CN106784784B - nickel-cobalt-manganese precursor and preparation method thereof - Google Patents

nickel-cobalt-manganese precursor and preparation method thereof Download PDF

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CN106784784B
CN106784784B CN201510815143.2A CN201510815143A CN106784784B CN 106784784 B CN106784784 B CN 106784784B CN 201510815143 A CN201510815143 A CN 201510815143A CN 106784784 B CN106784784 B CN 106784784B
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nickel
cobalt
manganese
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primary particles
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CN106784784A (en
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顾庆文
赛喜雅勒图
夏永高
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • 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
    • 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
    • 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
    • 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

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Abstract

The invention provides a nickel-cobalt-manganese precursor, which is a secondary particle formed by stacking primary particles with a general formula of NixCoyMn1-x-yM and primary particles with a general formula of M' @ NixCoyMn 1-x-yM; wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1; the grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m. Compared with the prior art, the nickel-cobalt-manganese precursor provided by the invention effectively controls the appearance, the particle size and the stacking effect of primary particles by optimizing the coprecipitation reaction, and obtains secondary particles with higher tap density, thereby being beneficial to the improvement of the energy density of a lithium ion battery. Experimental results show that the tap density of the nickel-cobalt-manganese precursor provided by the invention is more than 2.3g/cm 3.

Description

Nickel-cobalt-manganese precursor and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel-cobalt-manganese precursor and a preparation method thereof.
background
The lithium ion battery is widely applied to digital products such as mobile phones and notebook computers, and has the advantages of high discharge voltage, good safety, long charge and discharge life, environmental friendliness and the like. Currently, lithium ion battery positive electrode materials that have been commercially produced on a large scale include lithium cobaltate, lithium manganate, lithium iron phosphate, and ternary materials. Wherein, the lithium cobaltate has higher specific discharge capacity, but high price and poor safety performance; the lithium iron phosphate has good safety performance but poor material consistency; the ternary material has moderate price but poor safety performance; the lithium manganate has the advantages of high discharge voltage, low price, abundant reserves, high safety performance and the like, and becomes the main development direction of the anode material of the lithium ion battery. However, the lithium manganate anode material has poor high-temperature cycle performance, and the application of the lithium manganate anode material in the fields of power batteries and energy storage is limited. The nickel cobalt lithium manganate has the advantages of high specific capacity, good thermal stability and the like, becomes the most potential lithium ion battery anode material, and has good application prospect in the field of power such as electric vehicles and the like.
At present, the common methods for preparing nickel cobalt lithium manganate (LiNixCoyMn1-x-yO2) comprise a high-temperature solid phase method and a coprecipitation-high-temperature solid phase method. The method has the defects that three elements of nickel, cobalt and manganese are difficult to be uniformly mixed, so that the synergistic effect of the three elements cannot be fully exerted, the specific capacity of the material is difficult to normally exert, the morphology of the material prepared by the method is difficult to control, the particle morphology of the commonly synthesized powder material is irregular, the stacking density of the material is low, the flowability is poor, the preparation of the anode material is not facilitated, and the practical application of the material is hindered; the coprecipitation-high temperature solid phase method can effectively solve the defects of the high temperature solid phase method by firstly preparing a nickel-cobalt-manganese precursor, mixing the nickel-cobalt-manganese precursor with a lithium source and then calcining at high temperature.
However, the tap density of the nickel-cobalt-manganese precursor prepared by the prior art is not high, and the improvement of the energy density of the lithium ion battery is limited.
Disclosure of Invention
In view of the above, the present invention provides a nickel-cobalt-manganese precursor and a preparation method thereof, and the nickel-cobalt-manganese precursor provided by the invention has a higher tap density.
the invention provides a nickel-cobalt-manganese precursor, which is a secondary particle formed by stacking a primary particle with a general formula (I) and a primary particle with a general formula (II);
NixCoyMn1-x-yM formula (I);
M' @ NixCoyMn1-x-yM formula (II);
Wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1;
The grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m.
preferably, the nucleating agent comprises one or more of a physisorbed nucleating agent, an ionically sorbed nucleating agent and a self-dissociating nucleating agent.
Preferably, the primary particles of formula (I) have a particle size of 1 to 7 μm;
The particle diameter ratio of the primary particles with the general formula (I) to the primary particles with the general formula (II) is (0.1-0.4): 1.
the invention also provides a preparation method of the nickel-cobalt-manganese precursor, which comprises the following steps:
a) Mixing a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain primary particles with a general formula (I); the precipitant comprises one or more of carbonate-containing salt, hydrogen carbonate-containing salt and hydroxide-containing salt;
b) mixing the primary particles with the general formula (I) with a nucleating agent, and carrying out secondary precipitation reaction to obtain a nickel-cobalt-manganese precursor;
The nickel-cobalt-manganese precursor is a secondary particle formed by stacking primary particles with a general formula (I) and primary particles with a general formula (II);
NixCoyMn1-x-yM formula (I);
M' @ NixCoyMn1-x-yM formula (II);
Wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1;
The grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m.
Preferably, the complexing agent is one or more of ammonia water, ammonium bicarbonate, ammonium phosphate and ammonium hydrogen phosphate.
Preferably, the coprecipitation reaction in step a) is specifically performed by:
mixing the mixed solution of a nickel source, a cobalt source and a manganese source with a precipitator and a complexing agent, and reacting to obtain primary particles with a general formula (I).
Preferably, the ratio of the total mole number of the nickel ions, the cobalt ions and the manganese ions in the mixed solution to the mole number of the complexing agent is 2: (0.5 to 1.5).
Preferably, the reaction in the step a) has a pH value of 7.5-9.5 and a time of 1-50 h.
