co0.1665Mn0.667CO3Primary particle.
(3) formula will be obtained for Ni0.1665Co0.1665Mn0.667CO3Primary particle and 0.5mol/L nitric acid
Aluminum solutions mix, and control the addition of aluminum nitrate solution and make formula be Ni0.1665Co0.1665Mn0.667CO3's
Primary particle is 1 with aluminum ions mol ratio：0.05, proceed secondary precipitation reaction 20h, led to
Formula is Al (OH)3@Ni0.1665Co0.1665Mn0.667CO3Primary particle, the formula is
Al(OH)3@Ni0.1665Co0.1665Mn0.667CO3Primary particle be with the formula not reacted
Ni0.1665Co0.1665Mn0.667CO3Primary particle second particle is formed by accumulation, separating, washing is to obtain
Nickel cobalt manganese presoma.
Using the FEG types ESEMs of FEI QUANTA 250 to the nickel cobalt manganese forerunner that is obtained in embodiment 1
Body is analyzed, and its stereoscan photograph is obtained, as shown in Fig. 1~2.Wherein, Fig. 1 is of the invention real
The stereoscan photograph under the conditions of 4500 times of the nickel cobalt manganese presoma amplification of the offer of example 1 is applied, Fig. 2 is this
The nickel cobalt manganese presoma that inventive embodiments 1 are provided amplifies the stereoscan photograph under the conditions of 1500 times.
Tested using S3500-special type laser fineness gages, obtained its size distribution curve,
As shown in Figure 3.Fig. 3 is the nickel cobalt manganese presoma size distribution curve figure that the embodiment of the present invention 1 is provided.
Test result shows that the nickel cobalt manganese granular precursor that the embodiment of the present invention 1 is prepared is relatively uniform, ball
Shape degree is good, good fluidity, and its particle diameter is 19.5 μm, wherein, formula is Ni0.1665Co0.1665Mn0.667CO3
Primary particle particle diameter be 5.2 μm, formula be Al (OH)3@Ni0.1665Co0.1665Mn0.667CO3One
The particle diameter of secondary particle is 20.3 μm, and the two particle diameter ratio is 0.2562.
The accumulation effect of the nickel cobalt manganese presoma provided above-described embodiment 1 is analyzed, as shown in figure 4,
Fig. 4 is the accumulation effect diagram of the nickel cobalt manganese presoma that the embodiment of the present invention 1 is provided.
Tested using BT-300 type tap density testers, as a result shown, the embodiment of the present invention 1
The tap density of the nickel cobalt manganese presoma of offer is 2.5g/cm3。
Embodiment 2
(1) it is 1/3 first by mol ratio：1/3：1/3 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 3mol/L are the ammonia spirit of 1mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonia spirit is added in the reactor with stirring, is reacted, control nickel sulfate, cobaltous sulfate and sulfuric acid
The mixed solution of manganese is 1 with the volume ratio of ammonia spirit：1, by the addition control for adjusting sodium carbonate liquor
The pH value for making reaction is 8.3, carries out coprecipitation reaction 5h, obtains formula for Ni0.333Co0.333Mn0.334CO3
Primary particle.
(3) formula will be obtained for Ni0.333Co0.333Mn0.334CO3Primary particle and 0.02mol/L hydrogen-oxygens
Change aluminum solutions mixing, controlling the addition of aluminum hydroxide solution makes formula be Ni0.333Co0.333Mn0.334CO3
The mol ratio of primary particle and aluminium hydroxide be 1：0.02, proceed secondary precipitation reaction 15h, obtain
It is Al (OH) to formula3@Ni0.333Co0.333Mn0.334CO3Primary particle, the formula is
Al(OH)3@Ni0.333Co0.333Mn0.334CO3Primary particle be with the formula not reacted
Ni0.333Co0.333Mn0.334CO3Primary particle second particle is formed by accumulation, separating, washing is to obtain
Nickel cobalt manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 2
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 2 is provided is 17.5
μm, wherein, formula is Ni0.333Co0.333Mn0.334CO3Primary particle particle diameter be 4.1 μm, lead to
Formula is Al (OH)3@Ni0.333Co0.333Mn0.334CO3Primary particle particle diameter be 18.6 μm, the two grain
Footpath ratio is 0.2204.
