CN103904319A - Preparation method of power type nickel-cobalt lithium manganate positive electrode material - Google Patents

Preparation method of power type nickel-cobalt lithium manganate positive electrode material Download PDF

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CN103904319A
CN103904319A CN201410076330.9A CN201410076330A CN103904319A CN 103904319 A CN103904319 A CN 103904319A CN 201410076330 A CN201410076330 A CN 201410076330A CN 103904319 A CN103904319 A CN 103904319A
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preparation
nickel
solution
cobalt
shower nozzle
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CN103904319B (en
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谢英豪
余海军
李长东
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Ningde Bangpu Recycling Technology Co.,Ltd.
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Waste And Old Materials Recovery Co Ltd
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • 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
    • 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 discloses a preparation method of a power type nickel-cobalt lithium manganate positive electrode material. The preparation method comprises the following steps: firstly dissolving partial lithium source as well as nickel, cobalt and manganese sources in an organic solvent; then dissolving the rest of lithium source in water, and meanwhile pelleting through a double-nozzle pyrolyzing furnace; blending in the furnace; and then carrying out high temperature sintering on mixed powder so as to obtain the nickel-cobalt lithium manganate positive electrode material. Irons of NH4<+>, Na<+> and the like are not produced in the preparation process, so that the pollution to the environment is greatly reduced; the obtained nickel-cobalt lithium manganate material is good in degree of sphericity, uniform in component distribution, high in tap density and excellent in cycling stability during the charging and discharging cyclic process; the initial discharge specific capacity is obviously improved.

Description

A kind of preparation method of power type nickel-cobalt lithium manganate cathode material
Technical field
The invention belongs to cell positive material preparing technical field, particularly a kind of preparation method of power type nickel-cobalt lithium manganate cathode material.
Background technology
China's " energy-conservation and new-energy automobile industrial development planning (2012-2020) " electric automobile accumulative total is sold to 2015 and reaches 500,000, and the year two thousand twenty reaches 5,000,000.Under the guidance of national policy, electrokinetic cell industry obtains develop rapidly.The advantages such as to have fail safe good because of lithium ion battery, and electric discharge specific energy is high, discharges and recharges the life-span long, pollution-free be it is believed that it is one of the most promising electrokinetic cell.
Positive electrode directly determines the performance of lithium ion battery.Nickel-cobalt lithium manganate cathode material adopts relatively inexpensive nickel and manganese to replace a large amount of cobalt in cobalt acid lithium, thereby it has very significantly advantage aspect reducing costs, simultaneously because of considerable charge/discharge capacity and excellent cyclical stability, the production of nickel-cobalt lithium manganate cathode material and use increasingly extensively, demonstrates huge market prospects.
The pattern of nickle cobalt lithium manganate self and size play an important role to the performance of electrical property.Research shows, sphere material particle can make material have larger tap density and useful life.In addition, good nickel-cobalt lithium manganate material must have suitable size and narrower particle size distribution, and is the bead of non-reunion.Routine is prepared the coprecipitation of spherical nickel-cobalt LiMn2O4, owing to adopting the alkali lye such as ammoniacal liquor or NaOH to precipitate in technical process, and NH 4 +, Na +plasma easily pollutes water body and context.And coprecipitation causes being difficult in same system the coprecipitate of being stablized and stoichiometric proportion is fixing because of the difference of the solubility product of nickel, cobalt, hydroxide that the each element of manganese is corresponding.The conventional solid phase method adopting, in its technical process, before sintering, need to material pulverize, batch mixing, although and grind through long-time before roasting, lithium salts, nickel salt and cobalt salt are all difficult to reach other even contact of molecular level, and poor its stable electrochemical property that causes of the uniformity of material is not high.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of power type nickel-cobalt lithium manganate cathode material is provided.