Preferably, the molar ratio of the primary particles of formula (I) to nucleating agent in step b) is 1: (0.001-0.5).
Preferably, the time of the secondary precipitation reaction in the step b) is 8-24 h.
the invention provides a nickel-cobalt-manganese precursor, which is a secondary particle formed by stacking primary particles with a general formula of NixCoyMn1-x-yM and primary particles with a general formula of M' @ NixCoyMn 1-x-yM; wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1; the grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m. Compared with the prior art, the nickel-cobalt-manganese precursor provided by the invention effectively controls the appearance, the particle size and the stacking effect of primary particles by optimizing the coprecipitation reaction, and obtains secondary particles with higher tap density, thereby being beneficial to the improvement of the energy density of a lithium ion battery. Experimental results show that the tap density of the nickel-cobalt-manganese precursor provided by the invention is more than 2.3g/cm 3.
drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a scanning electron microscope photograph of a nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention, magnified 4500 times;
Fig. 2 is a scanning electron microscope photograph of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention under a condition of 100 times magnification;
Fig. 3 is a particle size distribution graph of a nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention;
Fig. 4 is a schematic diagram illustrating a deposition effect of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a Ni-Co-Mn precursor provided by a comparative example of the present invention magnified 500 times;
FIG. 6 is a particle size distribution graph of a Ni-Co-Mn precursor according to a comparative example of the present invention;
fig. 7 is a schematic diagram of the deposition effect of the nickel-cobalt-manganese precursor provided by the comparative example of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a nickel-cobalt-manganese precursor, which is a secondary particle formed by stacking a primary particle with a general formula (I) and a primary particle with a general formula (II);
NixCoyMn1-x-yM formula (I);
M' @ NixCoyMn1-x-yM formula (II);
Wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1;
the grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m.
In the invention, the nickel-cobalt-manganese precursor is a secondary particle formed by stacking primary particles with a general formula of NixCoyMn1-x-yM and primary particles with a general formula of M' @ NixCoyMn 1-x-yM. In the present invention, M is CO 32-Or (OH)22-, preferably CO 32-.
in the present invention, M' is a nucleating agent; in the present invention, the nucleating agent preferably includes one or more of a physically adsorbed nucleating agent, an ion-adsorbed nucleating agent and a self-dissociating nucleating agent. In the invention, the physically adsorbed nucleating agent can adsorb suspended small particles to form secondary crystallization nuclei, and then secondary precipitation reaction is carried out continuously; in the present invention, the physically adsorbed nucleating agent is preferably one or more of activated carbon, silica gel, adsorption resin, kaolin, montmorillonite, attapulgite, diatomaceous earth, molecular sieve, alumina, aluminum hydroxide, aluminum carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, and calcium carbonate, and more preferably one or more of activated carbon, kaolin, montmorillonite, attapulgite, diatomaceous earth, alumina, aluminum hydroxide, and magnesium oxide. The source of the physically adsorbed nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the nucleating agent adsorbed by the ions has negative charges in an aqueous solution, and can aggregate metal ions and metal ion compounds with positive charges into clusters to form secondary crystallization nuclei, and then secondary precipitation reaction is carried out continuously; in the present invention, the ion-adsorbing nucleating agent is preferably one or more of an alkyl group-containing organic compound, an aldehyde group-containing organic compound, a hydroxyl group-containing organic compound and a phenol group-containing organic compound, more preferably one or more of methane, ethane, butane, hexane, formic acid, acetic acid, ascorbic acid, citric acid, methanol, ethanol, propanol, 2-propanol, n-butanol, 2-butanol, n-undecanol, cycloethanol, t-butanol, trityl alcohol, phenol, cresol, aminophenol and nitrophenol, and most preferably one or more of methane, ethane, formic acid, acetic acid, ascorbic acid, citric acid, ethanol, phenol, cresol and aminophenol. The source of the ion-adsorbing nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the self-release nucleating agent can be dissociated in the reaction solution and mixed with the salt solution to form a new reaction solution, so as to form secondary crystallization nuclei and continue to perform secondary precipitation reaction; in the present invention, the self-dissociative nucleating agent is preferably one or more of nickel carbonate, manganese carbonate, cobalt carbonate, nickel hydroxide, manganese hydroxide and cobalt hydroxide, and more preferably one or more of manganese carbonate, nickel hydroxide, manganese hydroxide or cobalt hydroxide. The source of the self-disintegrable nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, 0 < x <1, 0 < y <1, and x + y <1, preferably 1/6. ltoreq. x.ltoreq. 1/2, and 1/6. ltoreq. y.ltoreq. 1/3. In a preferred embodiment of the present invention, M is CO32-, M' is aluminum hydroxide, x is 1/6, y is 1/6, and the nickel-cobalt-manganese precursor is a secondary particle formed by stacking a primary particle having a formula of ni0.1665co0.1665mn0.667co3 and a primary particle having a formula of al (oh)3@ ni0.1665co0.1665mn0.667co3; in another preferred embodiment of the present invention, M is (OH)22-, M' is alumina, x is 0.4, and y is 0.2, and the nickel-cobalt-manganese precursor is a secondary particle formed by stacking a primary particle having a general formula of ni0.4co0.2mn04(OH)2 and a primary particle having a general formula of Al2O3@ ni0.4co0.2mn0.4(OH) 2.
in the invention, the particle size of the nickel-cobalt-manganese precursor is 10-50 μm, preferably 12-25 μm. In the invention, the nickel-cobalt-manganese precursor is a secondary particle formed by stacking primary particles with a general formula of NixCoyMn1-x-yM and primary particles with a general formula of M' @ NixCoyMn 1-x-yM. In the present invention, the primary particles of the general formula NixCoyMn1-x-yM preferably have a particle size of 1 to 7 μm, more preferably 3.5 to 5.5 μm; the general formula M ' @ NixCoyMn1-x-yM represents primary particles which are formed by taking M ' as a nucleating agent and have different particle sizes from those of the general formula (I), and the nucleating agent M ' can aggregate the primary particles with the general formula NixCoyMn1-x-yM to a certain extent to form primary particles with larger particle sizes. In the present invention, the particle diameter ratio of the primary particles having a general formula of NixCoyMn1-x-yM to the primary particles having a general formula of M' @ NixCoyMn1-x-yM is preferably (0.1 to 0.4): 1, more preferably (0.17 to 0.32): 1.