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 2 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 2 is provided is
2.35g/cm3。
Embodiment 3
(1) it is 0.5 first by mol ratio：0.3：0.2 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 4mol/L are the ammonium bicarbonate soln of 4mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonium bicarbonate soln be added to stirring reactor in, reacted, control nickel sulfate, cobaltous sulfate and
The mixed solution of manganese sulfate is 4 with the volume ratio of ammonium bicarbonate soln：1, by adjusting sodium carbonate liquor
It is 8.95 that addition controls the pH value of reaction, carries out coprecipitation reaction 4h, and obtaining formula is
Ni0.5Co0.3Mn0.2CO3Primary particle.
(3) formula will be obtained for Ni0.5Co0.3Mn0.2CO3Primary particle and 0.2mol/L manganese carbonates hang
Turbid liquid mixing, controlling the addition of manganese carbonate suspension makes formula be Ni0.5Co0.3Mn0.2CO3Once
Grain is 1 with the mol ratio of manganese carbonate：0.02, proceed secondary precipitation reaction 12h, obtaining formula is
MnCO3@Ni0.5Co0.3Mn0.2CO3Primary particle, the formula is
MnCO3@Ni0.5Co0.3Mn0.2CO3Primary particle be with the formula not reacted
Ni0.5Co0.3Mn0.2CO3Primary particle second particle is formed by accumulation, separating, washing is to obtain nickel cobalt
Manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 3
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 3 is provided is 12.5
μm, wherein, formula is Ni0.5Co0.3Mn0.2CO3The particle diameter of primary particle be 3.6 μm, formula is
MnCO3@Ni0.5Co0.3Mn0.2CO3The particle diameter of primary particle be 16.1 μm, the two particle diameter ratio is
0.2236。
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 3 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 3 is provided is
2.32g/cm3。
Embodiment 4
(1) it is 0.5 first by mol ratio：0.3：0.2 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 3mol/L are the ammonia spirit of 1mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonia spirit is added in the reactor with stirring, is reacted, control nickel sulfate, cobaltous sulfate and sulfuric acid
The mixed solution of manganese is 1 with the volume ratio of ammonia spirit：1, by the addition control for adjusting sodium carbonate liquor
The pH value for making reaction is 8.95, carries out coprecipitation reaction 10h, obtains formula for Ni0.5Co0.3Mn0.2CO3
Primary particle.
(3) formula will be obtained for Ni0.5Co0.3Mn0.2CO3Primary particle and 0.1mol/L nickel hydroxides
Suspension mixes, and controls the addition of nickel hydroxide suspension and makes formula be Ni0.5Co0.3Mn0.2CO3One
Secondary particle is 1 with the mol ratio of nickel hydroxide：0.01, proceed secondary precipitation reaction 20h, led to
Formula is Ni (OH)2@Ni0.5Co0.3Mn0.2CO3Primary particle, the formula is
Ni(OH)2@Ni0.5Co0.3Mn0.2CO3Primary particle be with the formula not reacted
Ni0.5Co0.3Mn0.2CO3Primary particle second particle is formed by accumulation, separating, washing is to obtain nickel cobalt
Manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 4
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 4 is provided is 22.5
μm, wherein, formula is Ni0.5Co0.3Mn0.2CO3The particle diameter of primary particle be 4.6 μm, formula is
Ni(OH)2@Ni0.5Co0.3Mn0.2CO3The particle diameter of primary particle be 26.1 μm, the two particle diameter ratio is
0.1762。
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 4 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 4 is provided is
2.46g/cm3。
Embodiment 5
(1) it is 0.4 first by mol ratio：0.2：0.4 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 5mol/L are the ammonia spirit of 2.5mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonia spirit is added in the reactor with stirring, is reacted, control nickel sulfate, cobaltous sulfate and sulfuric acid
The mixed solution of manganese is 5 with the volume ratio of ammonia spirit：2, by the addition control for adjusting sodium carbonate liquor
The pH value for making reaction is 8.55, carries out coprecipitation reaction 8h, obtains formula for Ni0.4Co0.2Mn0.4CO3
Primary particle.
(3) formula will be obtained for Ni0.4Co0.2Mn0.4CO3Primary particle and 0.5mol/L
Ni0.33Co0.33Mn0.34(OH)2Suspension mixes, and controls Ni0.33Co0.33Mn0.34(OH)2The addition of suspension
Amount makes formula be Ni0.4Co0.2Mn0.4CO3Primary particle and Ni0.33Co0.33Mn0.34(OH)2Mol ratio
It is 1：0.05, proceed secondary precipitation reaction 8h, obtaining formula is
Ni0.33Co0.33Mn0.34(OH)2@Ni0.4Co0.2Mn0.4CO3Primary particle, the formula is
Ni0.33Co0.33Mn0.34(OH)2@Ni0.4Co0.2Mn0.4CO3Primary particle and the formula that does not react
It is Ni0.4Co0.2Mn0.4CO3Primary particle second particle is formed by accumulation, separating, washing is to obtain nickel
Cobalt manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 5
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 5 is provided is 15.2
μm, wherein, formula is Ni0.4Co0.2Mn0.4CO3The particle diameter of primary particle be 5.2 μm, formula is
Ni0.33Co0.33Mn0.34(OH)2@Ni0.4Co0.2Mn0.4CO3Primary particle particle diameter be 16.5 μm, two
Person's particle diameter ratio is 0.3152.
