CN113346061A - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

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Publication number
CN113346061A
CN113346061A CN202110606841.7A CN202110606841A CN113346061A CN 113346061 A CN113346061 A CN 113346061A CN 202110606841 A CN202110606841 A CN 202110606841A CN 113346061 A CN113346061 A CN 113346061A
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lithium
ion battery
lithium ion
carbon
cobalt
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孙宇星
王浩兰
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Henan Yingneng New Material Technology Co ltd
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Henan Yingneng New Material 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M4/50—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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • C01P2006/40—Electric properties
    • 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 relates to a lithium ion battery anode material, which comprises nickel-cobalt-manganese ternary material powder with the particle size range of 8-12 mu m and a lithium iron phosphate composite layer coated on the surface, wherein the lithium iron phosphate composite layer consists of lithium iron phosphate, a carbon nano material, other carbon materials and an auxiliary agent, and the nickel-cobalt-manganese ternary material powder comprises 70-85 wt%, 10-20 wt%, 0.5-3.5 wt%, 0.5-5 wt% and 0.2-5 wt% of the auxiliary agent; the invention also provides a preparation method of the lithium ion battery anode material, which comprises the steps of S1 coating lithium iron phosphate, carbon nano-material and other carbon materials on the surface of the nickel-cobalt-manganese ternary material powder, S2 spray drying granulation, S3 sintering and S4 auxiliary agent addition coating, wherein the step S4 is after the step S3 or between the step S1 and the step S2; the lithium ion battery anode material has high initial effect and good compaction density, the initial effect can be improved by 2 to 3.5 percent and reaches 93 to 95 percent, and the 1C cycle frequency is increased by 20 to 30 percent.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a lithium ion battery anode material and a preparation method thereof.
Background
In the known positive electrode materials, the specific energy of the high-nickel-cobalt-manganese ternary monomer battery can reach over 300Wh/kg, and the high-nickel-cobalt-manganese ternary positive electrode material is very suitable for being used as a new-generation high-energy-density power lithium battery positive electrode material, but the cycle performance and the rate capability performance of the high-nickel-cobalt-manganese ternary positive electrode material are relatively poor. The lithium iron silicate is concerned due to the advantages of high theoretical specific capacity up to 330mAh/g, good safety, low cost, greenness, no pollution and the like, and the commercialization process of the material is severely restricted due to the problems of low conductivity, small lithium ion diffusion rate and the like, and the specific capacity is limited to about 160mAh/g for a long time in the past period.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lithium ion battery anode material with high first effect and good compaction density and a preparation method thereof.
The technical scheme of the invention is as follows:
the lithium ion battery anode material comprises nickel-cobalt-manganese ternary material powder with the particle size range of 8-12 mu m and a lithium iron phosphate composite layer coated on the surface, wherein the lithium iron phosphate composite layer consists of lithium iron phosphate, a carbon nano material, other carbon materials and an auxiliary agent, and the nickel-cobalt-manganese ternary material powder comprises, by weight, 70-85% of lithium iron phosphate, 10-20% of lithium iron phosphate, 0.5-3.5% of the carbon nano material, 0.5-5% of the other carbon materials and 0.2-5% of the auxiliary agent; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
Furthermore, the particle size range of the nickel-cobalt-manganese ternary material is 2-8 μm, the particle size range of the lithium iron phosphate is 100-500nm, the particle size range of the carbon nano material is 2-100nm, the particle size range of other carbon materials is 2-100nm, and the particle size range of the auxiliary agent is 10-500 nm; the carbon nano material is one or more of carbon nanohorn, carbon nano onion, carbon nanotube, graphene and carbon nanofiber; the specific surface area of the anode material is 0.5-3m2The compacted density of the nickel-cobalt-manganese ternary material powder is 3.4 to 3.7g/cm3The compacted density of the lithium iron phosphate is between 2.2 and 2.3g/cm3(ii) a The compacted density of the finally mixed lithium ion battery anode material is 2.8-3.2g/cm3。
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
s1 coating lithium iron phosphate, carbon nano-materials and other carbon materials on the surface of the nickel-cobalt-manganese ternary material powder to obtain a precursor;
s2 spray drying and granulating, wherein the particle size is controlled to be 8-12 μm;
s3, putting the lithium ion battery into an inert gas furnace for primary sintering to obtain the lithium ion battery composite anode material with the particle size of 5-12 mu m;
further comprising step S4 of adding an adjuvant for coating, step S4 after step S3 or between step S1 and step S2; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
Further, before step S1, grinding the phosphoric acid source, lithium source and iron source material powder for 1-4 hours, and controlling the grinding particle size at 100-500 nm; the coating is carried out by coprecipitation, gas phase, liquid phase or solid phase.
Further, in step S1, the coating is performed by a liquid phase method, the ground powders of the phosphoric acid source, the lithium source and the iron source are introduced into a carbon source solution dissolved or dispersed by deionized water, and then mixed, and then the nickel-cobalt-manganese ternary powder is added and stirred for 1-4 hours to obtain a precursor; the carbon source solution is a solution of carbon nano-materials and other carbon materials.