The nickel-cobalt-manganese precursor provided by the invention is formed by stacking two primary particles with different shapes and particle sizes, and has higher tap density, the nickel-cobalt-manganese precursor obtained by the invention is prepared into the anode material by adopting a high-temperature solid-phase method well known by the technical personnel in the field, and the further prepared lithium ion battery has higher energy density.
The invention also provides a preparation method of the nickel-cobalt-manganese precursor, which comprises the following steps:
a) Mixing a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain primary particles with a general formula (I); the precipitant comprises one or more of carbonate-containing salt, hydrogen carbonate-containing salt and hydroxide-containing salt;
b) Mixing the primary particles with the general formula (I) with a nucleating agent, and carrying out secondary precipitation reaction to obtain a nickel-cobalt-manganese precursor;
The nickel-cobalt-manganese precursor is a secondary particle formed by stacking primary particles with a general formula (I) and primary particles with a general formula (II);
NixCoyMn1-x-yM formula (I);
M' @ NixCoyMn1-x-yM formula (II);
Wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y < 1;
The grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m.
In the invention, a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent are mixed for coprecipitation reaction to obtain primary particles with a general formula (I). In the present invention, the nickel source preferably includes one or more of nickel sulfate, nickel nitrate and nickel chloride, more preferably nickel sulfate. The source of the nickel source is not particularly limited in the present invention, and commercially available products of the above nickel sulfate, nickel nitrate and nickel chloride, which are well known to those skilled in the art, may be used.
in the present invention, the cobalt source preferably includes one or more of cobalt sulfate, cobalt nitrate and cobalt chloride, more preferably cobalt sulfate. The source of the cobalt source is not particularly limited in the present invention, and commercially available products of the above-mentioned cobalt sulfate, cobalt nitrate and cobalt chloride known to those skilled in the art may be used.
in the present invention, the manganese source preferably comprises one or more of manganese sulfate, manganese nitrate and manganese chloride, more preferably manganese sulfate. The source of the manganese source is not particularly limited in the present invention, and commercially available manganese sulfate, manganese nitrate and manganese chloride as described above, which are well known to those skilled in the art, may be used.
Firstly, mixing a nickel source, a cobalt source and a manganese source to obtain a nickel-cobalt-manganese mixed solution, wherein the molar ratio of nickel to cobalt to manganese in the mixed solution is x: y: (1-x-y); wherein x is more than 0 and less than 1, y is more than 0 and less than 1, x + y is less than 1, x is more than or equal to 1/6 and less than or equal to 1/2, and y is more than or equal to 1/6 and less than or equal to 1/3. The method of mixing is not particularly limited in the present invention, and mechanical stirring or manual stirring known to those skilled in the art may be employed. In the present invention, the molar concentration of the nickel ions, the cobalt ions and the manganese ions in the nickel-cobalt-manganese mixed solution is preferably 1.5mol/L to 3.5mol/L, and more preferably 2 mol/L.
In the invention, a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent are mixed for coprecipitation reaction to obtain primary particles with a general formula (I); the preferable process of the coprecipitation reaction is as follows:
Mixing the mixed solution of a nickel source, a cobalt source and a manganese source with a precipitator and a complexing agent, and reacting to obtain primary particles with a general formula (I). In the present invention, the precipitant preferably includes one or more of a carbonate-containing salt, a hydrogen carbonate-containing salt, and a hydroxide-containing salt, and more preferably one or more of sodium carbonate, sodium bicarbonate, and sodium hydroxide. In the invention, the precipitant can adjust the pH value of the mixed solution to form uniform precipitate; the source of the precipitant is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the precipitant is added into a mixed solution of a nickel source, a cobalt source and a manganese source in the form of an aqueous solution and mixed, and the molar concentration of the aqueous solution of the precipitant is preferably 2 mol/L-6 mol/L, and more preferably 3 mol/L-5 mol/L. The method of mixing is not particularly limited in the present invention, and mechanical stirring or manual stirring known to those skilled in the art may be employed.
in the invention, the complexing agent is preferably one or more of ammonia water, ammonium bicarbonate, ammonium phosphate and ammonium hydrogen phosphate, and more preferably ammonia water. The source of the complexing agent in the present invention is not particularly limited, and commercially available products of the above-mentioned aqueous ammonia, ammonium hydrogen carbonate, ammonium phosphate and ammonium hydrogen phosphate known to those skilled in the art may be used. In the invention, the complexing agent is added into a mixed solution of a nickel source, a cobalt source and a manganese source in the form of an aqueous solution and mixed, and the molar concentration of the aqueous solution of the complexing agent is preferably 0.5-4.5 mol/L, and more preferably 1-4 mol/L. The method of mixing is not particularly limited in the present invention, and mechanical stirring or manual stirring known to those skilled in the art may be employed.