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 5 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 5 is provided is
2.42g/cm3。
Embodiment 6
(1) it is 0.4 first by mol ratio：0.2：0.4 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium hydroxide solution and molar concentration of 5mol/L are the ammonia spirit of 2.5mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium hydroxide solution for preparing
It is added in the reactor with stirring with ammonia spirit, is reacted, control nickel sulfate, cobaltous sulfate and sulphur
The mixed solution of sour manganese is 5 with the volume ratio of ammonia spirit：2, by the addition for adjusting sodium hydroxide solution
It is 8.55 that amount controls the pH value of reaction, carries out coprecipitation reaction 20h, and obtaining formula is
Ni0.4Co0.2Mn0.4(OH)2Primary particle.
(3) formula will be obtained for Ni0.4Co0.2Mn0.4(OH)2Primary particle and 0.001mol/L aoxidize
Aluminium suspension mixes, and controls the addition of aluminum oxide suspension and makes formula be Ni0.4Co0.2Mn0.4(OH)2's
Primary particle is 1 with the mol ratio of aluminum oxide：0.01, proceed secondary precipitation reaction 20h, led to
Formula is Al2O3@Ni0.4Co0.2Mn0.4(OH)2Primary particle, the formula is
Al2O3@Ni0.4Co0.2Mn0.4(OH)2Primary particle be with the formula not reacted
Ni0.4Co0.2Mn0.4(OH)2Primary particle second particle is formed by accumulation, separating, washing is to obtain nickel
Cobalt manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 6
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 6 is provided is 14.8
μm, wherein, formula is Ni0.4Co0.2Mn0.4(OH)2Primary particle particle diameter be 3.8 μm, formula
It is Al2O3@Ni0.4Co0.2Mn0.4(OH)2The particle diameter of primary particle be 18.1 μm, the two particle diameter ratio is
0.2652。
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 6 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 6 is provided is
2.42g/cm3。
Embodiment 7
(1) it is 1/6 first by mol ratio：1/6：2/3 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium hydroxide solution and molar concentration of 4mol/L are the ammonia spirit of 2mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium hydroxide solution for preparing
It is added in the reactor with stirring with ammonia spirit, is reacted, control nickel sulfate, cobaltous sulfate and sulphur
The mixed solution of sour manganese is 2 with the volume ratio of ammonia spirit：1, by the addition for adjusting sodium hydroxide solution
It is 8.05 that amount controls the pH value of reaction, carries out coprecipitation reaction 15h, and obtaining formula is
Ni0.1665Co0.1665Mn0.667(OH)2Primary particle.
(3) formula will be obtained for Ni0.1665Co0.1665Mn0.667(OH)2Primary particle and 0.02mol/L
Ascorbic acid solution mixes, and controls the addition of ascorbic acid solution and makes the formula be
Ni0.1665Co0.1665Mn0.667(OH)2The mol ratio of primary particle and ascorbic acid be 1：0.02, continue
Secondary precipitation reaction 10h is carried out, formula is obtained for ascorbic acid@Ni0.1665Co0.1665Mn0.667(OH)2's
Primary particle, the formula is ascorbic acid@Ni0.1665Co0.1665Mn0.667(OH)2Primary particle with not
The formula for reacting is Ni0.1665Co0.1665Mn0.667(OH)2Primary particle form secondary by accumulation
Particle, separating, washing is to obtain nickel cobalt manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 7
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 7 is provided is 19.5
μm, wherein, formula is Ni0.1665Co0.1665Mn0.667(OH)2Primary particle particle diameter be 6.3 μm,
Formula is ascorbic acid@Ni0.1665Co0.1665Mn0.667(OH)2Primary particle particle diameter be 20.1 μm,
The two particle diameter ratio is 0.3134.