The technical solution used in the present invention is:
A preparation method for power type nickel-cobalt lithium manganate cathode material, comprises the following steps:
(1) by lithium source, nickel source, cobalt source, manganese source Li:Ni:Co:Mn=x:y:z:(1-y-z in molar ratio) be dissolved in organic solvent, add appropriate viscosity-controlling agent, mix, obtain solution I; Wherein, 0.1≤x≤0.3,0.1≤y≤0.9,0.1≤z≤0.5, y+z<1;
(2) by water-soluble the lithium source of (1.0～1.1)-x, add appropriate viscosity-controlling agent, mix, obtain solution II;
(3) solution I is carried out to press atomization granulation by shower nozzle A, the solution II of two shower nozzle pyrolysis ovens by shower nozzle B simultaneously, obtain the mixed-powder in presoma and lithium source;
(4) mixed-powder step (3) being obtained is sintering 5～20h at 600～1000 ℃ of temperature, obtains nickel-cobalt lithium manganate cathode material.
Preferably, the straight-chain carboxylic acid that the carbon number that the described organic solvent of step (1) is molten condition is 12～18.
Preferably, in solution I, concentration of metal ions is 0.5～3mol/L.
Preferably, in solution II, lithium concentration is 1～5mol/L.
Preferably, the described viscosity-controlling agent of step (1) is at least one in triethylamine, glyoxal, glutaraldehyde, benzaldehyde, benzoic acid, isobutylaldehyde, cinnamic acid, cinnamic acid; The described viscosity-controlling agent of step (2) is at least one in ethylene glycol, glycerol, triethanolamine, ethylenediamine, tetraethylene glycol, ethylenimine, acetamide, dibutyl ethers, isobutyl amine, 2-butanone, propylamine, 2-propyl alcohol.
Preferably, in solution I, the concentration of viscosity-controlling agent is 1～5 g/L.
Preferably, in solution II, the concentration of viscosity-controlling agent is 2～10g/L.
Preferably, in step (3), the operating pressure of controlling shower nozzle A is 0.1～0.6MPa, and charging rate is 500～5000mL/h; The operating pressure of controlling shower nozzle B is 0.05～0.3MPa, and charging rate is 300～2050mL/h.
Preferably, in step (3), controlling prilling temperature in pyrolysis oven stove is 400～600 ℃.
Preferably, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section in pyrolysis oven stove from top to bottom, blast hot-air in after-flame section, make particle that step (3) makes in rolling state, particle is 1～5min at residing time in furnace.
Preferably, described lithium source is at least one in lithium acetate, lithium oxalate, lithium citrate, lithium hydroxide; Described nickel source is at least one in nickel acetate, nickel oxalate, citric acid nickel, nickel hydroxide; Described cobalt source is at least one in cobalt acetate, cobalt oxalate, citric acid cobalt, cobalt hydroxide; Described manganese source is at least one in manganese acetate, manganese oxalate, manganese citrate, manganous hydroxide.
The invention has the beneficial effects as follows:
1, the present invention adopts melting carboxylic acid as solvent, and carboxylic acid solvent has solvent, compounding ingredient, surfactant triple role concurrently simultaneously, makes the uniform and stable mixing in liquid phase of each metal ion species, also can avoid the hydrolysis of water to slaine.The structures such as carboxylic acid solvent's molecule and intermolecular formation hydrogen bond association, make to be wound around point between molecule and increase, and between molecule, active force strengthens, and therefore, makes the nickle cobalt lithium manganate that sintering obtains have larger tap density.
2, the present invention mixes part lithium source with nickel, cobalt, manganese source solution, and each component is mixed at atomic level, and lithium source will be evenly distributed in precursor solution; The precursor solution that includes lithium source sprays from the shower nozzle A of two shower nozzle pyrolysis ovens, and another part lithium source solution sprays from shower nozzle B, under air-flow drives, mixes with it, obtains the even mixed-powder in presoma and lithium source; Mixed-powder is carried out to high temperature sintering, and organic solvent is given granular precursor loose structure after at high temperature burning, and is conducive to make the Li in molten lithium source 2o fully diffuses into presoma inside from hole, material composition is distributed more even.Introduce in two steps in lithium source, further optimizes material composition and distribute, and obtains more preferably measuring and compare chemicals after sintering.