In the present invention, the complexing agent is capable of complexing with nickel ions, cobalt ions and manganese ions; the ratio of the total mole number of nickel ions, cobalt ions and manganese ions to the mole number of the complexing agent in the mixed solution is preferably 2: (0.5 to 1.5), more preferably 2: 1.
In the invention, the mixed solution of a nickel source, a cobalt source and a manganese source is mixed with a precipitator and a complexing agent for reaction to obtain the primary particles with the general formula (I). In the invention, the pH value of the reaction is preferably 7.5-9.5, and more preferably 8-9; the reaction time is preferably 1 to 50 hours, more preferably 4 to 20 hours.
After the primary particles with the general formula (I) are obtained, the primary particles with the general formula (I) are mixed with a nucleating agent for secondary precipitation reaction to obtain the nickel-cobalt-manganese precursor. In the present invention, the nucleating agent preferably includes one or more of a physically adsorbed nucleating agent, an ion-adsorbed nucleating agent and a self-dissociating nucleating agent. In the invention, the physically adsorbed nucleating agent can adsorb suspended small particles to form secondary crystallization nuclei, and then secondary precipitation reaction is carried out continuously; in the present invention, the physically adsorbed nucleating agent is preferably one or more of activated carbon, silica gel, adsorption resin, kaolin, montmorillonite, attapulgite, diatomaceous earth, molecular sieve, alumina, aluminum hydroxide, aluminum carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, and calcium carbonate, and more preferably one or more of activated carbon, kaolin, montmorillonite, attapulgite, diatomaceous earth, alumina, aluminum hydroxide, and magnesium oxide. The source of the physically adsorbed nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the nucleating agent adsorbed by the ions has negative charges in an aqueous solution, and can aggregate metal ions and metal ion compounds with positive charges into clusters to form secondary crystallization nuclei, and then secondary precipitation reaction is carried out continuously; in the present invention, the ion-adsorbing nucleating agent is preferably one or more of an alkyl group-containing organic compound, an aldehyde group-containing organic compound, a hydroxyl group-containing organic compound and a phenol group-containing organic compound, more preferably one or more of methane, ethane, butane, hexane, formic acid, acetic acid, ascorbic acid, citric acid, methanol, ethanol, propanol, 2-propanol, n-butanol, 2-butanol, n-undecanol, cycloethanol, t-butanol, trityl alcohol, phenol, cresol, aminophenol and nitrophenol, and most preferably one or more of methane, ethane, formic acid, acetic acid, ascorbic acid, citric acid, ethanol, phenol, cresol and aminophenol. The source of the ion-adsorbing nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the self-release nucleating agent can be dissociated in the reaction solution and mixed with the salt solution to form a new reaction solution, so as to form secondary crystallization nuclei and continue to perform secondary precipitation reaction; in the present invention, the self-dissociative nucleating agent is preferably one or more of nickel carbonate, manganese carbonate, cobalt carbonate, nickel hydroxide, manganese hydroxide and cobalt hydroxide, and more preferably one or more of manganese carbonate, nickel hydroxide, manganese hydroxide or cobalt hydroxide. The source of the self-disintegrable nucleating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
in the present invention, primary particles of formula (I) are mixed with a nucleating agent, preferably in a molar ratio of 1: (0.001 to 0.5), more preferably 1: (0.01-0.1). In the present invention, the nucleating agent is mixed with the primary particles of the formula (I) in the form of a solution or suspension obtained by mixing with water, and the molar concentration of the aqueous solution or suspension of the nucleating agent is preferably 0.001mol/L to 0.5 mol/L.
In the present invention, the time of the secondary precipitation reaction is preferably 8 to 24 hours, and more preferably 10 to 20 hours. In the invention, a small amount of nucleating agent can form secondary crystallization nuclei, secondary precipitation reaction is continued to be carried out to obtain primary particles with a general formula (II), and the primary particles with the general formula (II) and unreacted primary particles with the general formula (I) are stacked to form secondary particles, thus obtaining the nickel-cobalt-manganese precursor.
The invention provides a nickel-cobalt-manganese precursor, which is a secondary particle formed by stacking primary particles with a general formula of NixCoyMn1-x-yM and primary particles with a general formula of M' @ NixCoyMn 1-x-yM; wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1; the grain diameter of the nickel-cobalt-manganese precursor is 10-50 mu m. Compared with the prior art, the nickel-cobalt-manganese precursor provided by the invention effectively controls the appearance, the particle size and the stacking effect of primary particles by optimizing the coprecipitation reaction, and obtains secondary particles with higher tap density, thereby being beneficial to the improvement of the energy density of a lithium ion battery. Experimental results show that the tap density of the nickel-cobalt-manganese precursor provided by the invention is more than 2.3g/cm 3.
in addition, the preparation method provided by the invention has high production efficiency, can realize continuous production, has higher economic benefit, reduces the emission of heavy metal ions in the production process, and is environment-friendly.
To further illustrate the present invention, the following examples are provided for illustration. The sources of the drugs used in the following examples of the present invention are shown in Table 1.