Further, in step S1, the coating is performed by a liquid phase method, and in step S4, between step S1 and step S2, after the precursor is obtained, the adjuvant powder is added into the mixed solution and stirred for 1-4 hours to be uniformly mixed.
Further, in step S4, after step S3, the lithium ion battery composite positive electrode material obtained by primary sintering is mixed with a propping agent and an auxiliary agent by a gas phase method, a liquid phase method or a solid phase method, and then is sintered again, wherein the particle size after sintering is controlled to be 8-12 um.
Further, the other carbon material is a carbon-containing organic material including, for example, glucose, sucrose, citric acid, pitch, starch, acetylene black, polypropylene, phenol resin, vitamin C, chitosan, polyethylene glycol, polyvinyl alcohol, and polyvinyl pyrrolidone;
the auxiliary agent is non-conductive, and comprises at least two of aluminum oxide, zirconium oxide, niobium oxide, tin oxide and SEI film forming agent.
Further, in step S1, the nickel-cobalt-manganese ternary material powder is an industrialized single crystal nickel-cobalt-manganese ternary material, and the molar ratio of nickel, cobalt and manganese is 5: 2: 3 or 6: 2; the lithium iron phosphate adopts at least one phosphoric acid source selected from ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate, the lithium source is at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate, and the iron source is at least one selected from ferrous oxalate, ferrous acetate and ferrous sulfate.
Further, before step S1, the phosphoric acid source, the lithium source, and the iron source material powder are milled by sand milling or ball milling, the milling medium is absolute ethyl alcohol, the milling time is 4-8 hours, and the milling particle size D50 is controlled at about 50 nm.
The principle of the invention is as follows:
in the anode material for the new energy automobile, the lithium iron phosphate material has outstanding cycle performance and safety performance by virtue of a stable olivine crystal structure, the first effect of the high-nickel ternary material is low, and the first effect of the iron-lithium phosphate material is high, so that the utilization rate of the material can be improved by coating nano lithium iron phosphate on the surface of the high-nickel-cobalt-manganese ternary anode material through the first effect, and the cycle performance of the material is improved. Meanwhile, in order to pursue the stability of the material, the invention mainly adopts the sintered single crystal ternary material as the corresponding raw material to carry out the experiment, if the conventional nano secondary ball ternary material is adopted;
meanwhile, the specific surface area and functional groups are increased by the carbon nanohorns and other carbon materials coated on the surface of the lithium iron phosphate, the provided functional groups can keep the concentration difference of the electrolyte, and the conductivity among lithium iron phosphate particles is effectively improved; the pore-plugging agent and the propping agent are used as auxiliary agents, so that the specific surface area of the composite material is further reduced, and the structure of the material is kept stable and is not easy to collapse.
Compared with the prior art, the invention has the beneficial effects that:
the lithium ion battery anode material has high first effect and good compaction density, has the characteristics of high energy density and high compaction of a nickel-cobalt-manganese ternary material, and has the corresponding characteristics of high multiplying power and cyclicity, higher first effect and the like of lithium iron phosphate; the first effect and the cycle of the lithium ion battery anode material after being compounded are greatly improved, the first effect can be improved by 2 to 3.5 percent, the first effect reaches 93 to 95 percent, and the 1C cycle frequency is increased by 20 to 30 percent;
the added carbon nano materials such as carbon nano horns, carbon nano onions and the like improve the problem that the back of the lithium iron phosphate has relatively poor conductivity; the carbon nano material and other carbon materials are used as composite coating materials, and the materials have high ion conductivity, so that the cycle performance of the lithium ion battery anode material is greatly improved; the pore-plugging agent and the propping agent are used as auxiliary agents, and the pore-plugging agent mainly has the functions of reducing the specific surface area of the composite material and further improving the first effect of the material; the proppant mainly keeps the structure of the material stable and is not easy to collapse or break, so that the material is inactivated, and the cycle performance of the material is further improved;
the lithium ion battery anode material prepared by the preparation method has the characteristics, and in addition, the powder can be well mixed uniformly by adopting a wet mixing method and a spray drying or coprecipitation method, separately adding the carbon material and the auxiliary agent, and uniformly mixing for a long time, the preparation process is simple, and the prepared material particles are uniform.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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.