3, the present invention adopts two shower nozzle pyrolysis ovens simultaneously to presoma and the granulation of lithium source, and in stove, the drive by air-flow mixes, and has avoided the mixing method of conventional ball milling may destroy the defect of the spherical porous structure of presoma.
4, in technical process of the present invention, do not adopt the alkali such as ammoniacal liquor or NaOH to precipitate, do not produce NH in traditional handicraft 4 +, Na +the pollution of plasma to water, greatly reduces the pollution to environment.Gained nickle cobalt lithium manganate product yield is high, good sphericity, and tap density is high, have excellent cyclical stability, and first discharge specific capacity significantly improves in charge and discharge cycles process.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nickel-cobalt lithium manganate cathode material;
Fig. 2 is the charging and discharging curve figure of nickel-cobalt lithium manganate cathode material assembled battery;
Fig. 3 is the cycle performance figure of nickel-cobalt lithium manganate cathode material assembled battery.
Embodiment
Below in conjunction with specific embodiment, further set forth content of the present invention.
embodiment 1
A preparation method for power type nickle cobalt lithium manganate, comprises following concrete steps:
(1) lithium acetate, nickel acetate, four hydration cobalt acetates, manganese acetate are joined in the dodecylic acid of 50 ℃ that volume is 2.2L and dissolved by quality 6.60g, 17.68g, 124.54g, 69.2g respectively, stirring 2h mixes, then be added dropwise to while stirring 2.2g triethylamine, continue to stir 3h and mix, obtain solution I;
(2) 59.39g lithium acetate is dissolved in 0.9L water, adds 1.8g ethylene glycol, stir 1h and mix, obtain solution II;
(3) solution I is carried out to press atomization granulation at the shower nozzle A of two shower nozzle pyrolysis ovens, controlled pressure is 0.6MPa, and charging rate is 5000mL/h, simultaneously, solution II is carried out to press atomization granulation at the shower nozzle B of two shower nozzle pyrolysis ovens, and controlled pressure is 0.3MPa, and charging rate is 2050mL/h; Between shower nozzle A, B, there is the adjustable baffle plate of a block length, in stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, the particle making is in rolling state, and to control in stove prilling temperature be that 400 ℃, particle stop 5min in stove; Granulation completes, and obtains presoma and lithium source mixed-powder;
(4) presoma step (3) being obtained and lithium source mixed-powder are placed in Muffle furnace and carry out sintering at air, and 600 ℃ of constant temperature sintering 20h, obtain power type nickel-cobalt lithium manganate cathode material.
embodiment 2
A preparation method for power type nickle cobalt lithium manganate, comprises following concrete steps:
(1) lithium acetate, nickel acetate, four hydration cobalt acetates, manganese acetate are joined in the tetracosandioic acid of 135 ℃ that volume is 1.5L and dissolved by quality 6.60g, 17.68g, 124.54g, 69.2g respectively, stirring 2h mixes, then be added dropwise to while stirring 3.0g glyoxal, continue to stir 3h and mix, obtain solution I;
(2) 59.39g lithium acetate is dissolved in 0.6L water, adds 2.0g glycerol, stir 1h and mix, obtain solution II;
(3) solution I is carried out to press atomization granulation at the shower nozzle A of two shower nozzle pyrolysis ovens, controlled pressure is 0.5MPa, and charging rate is 4000mL/h, simultaneously, solution II is carried out to press atomization granulation at the shower nozzle B of two shower nozzle pyrolysis ovens, and controlled pressure is 0.2MPa, and charging rate is 1600mL/h; Between shower nozzle A, B, there is the adjustable baffle plate of a block length, in stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, the particle making is in rolling state, and to control in stove prilling temperature be that 450 ℃, particle stop 4min in stove; Granulation completes, and obtains presoma and lithium source mixed-powder;
(4) presoma step (3) being obtained and lithium source mixed-powder are placed in Muffle furnace and carry out sintering at air, and 700 ℃ of constant temperature sintering 15h, obtain power type nickel-cobalt lithium manganate cathode material.