TABLE 1 sources of drugs used in the examples of the present invention
Name of medicine Manufacturer of the product Specification of
Nickel sulfate Chemical reagents of national drug group Co Ltd Analytically pure 98.5%
Cobalt sulfate Chemical reagents of national drug group Co Ltd Analytically pure 99.5%
Manganese sulfate Chemical reagents of national drug group Co Ltd Analytically pure 99.0%
sodium carbonate Chemical reagents of national drug group Co Ltd Analytically pure 99.0%
Aqueous ammonia chemical reagents of national drug group Co Ltd 25％～28％
Aluminium nitrate Chemical reagents of national drug group Co Ltd analytically pure 99%
Aluminum hydroxide chemical reagents of national drug group Co Ltd Analytically pure 99%
Manganese carbonate chemical reagents of national drug group Co Ltd Analytically pure 98.5%
Nickel hydroxide Chemical reagents of national drug group Co Ltd Analytically pure 99.0%
Cobalt hydroxide Chemical reagents of national drug group Co Ltd analytically pure 99.0%
sodium hydroxide Chemical reagents of national drug group Co Ltd Analytically pure 99.0%
alumina oxide Chemical reagents of national drug group Co Ltd Analytically pure 98.0%
Ascorbic acid Chemical reagents of national drug group Co Ltd analytically pure 98.0%
Activated carbon chemical reagents of national drug group Co Ltd 98.0％
Citric acid Chemical reagents of national drug group Co Ltd 99.5％
Example 1
(1) firstly, mixing the molar ratio of 1/6: 1/6: 2/3, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with a molar concentration of 4mol/L and an ammonia water solution with a molar concentration of 2mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 2: 1, controlling the pH value of the reaction to be 8.1 by adjusting the adding amount of a sodium carbonate solution, and carrying out coprecipitation reaction for 10 hours to obtain primary particles with a general formula of Ni0.1665Co0.1665Mn0.667CO3.
(3) The primary particles obtained with the general formula of ni0.1665co0.1665mn0.667co3 were mixed with 0.5mol/L of an aluminum nitrate solution, and the amount of the aluminum nitrate solution added was controlled so that the molar ratio of the primary particles with the general formula of ni0.1665co0.1665mn0.667co3 to aluminum ions was 1: and 0.05, continuing to perform secondary precipitation reaction for 20 hours to obtain primary particles with the general formula of Al (OH)3@ Ni0.1665Co0.1665Mn0.667CO3, stacking the primary particles with the general formula of Al (OH)3@ Ni0.1665Co0.1665Mn0.667CO3 and unreacted primary particles with the general formula of Ni0.1665Co0.1665Mn0.667CO3 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The nickel-cobalt-manganese precursor obtained in example 1 was analyzed by FEI QUANTA 250 FEG scanning electron microscope to obtain a scanning electron micrograph, as shown in fig. 1 to 2. Fig. 1 is a scanning electron microscope photograph of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention under a condition of 4500 times magnification, and fig. 2 is a scanning electron microscope photograph of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention under a condition of 1500 times magnification.
The particle size distribution curve is obtained by testing with an S3500-special laser particle size distribution instrument, as shown in FIG. 3. Fig. 3 is a particle size distribution curve diagram of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention. The test result shows that the nickel-cobalt-manganese precursor particles prepared in the embodiment 1 of the invention are relatively uniform, have good sphericity and good fluidity, and have particle diameters of 19.5 micrometers, wherein the particle diameter of the primary particle with the general formula of ni0.1665co0.1665mn0.667co3 is 5.2 micrometers, the particle diameter of the primary particle with the general formula of al (oh)3@ ni0.1665co0.1665mn0.667co3 is 20.3 micrometers, and the diameter ratio of the two particle diameters is 0.2562.
As shown in fig. 4, fig. 4 is a schematic diagram illustrating the deposition effect of the nickel-cobalt-manganese precursor provided in embodiment 1 of the present invention.
The test is carried out by using a BT-300 tap density tester, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided by the embodiment 1 of the invention is 2.5g/cm 3.
Example 2
(1) Firstly, mixing the molar ratio of 1/3: 1/3: 1/3, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with the molar concentration of 3mol/L and an ammonia water solution with the molar concentration of 1mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 1: 1, controlling the pH value of the reaction to be 8.3 by adjusting the adding amount of a sodium carbonate solution, and carrying out coprecipitation reaction for 5 hours to obtain primary particles with the general formula of Ni0.333Co0.333Mn0.334CO3.
(3) Mixing the obtained primary particles with the general formula of Ni0.333Co0.333Mn0.334CO3 with 0.02mol/L of aluminum hydroxide solution, and controlling the adding amount of the aluminum hydroxide solution to ensure that the molar ratio of the primary particles with the general formula of Ni0.333Co0.333Mn0.334CO3 to the aluminum hydroxide is 1: and 0.02, continuing carrying out secondary precipitation reaction for 15h to obtain primary particles with the general formula of Al (OH)3@ Ni0.333Co0.333Mn0.334CO3, wherein the primary particles with the general formula of Al (OH)3@ Ni0.333Co0.333Mn0.334CO3 and the unreacted primary particles with the general formula of Ni0.333Co0.333Mn0.334CO3 are stacked to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
the morphology and particle size of the ni — co-mn precursor obtained in example 2 were analyzed according to the method provided in example 1, and the results showed that the ni — co-mn precursor provided in example 2 of the present invention had a particle size of 17.5 μm, wherein the primary particles of the general formula ni0.333co0.333mn0.334co3 had a particle size of 4.1 μm, and the primary particles of the general formula al (oh)3@ ni0.333co0.333mn0.334co3 had a particle size of 18.6 μm, and the ratio of the particle sizes was 0.2204.
The tap density of the nickel-cobalt-manganese precursor provided in example 2 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 2 of the present invention is 2.35g/cm 3.
example 3
(1) Firstly, the molar ratio is 0.5: 0.3: 0.2 of nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with a molar concentration of 4mol/L and an ammonium bicarbonate solution with a molar concentration of 4mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonium bicarbonate solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonium bicarbonate solution is controlled to be 4: 1, controlling the pH value of the reaction to be 8.95 by adjusting the adding amount of a sodium carbonate solution, and carrying out coprecipitation reaction for 4 hours to obtain primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3.