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 7 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 7 is provided is
2.35g/cm3。
Embodiment 8
(1) it is 1/6 first by mol ratio：1/6：2/3 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium hydroxide solution and molar concentration of 3mol/L are the ammonia spirit of 1.2mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium hydroxide solution for preparing
It is added in the reactor with stirring with ammonia spirit, is reacted, control nickel sulfate, cobaltous sulfate and sulphur
The mixed solution of sour manganese is 1.2 with the volume ratio of ammonia spirit：1, by adjusting adding for sodium hydroxide solution
Enter amount to control the pH value of reaction is 8.25, carries out coprecipitation reaction 6h, and obtaining formula is
Ni0.1665Co0.1665Mn0.667(OH)2Primary particle.
(3) formula will be obtained for Ni0.1665Co0.1665Mn0.667(OH)2Primary particle and 0.015mol/L
Activated carbon suspension mixes, and controls the addition of activated carbon suspension and makes the formula be
Ni0.1665Co0.1665Mn0.667(OH)2The mol ratio of primary particle and activated carbon be 1：0.015, continue into
12h is reacted in row secondary precipitation, obtains formula for activated carbon@Ni0.1665Co0.1665Mn0.667(OH)2Once
Particle, the formula is activated carbon@Ni0.1665Co0.1665Mn0.667(OH)2Primary particle with do not occur it is anti-
The formula answered is Ni0.1665Co0.1665Mn0.667(OH)2Primary particle second particle is formed by accumulation, point
Nickel cobalt manganese presoma is obtained from washing.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 8
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 8 is provided is 12.5
μm, wherein, formula is Ni0.1665Co0.1665Mn0.667(OH)2Primary particle particle diameter be 2.6 μm,
Formula is activated carbon@Ni0.1665Co0.1665Mn0.667(OH)2Primary particle particle diameter be 14.2 μm, two
Person's particle diameter ratio is 0.1831.
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 8 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 8 is provided is
2.36g/cm3。
Embodiment 9
(1) it is 1/4 first by mol ratio：1/4：1/2 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium bicarbonate solution and molar concentration of 4mol/L are the ammonia spirit of 2mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium bicarbonate solution for preparing
It is added in the reactor with stirring with ammonia spirit, is reacted, control nickel sulfate, cobaltous sulfate and sulphur
The mixed solution of sour manganese is 2 with the volume ratio of ammonia spirit：1, by the addition for adjusting sodium bicarbonate solution
It is 8.95 that amount controls the pH value of reaction, carries out coprecipitation reaction 12h, and obtaining formula is
Ni0.25Co0.25Mn0.5CO3Primary particle.
(3) formula will be obtained for Ni0.25Co0.25Mn0.5CO3Primary particle and 0.08mol/L citric acids
Solution mixes, and controls the addition of citric acid solution and makes formula be Ni0.25Co0.25Mn0.5CO3Once
Grain is 1 with the mol ratio of citric acid：0.08, proceed secondary precipitation reaction 24h, formula is obtained for lemon
Lemon acid@Ni0.25Co0.25Mn0.5CO3Primary particle, the formula be citric acid
@Ni0.25Co0.25Mn0.5CO3Primary particle and the formula that does not react be Ni0.25Co0.25Mn0.5CO3
Primary particle second particle is formed by accumulation, separating, washing is to obtain nickel cobalt manganese presoma.
The pattern and grain of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in embodiment 9
Footpath is analyzed, and as a result shows, the particle diameter of the nickel cobalt manganese presoma that the embodiment of the present invention 9 is provided is 13.5
μm, wherein, formula is Ni0.25Co0.25Mn0.5CO3Primary particle particle diameter be 5.4 μm, formula
It is citric acid@Ni0.25Co0.25Mn0.5CO3The particle diameter of primary particle be 14.2 μm, the two particle diameter ratio is
0.3803。
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided embodiment 9 is entered
Row test, as a result shows, the tap density of the nickel cobalt manganese presoma that the embodiment of the present invention 9 is provided is
2.32g/cm3。
Comparative example
(1) it is 1/6 first by mol ratio：1/6：2/3 nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in
In deionized water, the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, nickel in the mixed solution are obtained
The total mol concentration of ion, cobalt ions and manganese ion is 2mol/L；Meanwhile, molar concentration is prepared respectively is
The sodium carbonate liquor and molar concentration of 4mol/L are the ammonia spirit of 2mol/L.
(2) by the mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate and the sodium carbonate liquor for preparing and
Ammonia spirit is added in the reactor with stirring, is reacted, control nickel sulfate, cobaltous sulfate and sulfuric acid
The mixed solution of manganese is 2 with the volume ratio of ammonia spirit：1, by the addition control for adjusting sodium carbonate liquor
The pH value for making reaction is 8.1, carries out coprecipitation reaction 30h, and obtaining formula is
Ni0.1665Co0.1665Mn0.667CO3Primary particle by piling up the second particle for being formed, separating, washing obtains final product
To nickel cobalt manganese presoma.