embodiment 3
A preparation method for power type nickle cobalt lithium manganate, comprises following concrete steps:
(1) lithium oxalate, nickel oxalate, cobalt oxalate, manganese oxalate are joined in the hexadecanoic acid of 65 ℃ that volume is 0.8L and dissolved by quality 19.19g, 48.90g, 48.97g, 47.65g respectively, stir 3h, then be added dropwise to while stirring 2.4g glutaraldehyde, continue to stir 2h, obtain solution I;
(2) 76.78g lithium oxalate is dissolved in 0.267L water, adds 1.33g triethanolamine, stir 2h and mix, obtain solution II;
(3) solution I is carried out to press atomization granulation at the shower nozzle A of two shower nozzle pyrolysis ovens, controlled pressure is 0.3MPa, and charging rate is 3000mL/h; Meanwhile, solution II is carried out to press atomization granulation at the shower nozzle B of two shower nozzle pyrolysis ovens, controlled pressure is 0.15MPa, and charging rate is 1000mL/h; In stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, the particle making is in rolling state, and to control in stove prilling temperature be that 500 ℃, particle stop 3min in stove; Granulation completes, and obtains presoma and lithium source mixed-powder;
(4) presoma step (3) being obtained and lithium source mixed-powder are placed in Muffle furnace and carry out sintering at air, and 800 ℃ of sintering 10h, obtain power type nickel-cobalt lithium manganate cathode material.
embodiment 4
A preparation method for power type nickle cobalt lithium manganate, comprises following concrete steps:
(1) lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganous hydroxide are joined in the hexadecandioic acid (hexadecane diacid) of 130 ℃ that volume is 0.6L and dissolved by quality 7.18g, 74.17g, 9.29g, 8.89g respectively, stir 4h, then be added dropwise to while stirring 2.5g benzaldehyde, continue to stir 1h, obtain solution I;
(2) 76.78g lithium oxalate is dissolved in 0.3L water, adds 2.25g ethylenediamine, stir 2h and mix, obtain solution II;
(3) solution I is carried out to press atomization granulation at the shower nozzle A of two shower nozzle pyrolysis ovens, controlled pressure is 0.2MPa, and charging rate is 1500mL/h, simultaneously, solution II is carried out to press atomization granulation at the shower nozzle B of two shower nozzle pyrolysis ovens, and controlled pressure is 0.1MPa, and charging rate is 750mL/h; In stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, the particle making is in rolling state, and to control in stove prilling temperature be that 550 ℃, particle stop 1min in stove; Granulation completes, and obtains presoma and lithium source mixed-powder;
(4) presoma step (3) being obtained and lithium source mixed-powder are placed in Muffle furnace and carry out sintering at air, and 900 ℃ of sintering 8h, obtain power type nickel-cobalt lithium manganate cathode material.
embodiment 5
A preparation method for power type nickle cobalt lithium manganate, comprises following concrete steps:
(1) lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganous hydroxide are joined in the octadecanoid acid of 85 ℃ that volume is 0.433L and dissolved by quality 7.18g, 74.17g, 9.29g, 8.89g respectively, stir 5h, then be added dropwise to while stirring 2.17g benzoic acid, continue to stir 1h, obtain solution I;
(2) 76.78g lithium oxalate is dissolved in 0.267L water, adds 1.34g tetraethylene glycol, stir 2h and mix, obtain solution II;
(3) solution I is carried out to press atomization granulation at the shower nozzle A of two shower nozzle pyrolysis ovens, controlled pressure is 0.1MPa, and charging rate is 500mL/h, simultaneously, solution II is carried out to press atomization granulation at the shower nozzle B of two shower nozzle pyrolysis ovens, and controlled pressure is 0.05MPa, and charging rate is 300mL/h; In stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, the particle making is in rolling state, and to control in stove prilling temperature be that 600 ℃, particle stop 1min in stove; Granulation completes, and obtains presoma and lithium source mixed-powder;
(4) presoma step (3) being obtained and lithium source mixed-powder are placed in Muffle furnace and carry out sintering at air, and 1000 ℃ of sintering 5h, obtain power type nickel-cobalt lithium manganate cathode material.