(3) Mixing the obtained primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 with 0.2mol/L manganese carbonate suspension, and controlling the adding amount of the manganese carbonate suspension to ensure that the molar ratio of the primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 to the manganese carbonate is 1: and 0.02, continuing carrying out secondary precipitation reaction for 12 hours to obtain primary particles with the general formula of MnCO3@ Ni0.5Co0.3Mn0.2CO3, stacking the primary particles with the general formula of MnCO3@ Ni0.5Co0.3Mn0.2CO3 and unreacted primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The morphology and particle size of the nickel-cobalt-manganese precursor obtained in example 3 were analyzed according to the method provided in example 1, and the results show that the particle size of the nickel-cobalt-manganese precursor provided in example 3 of the present invention was 12.5 μm, where the particle size of the primary particle with the general formula ni0.5co0.3mn0.2co3 was 3.6 μm, the particle size of the primary particle with the general formula MnCO3@ ni0.5co0.3mn0.2co3 was 16.1 μm, and the particle size ratio of the two particles was 0.2236.
The tap density of the nickel-cobalt-manganese precursor provided in example 3 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 3 of the present invention is 2.32g/cm 3.
Example 4
(1) Firstly, the molar ratio is 0.5: 0.3: 0.2 of nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with the molar concentration of 3mol/L and an ammonia water solution with the molar concentration of 1mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 1: 1, controlling the pH value of the reaction to be 8.95 by adjusting the adding amount of a sodium carbonate solution, and carrying out coprecipitation reaction for 10 hours to obtain primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3.
(3) Mixing the primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 with 0.1mol/L nickel hydroxide suspension, and controlling the adding amount of the nickel hydroxide suspension to ensure that the molar ratio of the primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 to the nickel hydroxide is 1: and 0.01, continuing to perform secondary precipitation reaction for 20 hours to obtain primary particles with the general formula of Ni (OH)2@ Ni0.5Co0.3Mn0.2CO3, stacking the primary particles with the general formula of Ni (OH)2@ Ni0.5Co0.3Mn0.2CO3 and unreacted primary particles with the general formula of Ni0.5Co0.3Mn0.2CO3 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The morphology and the particle size of the nickel-cobalt-manganese precursor obtained in example 4 were analyzed according to the method provided in example 1, and the result shows that the particle size of the nickel-cobalt-manganese precursor provided in example 4 of the present invention was 22.5 μm, wherein the particle size of the primary particle with the general formula ni0.5co0.3mn0.2co3 was 4.6 μm, the particle size of the primary particle with the general formula ni (oh)2@ ni0.5co0.3mn0.2co3 was 26.1 μm, and the particle size ratio of the two was 0.1762.
The tap density of the nickel-cobalt-manganese precursor provided in example 4 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 4 of the present invention is 2.46g/cm 3.
example 5
(1) Firstly, the molar ratio is 0.4: 0.2: 0.4 of nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with the molar concentration of 5mol/L and an ammonia water solution with the molar concentration of 2.5mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 5: 2, controlling the pH value of the reaction to be 8.55 by adjusting the adding amount of the sodium carbonate solution, and carrying out coprecipitation reaction for 8 hours to obtain primary particles with the general formula of Ni0.4Co0.2Mn0.4CO3.
(3) The primary particles having the formula of ni0.4co0.2mn0.4co3 obtained were mixed with a suspension of 0.5mol/l ni0.33co0.33mn0.34(OH)2, and the amount of ni0.33co0.33mn0.34(OH)2 suspension added was controlled so that the molar ratio of the primary particles having the formula of ni0.4co0.2mn0.4co3 to ni0.33co0.33mn0.34(OH)2 was 1: and 0.05, continuing carrying out secondary precipitation reaction for 8h to obtain primary particles with the general formula of Ni0.33Co0.33Mn0.34(OH)2@ Ni0.4Co0.2Mn0.4CO3, wherein the primary particles with the general formula of Ni0.33Co0.33Mn0.34(OH)2@ Ni0.4Co0.2Mn0.4CO3 and the unreacted primary particles with the general formula of Ni0.4Co0.2Mn0.4CO3 are stacked to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The morphology and particle size of the nickel-cobalt-manganese precursor obtained in example 5 were analyzed according to the method provided in example 1, and the results show that the particle size of the nickel-cobalt-manganese precursor provided in example 5 of the present invention was 15.2 μm, wherein the particle size of the primary particle with the general formula ni0.4co0.2mn0.4co3 was 5.2 μm, the particle size of the primary particle with the general formula ni0.33co0.33mn0.34(OH)2@ ni0.4co0.2mn0.4co3 was 16.5 μm, and the particle size ratio of the two was 0.3152.
The tap density of the nickel-cobalt-manganese precursor provided in example 5 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 5 of the present invention is 2.42g/cm 3.
Example 6
(1) Firstly, the molar ratio is 0.4: 0.2: 0.4 of nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium hydroxide solution with the molar concentration of 5mol/L and an ammonia water solution with the molar concentration of 2.5mol/L are respectively prepared.
(2) adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium hydroxide solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 5: 2, controlling the pH value of the reaction to be 8.55 by adjusting the adding amount of the sodium hydroxide solution, and carrying out coprecipitation reaction for 20 hours to obtain primary particles with the general formula of Ni0.4Co0.2Mn0.4(OH) 2.