The pattern and particle diameter of the nickel cobalt manganese presoma according to the method for the offer of embodiment 1 to being obtained in comparative example
It is analyzed, obtains its stereoscan photograph, as shown in Figure 5.Fig. 5 is provided for comparative example of the present invention
Nickel cobalt manganese presoma amplifies the stereoscan photograph under the conditions of 500 times.Carried out using laser fineness gage
Test, obtains its size distribution curve, as shown in Figure 6.The nickel cobalt that Fig. 6 is provided for comparative example of the present invention
Manganese presoma size distribution curve figure.Test result shows, the nickel cobalt manganese that comparative example of the present invention is prepared
Granular precursor is relatively uniform, good sphericity, good fluidity, and its particle diameter is 23.8 μm.
The accumulation effect of the nickel cobalt manganese presoma provided above-mentioned comparative example is analyzed, as shown in fig. 7,
The accumulation effect diagram of the nickel cobalt manganese presoma that Fig. 7 is provided for comparative example of the present invention.
The tap density of the nickel cobalt manganese presoma that the method provided according to embodiment 1 is provided comparative example is carried out
Test, as a result shows, the tap density of the nickel cobalt manganese presoma that comparative example of the present invention is provided is 2.0g/cm3。
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses this
Invention.Various modifications to these embodiments will be for those skilled in the art apparent
, generic principles defined herein can without departing from the spirit or scope of the present invention,
Realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein,
And it is to fit to the most wide scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. a kind of nickel cobalt manganese presoma, it is characterised in that it by formula is formula (I) that the nickel cobalt manganese presoma is
Primary particle and formula for formula (II) primary particle pile up second particle；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
2. nickel cobalt manganese presoma according to claim 1, it is characterised in that the nucleator includes
The nucleator of physical absorption, the nucleator of ionic adsorption and one or more from the nucleator of dissociative type.
3. nickel cobalt manganese presoma according to claim 1, it is characterised in that the formula is formula (I)
Primary particle particle diameter be 1 μm~7 μm；
The formula is for the particle diameter ratio of the primary particle that primary particle and the formula of formula (I) are formula (II)
(0.1~0.4)：1.
4. a kind of preparation method of nickel cobalt manganese presoma, it is characterised in that comprise the following steps：
A) nickel source, cobalt source, manganese source, precipitating reagent and complexing agent are mixed, carries out coprecipitation reaction, obtained
Formula is the primary particle of formula (I)；Precipitating reagent includes the salt containing carbonate, the salt containing bicarbonate radical and contains
One or more in salt hydroxy；
B) formula is carried out into secondary precipitation reaction for the primary particle of formula (I) mixes with nucleator, is obtained
Nickel cobalt manganese presoma；
The nickel cobalt manganese presoma is for the primary particle and formula of formula (I) are the one of formula (II) by formula
The second particle of secondary particle packing；
NixCoyMn1-x-yM formulas (I)；
M’@NixCoyMn1-x-yM formulas (II)；
Wherein, M is CO3 2-Or (OH)2 2-；M ' is nucleator；0 ＜ x ＜ 1；0 ＜ y ＜ 1；X+y ＜ 1；
The particle diameter of the nickel cobalt manganese presoma is 10 μm~50 μm.
5. preparation method according to claim 4, it is characterised in that the complexing agent be ammoniacal liquor,
One or more in ammonium hydrogen carbonate, ammonium phosphate and phosphoric acid hydrogen ammonia.
6. preparation method according to claim 4, it is characterised in that carried out described in step a)
The process of coprecipitation reaction is specially：
The mixed solution of nickel source, cobalt source and manganese source is mixed with precipitating reagent and complexing agent, is reacted, obtained
It is the primary particle of formula (I) to formula.
7. preparation method according to claim 5, it is characterised in that in the mixed solution nickel from
The ratio between molal quantity of son, cobalt ions and the total molal quantity of manganese ion and complexing agent is 2：(0.5~1.5).
8. preparation method according to claim 5, it is characterised in that reacted described in step a)
PH value be 7.5~9.5, the time be 1h~50h.
9. preparation method according to claim 4, it is characterised in that formula described in step b)
For the primary particle of formula (I) and the mol ratio of nucleator are 1：(0.001~0.5).
10. preparation method according to claim 4, it is characterised in that secondary described in step b)
The time of precipitation reaction is 8h~24h.
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