comparative example
Take respectively 65.99g lithium acetate, 58.93g nickel acetate, 82.03g four hydration cobalt acetates, 57.67g manganese acetate, add 200mL absolute ethyl alcohol to make dispersant, with planetary ball mill ball milling 2h, after 105 ℃ of oven dry of baking oven, the powder obtaining is placed in to Muffle furnace and carries out sintering at air, sintering temperature is 600 ℃, constant temperature 20h.Obtain nickle cobalt lithium manganate comparative sample.
performance Detection:
1, Fig. 1 is the SEM figure that embodiment 1 makes nickel-cobalt lithium manganate cathode material, can find out, gained sample is the spherical of rule, pattern rule, good dispersion, particle size high conformity, particle diameter is distributed between 6～12 μ m, the bulk density of material, the volume energy density of increase battery can not only be improved, and the processing characteristics in slurry coating, electrode production process can be significantly improved.The SEM figure of nickel-cobalt lithium manganate cathode material prepared by other embodiment and embodiment 1 are without bigger difference.
2, the nickle cobalt lithium manganate making take embodiment 3 and comparative example respectively, as anodal, take lithium metal as negative pole, is assembled into battery, carries out discharge test first with 1C multiplying power, and result as shown in Figure 2.Result demonstration, under 1C multiplying power, the first discharge specific capacity of nickel-cobalt lithium manganate cathode material prepared by embodiment 3 is than the height of common solid phase method, and the specific capacity of embodiment 3 is 151.9mAh/g, and the specific capacity of comparative example only has 136.2mAh/g.
Carry out 100 charge and discharge cycles tests with 1C multiplying power, as shown in Figure 3.Result demonstration, the specific capacity of nickel-cobalt lithium manganate cathode material prepared by embodiment 3 is after 100 circulations, and than the height of common solid phase method, the capability retention of embodiment 3 is 90.7%, and the capability retention of comparative example only has 82.4%.

Claims (10)

1. a preparation method for power type nickel-cobalt lithium manganate cathode material, comprises the following steps:
(1) by lithium source, nickel source, cobalt source, manganese source Li:Ni:Co:Mn=x:y:z:(1-y-z in molar ratio) be dissolved in organic solvent, add appropriate viscosity-controlling agent, mix, obtain solution I; Wherein, 0.1≤x≤0.3,0.1≤y≤0.9,0.1≤z≤0.5, y+z<1;
(2) by water-soluble the lithium source of (1.0～1.1)-x, add appropriate viscosity-controlling agent, mix, obtain solution II;
(3) solution I is carried out to press atomization granulation by shower nozzle A, the solution II of two shower nozzle pyrolysis ovens by shower nozzle B simultaneously, obtain the mixed-powder in presoma and lithium source;
(4) mixed-powder step (3) being obtained is sintering 5～20h at 600～1000 ℃ of temperature, obtains nickel-cobalt lithium manganate cathode material.
2. preparation method according to claim 1, is characterized in that: the straight-chain carboxylic acid that the carbon number that the described organic solvent of step (1) is molten condition is 12～18.
3. preparation method according to claim 1, is characterized in that: in solution I, concentration of metal ions is 0.5～3mol/L.
4. preparation method according to claim 1, is characterized in that: in solution II, lithium concentration is 1～5mol/L.