(3) The primary particles having the general formula ni0.4co0.2mn0.4(OH)2 obtained were mixed with 0.001mol/L alumina suspension, and the amount of the alumina suspension added was controlled so that the molar ratio of the primary particles having the general formula ni0.4co0.2mn0.4(OH)2 to alumina was 1: and 0.01, continuing carrying out secondary precipitation reaction for 20h to obtain primary particles with the general formula of Al2O3@ Ni0.4Co0.2Mn0.4(OH)2, stacking the primary particles with the general formula of Al2O3@ Ni0.4Co0.2Mn0.4(OH)2 and unreacted primary particles with the general formula of Ni0.4Co0.2Mn0.4(OH)2 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
the morphology and particle size of the nickel-cobalt-manganese precursor obtained in example 6 were analyzed according to the method provided in example 1, and the results show that the particle size of the nickel-cobalt-manganese precursor provided in example 6 of the present invention was 14.8 μm, wherein the particle size of the primary particle with the general formula ni0.4co0.2mn0.4(OH)2 was 3.8 μm, the particle size of the primary particle with the general formula Al2O3@ ni0.4co0.2mn0.4(OH)2 was 18.1 μm, and the ratio of the particle sizes was 0.2652.
the tap density of the nickel-cobalt-manganese precursor provided in example 6 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 6 of the present invention is 2.42g/cm 3.
Example 7
(1) Firstly, mixing the molar ratio of 1/6: 1/6: 2/3, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium hydroxide solution with a molar concentration of 4mol/L and an ammonia water solution with a molar concentration of 2mol/L are respectively prepared.
(2) adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium hydroxide solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 2: 1, controlling the pH value of the reaction to be 8.05 by adjusting the adding amount of a sodium hydroxide solution, and carrying out coprecipitation reaction for 15 hours to obtain primary particles with the general formula of Ni0.1665Co0.1665Mn0.667(OH) 2.
(3) The primary particles obtained with the general formula of ni0.1665co0.1665mn0.667(OH)2 were mixed with 0.02mol/L ascorbic acid solution, and the amount of ascorbic acid solution added was controlled so that the molar ratio of the primary particles with the general formula of ni0.1665co0.1665mn0.667(OH)2 to ascorbic acid was 1: and 0.02, continuing performing secondary precipitation reaction for 10 hours to obtain primary particles with the general formula of ascorbic acid @ Ni0.1665Co0.1665Mn0.667(OH)2, stacking the primary particles with the general formula of ascorbic acid @ Ni0.1665Co0.1665Mn0.667(OH)2 and unreacted primary particles with the general formula of Ni0.1665Co0.1665Mn0.667(OH)2 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
As a result of analyzing the morphology and the particle size of the nickel-cobalt-manganese precursor obtained in example 7 according to the method provided in example 1, the particle size of the nickel-cobalt-manganese precursor provided in example 7 of the present invention was 19.5 μm, where the particle size of the primary particle having the general formula ni0.1665co0.1665mn0.667(OH)2 was 6.3 μm, the particle size of the primary particle having the general formula ascorbic acid @ ni0.1665co0.1665mn0.667(OH)2 was 20.1 μm, and the ratio of the particle sizes was 0.3134.
The tap density of the nickel-cobalt-manganese precursor provided in example 7 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 7 of the present invention is 2.35g/cm 3.
Example 8
(1) Firstly, mixing the molar ratio of 1/6: 1/6: 2/3, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium hydroxide solution with the molar concentration of 3mol/L and an ammonia water solution with the molar concentration of 1.2mol/L are respectively prepared.
(2) adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium hydroxide solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 1.2: 1, controlling the pH value of the reaction to be 8.25 by adjusting the adding amount of a sodium hydroxide solution, and carrying out coprecipitation reaction for 6 hours to obtain primary particles with the general formula of Ni0.1665Co0.1665Mn0.667(OH) 2.
(3) The primary particles obtained with the general formula of ni0.1665co0.1665mn0.667(OH)2 were mixed with 0.015mol/L activated carbon suspension, and the amount of the activated carbon suspension added was controlled so that the molar ratio of the primary particles with the general formula of ni0.1665co0.1665mn0.667(OH)2 to the activated carbon was 1: and 0.015, continuing to perform secondary precipitation reaction for 12 hours to obtain primary particles with a general formula of activated carbon @ Ni0.1665Co0.1665Mn0.667(OH)2, stacking the primary particles with the general formula of activated carbon @ Ni0.1665Co0.1665Mn0.667(OH)2 and unreacted primary particles with the general formula of Ni0.1665Co0.1665Mn0.667(OH)2 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
As a result of analyzing the morphology and the particle size of the nickel-cobalt-manganese precursor obtained in example 8 according to the method provided in example 1, the particle size of the nickel-cobalt-manganese precursor provided in example 8 of the present invention is 12.5 μm, where the particle size of the primary particle having the general formula ni0.1665co0.1665mn0.667(OH)2 is 2.6 μm, the particle size of the primary particle having the general formula activated carbon @ ni0.1665co0.1665mn0.667(OH)2 is 14.2 μm, and the ratio of the particle sizes is 0.1831.
The tap density of the nickel-cobalt-manganese precursor provided in example 8 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 8 of the present invention is 2.36g/cm 3.
example 9
(1) Firstly, mixing the molar ratio of 1/4: 1/4: 1/2, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium bicarbonate solution with a molar concentration of 4mol/L and an ammonia water solution with a molar concentration of 2mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium bicarbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 2: 1, controlling the pH value of the reaction to be 8.95 by adjusting the adding amount of a sodium bicarbonate solution, and carrying out coprecipitation reaction for 12 hours to obtain primary particles with the general formula of Ni0.25Co0.25Mn0.5CO3.