5. preparation method according to claim 1, is characterized in that: the described viscosity-controlling agent of step (1) is at least one in triethylamine, glyoxal, glutaraldehyde, benzaldehyde, benzoic acid, isobutylaldehyde, cinnamic acid, cinnamic acid; The described viscosity-controlling agent of step (2) is at least one in ethylene glycol, glycerol, triethanolamine, ethylenediamine, tetraethylene glycol, ethylenimine, acetamide, dibutyl ethers, isobutyl amine, 2-butanone, propylamine, 2-propyl alcohol.
6. preparation method according to claim 1 or 5, is characterized in that: in solution I, the concentration of viscosity-controlling agent is 1～5 g/L.
7. preparation method according to claim 1 or 5, is characterized in that: in solution II, the concentration of viscosity-controlling agent is 2～10g/L.
8. preparation method according to claim 1, is characterized in that: in step (3), the operating pressure of controlling shower nozzle A is 0.1～0.6MPa, and charging rate is 500～5000mL/h; The operating pressure of controlling shower nozzle B is 0.05～0.3MPa, and charging rate is 300～2050mL/h.
9. preparation method according to claim 1, is characterized in that: in step (3), controlling prilling temperature in pyrolysis oven stove is 400～600 ℃.
10. according to the preparation method described in claim 1,8 or 9, it is characterized in that: in pyrolysis oven stove, be divided into dryer section, pyrolysis section, burning zone, after-flame section and cooling section from top to bottom, blast hot-air in after-flame section, make particle that step (3) makes in rolling state, particle is 1～5min at residing time in furnace.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015131745A1 (en) * 2014-03-04 2015-09-11 广东邦普循环科技有限公司 Method for preparation of power-type nickel cobalt manganate lithium positive electrode material
WO2016011963A1 (en) * 2014-07-25 2016-01-28 台湾立凯电能科技股份有限公司 Method for preparing lithium nickel manganese oxide positive battery electrode material, and lithium nickel manganese oxide positive battery electrode material
CN108899513A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of preparation method of the trielement composite material containing organic salt
CN109546140A (en) * 2018-09-13 2019-03-29 德阳威旭锂电科技有限责任公司 A kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium
CN113178565A (en) * 2021-03-29 2021-07-27 广东邦普循环科技有限公司 Mixing process for preparing high-nickel anode material and application thereof
CN113735187A (en) * 2020-05-29 2021-12-03 东莞东阳光科研发有限公司 Preparation method of nickel cobalt lithium manganate precursor
CN113809319A (en) * 2021-08-03 2021-12-17 广东邦普循环科技有限公司 High-performance lithium nickel cobalt manganese oxide positive electrode material for power battery and preparation method of high-performance lithium nickel cobalt manganese oxide positive electrode material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110518209B (en) * 2019-08-27 2022-04-22 广东风华新能源股份有限公司 Preparation method of anode material and prepared anode material
CN114497530A (en) * 2022-01-11 2022-05-13 中科锂电新能源有限公司 Compression type lithium manganese iron phosphate cathode material and production process thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110229751A1 (en) * 2010-03-18 2011-09-22 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery
CN102300806A (en) * 2008-12-08 2011-12-28 蒂肖有限公司 Multicomponent nanoparticle materials and process and apparatus therefor
CN102583579A (en) * 2012-02-14 2012-07-18 佛山市邦普循环科技有限公司 Method for modifying rich lithium cobalt lithium manganite cathode material of lithium ion battery
CN102956884A (en) * 2012-11-29 2013-03-06 四川大学 Lithium-rich manganese-based material and preparation method thereof
CN103000893A (en) * 2012-12-20 2013-03-27 中国东方电气集团有限公司 Method for preparing lithium manganese phosphate positive material of lithium battery by spray pyrolysis
CN103094546A (en) * 2013-01-25 2013-05-08 湖南邦普循环科技有限公司 Method for preparing nickel-cobalt lithium aluminate as anode material of lithium ion battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904319B (en) * 2014-03-04 2015-10-07 广东邦普循环科技有限公司 A kind of preparation method of power type nickel-cobalt lithium manganate cathode material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102300806A (en) * 2008-12-08 2011-12-28 蒂肖有限公司 Multicomponent nanoparticle materials and process and apparatus therefor
US20110229751A1 (en) * 2010-03-18 2011-09-22 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery
CN102583579A (en) * 2012-02-14 2012-07-18 佛山市邦普循环科技有限公司 Method for modifying rich lithium cobalt lithium manganite cathode material of lithium ion battery
CN102956884A (en) * 2012-11-29 2013-03-06 四川大学 Lithium-rich manganese-based material and preparation method thereof
CN103000893A (en) * 2012-12-20 2013-03-27 中国东方电气集团有限公司 Method for preparing lithium manganese phosphate positive material of lithium battery by spray pyrolysis
CN103094546A (en) * 2013-01-25 2013-05-08 湖南邦普循环科技有限公司 Method for preparing nickel-cobalt lithium aluminate as anode material of lithium ion battery

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015131745A1 (en) * 2014-03-04 2015-09-11 广东邦普循环科技有限公司 Method for preparation of power-type nickel cobalt manganate lithium positive electrode material
WO2016011963A1 (en) * 2014-07-25 2016-01-28 台湾立凯电能科技股份有限公司 Method for preparing lithium nickel manganese oxide positive battery electrode material, and lithium nickel manganese oxide positive battery electrode material
TWI571439B (en) * 2014-07-25 2017-02-21 台灣立凱電能科技股份有限公司 Preparation method of lithium nickel manganese oxygen material of positive electrode of battery and lithium nickel manganese oxygen material of positive electrode of battery
CN106663791A (en) * 2014-07-25 2017-05-10 台湾立凯电能科技股份有限公司 Method for preparing lithium nickel manganese oxide positive battery electrode material, and lithium nickel manganese oxide positive battery electrode material
US10128500B2 (en) 2014-07-25 2018-11-13 Advanced Lithium Electrochemistry Co., Ltd. Preparation method of lithium nickel manganese oxide cathode material of battery and lithium nickel manganese oxide cathode material of battery
CN108899513A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of preparation method of the trielement composite material containing organic salt
CN109546140A (en) * 2018-09-13 2019-03-29 德阳威旭锂电科技有限责任公司 A kind of method that water/solvent-thermal method largely prepares carbon coating iron manganese phosphate for lithium
CN113735187A (en) * 2020-05-29 2021-12-03 东莞东阳光科研发有限公司 Preparation method of nickel cobalt lithium manganate precursor
CN113178565A (en) * 2021-03-29 2021-07-27 广东邦普循环科技有限公司 Mixing process for preparing high-nickel anode material and application thereof
CN113178565B (en) * 2021-03-29 2023-06-16 广东邦普循环科技有限公司 Mixing process for preparing high-nickel anode material and application thereof
CN113809319A (en) * 2021-08-03 2021-12-17 广东邦普循环科技有限公司 High-performance lithium nickel cobalt manganese oxide positive electrode material for power battery and preparation method of high-performance lithium nickel cobalt manganese oxide positive electrode material
CN113809319B (en) * 2021-08-03 2022-11-15 广东邦普循环科技有限公司 High-performance lithium nickel cobalt manganese oxide positive electrode material for power battery and preparation method of high-performance lithium nickel cobalt manganese oxide positive electrode material
WO2023010970A1 (en) * 2021-08-03 2023-02-09 广东邦普循环科技有限公司 Lithium nickel manganese cobalt oxide positive electrode material of high-performance power battery and preparation method therefor
GB2617724A (en) * 2021-08-03 2023-10-18 Guangdong Brunp Recycling Technology Co Ltd Lithium nickel manganese cobalt oxide positive electrode material of high-performance power battery and preparation method therefor

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