(3) The primary particles obtained with the general formula ni0.25co0.25mn0.5co3 were mixed with 0.08mol/L citric acid solution, and the amount of citric acid solution added was controlled so that the molar ratio of the primary particles with the general formula ni0.25co0.25mn0.5co3 to citric acid was 1: and 0.08, continuing performing secondary precipitation reaction for 24 hours to obtain primary particles with the general formula of citric acid @ Ni0.25Co0.25Mn0.5CO3, stacking the primary particles with the general formula of citric acid @ Ni0.25Co0.25Mn0.5CO3 and unreacted primary particles with the general formula of Ni0.25Co0.25Mn0.5CO3 to form secondary particles, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The morphology and particle size of the nickel-cobalt-manganese precursor obtained in example 9 were analyzed according to the method provided in example 1, and the result shows that the particle size of the nickel-cobalt-manganese precursor provided in example 9 of the present invention was 13.5 μm, where the particle size of the primary particle with the general formula ni0.25co0.25mn0.5co3 was 5.4 μm, the particle size of the primary particle with the general formula citric acid @ ni0.25co0.25mn0.5co3 was 14.2 μm, and the particle size ratio of the two was 0.3803.
The tap density of the nickel-cobalt-manganese precursor provided in example 9 was tested according to the method provided in example 1, and the result shows that the tap density of the nickel-cobalt-manganese precursor provided in example 9 of the present invention is 2.32g/cm 3.
Comparative example
(1) Firstly, mixing the molar ratio of 1/6: 1/6: 2/3, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water to obtain a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total molar concentration of nickel ions, cobalt ions and manganese ions in the mixed solution is 2 mol/L; meanwhile, a sodium carbonate solution with a molar concentration of 4mol/L and an ammonia water solution with a molar concentration of 2mol/L are respectively prepared.
(2) Adding a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, a prepared sodium carbonate solution and an ammonia water solution into a reaction kettle with a stirrer for reaction, wherein the volume ratio of the mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate to the ammonia water solution is controlled to be 2: 1, controlling the pH value of the reaction to be 8.1 by adjusting the adding amount of a sodium carbonate solution, carrying out coprecipitation reaction for 30 hours to obtain secondary particles formed by stacking primary particles with a general formula of Ni0.1665Co0.1665Mn0.667CO3, and separating and washing to obtain the nickel-cobalt-manganese precursor.
The morphology and particle size of the nickel-cobalt-manganese precursor obtained in the comparative example were analyzed according to the method provided in example 1, and a scanning electron micrograph thereof was obtained, as shown in fig. 5. Fig. 5 is a scanning electron micrograph of the nickel-cobalt-manganese precursor provided by the comparative example of the present invention at 500 times magnification. The particle size distribution curve is obtained by testing with a laser particle size distribution instrument, as shown in fig. 6. Fig. 6 is a particle size distribution curve diagram of a nickel-cobalt-manganese precursor according to a comparative example of the present invention. The test result shows that the nickel-cobalt-manganese precursor prepared by the comparative example has relatively uniform particles, good sphericity and good fluidity, and the particle size is 23.8 mu m.
The deposition effect of the nickel-cobalt-manganese precursor provided by the above comparative example was analyzed, as shown in fig. 7, fig. 7 is a schematic diagram of the deposition effect of the nickel-cobalt-manganese precursor provided by the comparative example of the present invention.
the tap density of the nickel-cobalt-manganese precursor provided by the comparative example was tested according to the method provided in example 1, and the results show that the tap density of the nickel-cobalt-manganese precursor provided by the comparative example of the present invention is 2.0g/cm 3.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. The nickel-cobalt-manganese precursor is characterized by being a secondary particle formed by stacking a primary particle with a general formula (I) and a primary particle with a general formula (II);
NixCoyMn1-x-yM formula (I);
M' @ NixCoyMn1-x-yM formula (II);
Wherein, M is CO 32-Or (OH) 22-; m' is a nucleating agent; x is more than 0 and less than 1; y is more than 0 and less than 1; x + y is less than 1;
the particle size of the nickel-cobalt-manganese precursor is 12.5-25 mu m;
The particle size of the primary particles with the general formula of (I) is 3.5-5.5 μm;
The particle diameter ratio of the primary particles with the general formula (I) to the primary particles with the general formula (II) is (0.17-0.32): 1;
The preparation method of the nickel-cobalt-manganese precursor comprises the following steps:
a) Mixing a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain primary particles with a general formula (I); the precipitant comprises one or more of carbonate-containing salt, hydrogen carbonate-containing salt and hydroxide-containing salt; the pH value of the coprecipitation reaction is 7.5-9.5, and the time is 1-50 h;
b) Mixing the primary particles with the general formula (I) with a nucleating agent, and carrying out secondary precipitation reaction to obtain a nickel-cobalt-manganese precursor; the time of the secondary precipitation reaction is 8-24 h.
2. The nickel-cobalt-manganese precursor of claim 1, wherein the nucleating agent comprises one or more of a physisorbed nucleating agent, an ionically sorbed nucleating agent, and a self-dissociating nucleating agent.
3. the nickel-cobalt-manganese precursor of claim 1, wherein the complexing agent is one or more of aqueous ammonia, ammonium bicarbonate, ammonium phosphate, and ammonium hydrogen phosphate.
4. the nickel-cobalt-manganese precursor according to claim 1, wherein the co-precipitation reaction in step a) is specifically performed by:
Mixing the mixed solution of a nickel source, a cobalt source and a manganese source with a precipitator and a complexing agent, and reacting to obtain primary particles with a general formula (I).
5. The nickel-cobalt-manganese precursor of claim 4, wherein the ratio of the total moles of nickel, cobalt and manganese ions to the moles of complexing agent in the mixed solution is 2: (0.5 to 1.5).
6. The nickel-cobalt-manganese precursor according to claim 1, wherein the molar ratio of primary particles of formula (I) to nucleating agent in step b) is 1: (0.001-0.5).
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