Example 1
The lithium ion battery anode material comprises nickel-cobalt-manganese ternary material powder with the particle size range of 8-12 mu m and a lithium iron phosphate composite layer coated on the surface, wherein the lithium iron phosphate composite layer consists of lithium iron phosphate, a carbon nano material, other carbon materials and an auxiliary agent, and the nickel-cobalt-manganese ternary material powder comprises, by weight, 70-85% of lithium iron phosphate, 10-20% of lithium iron phosphate, 0.5-3.5% of the carbon nano material, 0.5-5% of the other carbon materials and 0.2-5% of the auxiliary agent; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
Furthermore, the particle size range of the nickel-cobalt-manganese ternary material is 2-8 μm, the particle size range of the lithium iron phosphate is 100-500nm, the particle size range of the carbon nano material is 2-100nm, the particle size range of other carbon materials is 2-100nm, and the particle size range of the auxiliary agent is 10-500 nm; the carbon nano material is one or more of carbon nanohorn, carbon nano onion, carbon nanotube, graphene and carbon nanofiber; the specific surface area of the anode material is 0.5-3m2The compacted density of the nickel-cobalt-manganese ternary material powder is 3.4 to 3.7g/cm3The compacted density of the lithium iron phosphate is between 2.2 and 2.3g/cm3(ii) a The compacted density of the finally mixed lithium ion battery anode material is 2.8-3.2g/cm3。
The lithium ion battery anode material has high first effect and good compaction density, has the characteristics of high energy density and high compaction of a nickel-cobalt-manganese ternary material, and has the corresponding characteristics of high multiplying power and cyclicity, higher first effect and the like of lithium iron phosphate; the first effect and the cycle of the lithium ion battery anode material after being compounded are greatly improved, the first effect can be improved by 2 to 3.5 percent, the first effect reaches 93 to 95 percent, and the 1C cycle frequency is increased by 20 to 30 percent;
the added carbon nano materials such as carbon nano horns, carbon nano onions and the like improve the problem that the back of the lithium iron phosphate has relatively poor conductivity; the carbon nano material and other carbon materials are used as composite coating materials, and the materials have high ion conductivity, so that the cycle performance of the lithium ion battery anode material is greatly improved; the pore-plugging agent and the propping agent are used as auxiliary agents, and the pore-plugging agent mainly has the functions of reducing the specific surface area of the composite material and further improving the first effect of the material; the proppant mainly keeps the structure of the material stable and is not easy to collapse or break, so that the material is inactivated, and the cycle performance of the material is further improved.
Example 2
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
s1 coating lithium iron phosphate, carbon nano-materials and other carbon materials on the surface of the nickel-cobalt-manganese ternary material powder to obtain a precursor;
s2 spray drying and granulating, wherein the particle size is controlled to be 8-12 μm;
s3, putting the lithium ion battery into an inert gas furnace for primary sintering to obtain the lithium ion battery composite anode material with the particle size of 5-12 mu m;
s4, adding an auxiliary agent for coating, wherein the auxiliary agent is composed of a hole plugging agent for reducing the specific surface area of the composite material and a propping agent for keeping the structure of the material stable after the step S3 in the step S4; the final addition of the auxiliary agent is more beneficial to the first effect and the circulation of the anode material.
Further, before step S1, grinding the phosphoric acid source, lithium source and iron source material powder for 1-4 hours, and controlling the grinding particle size at 100-500 nm; the coating is carried out by coprecipitation, gas phase, liquid phase or solid phase.
Further, in step S1, the coating is performed by a liquid phase method, the ground powders of the phosphoric acid source, the lithium source and the iron source are introduced into a carbon source solution dissolved or dispersed by deionized water, and then mixed, and then the nickel-cobalt-manganese ternary powder is added and stirred for 1-4 hours to obtain a precursor; the carbon source solution is a solution of carbon nano-materials and other carbon materials.
Further, in step S4, after step S3, the lithium ion battery composite positive electrode material obtained by primary sintering is mixed with a propping agent and an auxiliary agent by a gas phase method, a liquid phase method or a solid phase method, and then is sintered again, wherein the particle size after sintering is controlled to be 8-12 um.
Further, the other carbon material is a carbon-containing organic material including, for example, glucose, sucrose, citric acid, pitch, starch, acetylene black, polypropylene, phenol resin, vitamin C, chitosan, polyethylene glycol, polyvinyl alcohol, and polyvinyl pyrrolidone;
the auxiliary agent is non-conductive, and comprises at least two of aluminum oxide, zirconium oxide, niobium oxide, tin oxide and SEI film forming agent.
Further, in step S1, the nickel-cobalt-manganese ternary material powder is an industrialized single crystal nickel-cobalt-manganese ternary material, and the molar ratio of nickel, cobalt and manganese is 5: 2: 3 or 6: 2; the lithium iron phosphate adopts at least one phosphoric acid source selected from ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate, the lithium source is at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate, and the iron source is at least one selected from ferrous oxalate, ferrous acetate and ferrous sulfate.
Further, before step S1, the phosphoric acid source, the lithium source, and the iron source material powder are milled by sand milling or ball milling, the milling medium is absolute ethyl alcohol, the milling time is 4-8 hours, and the milling particle size D50 is controlled at about 50 nm.
The lithium ion battery anode material prepared by the preparation method has the characteristics, and in addition, the powder can be well mixed uniformly by adopting a wet mixing method and a spray drying or coprecipitation method, separately adding the carbon material and the auxiliary agent, and uniformly mixing for a long time, the preparation process is simple, and the prepared material particles are uniform.
Example 3
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
s1 coating lithium iron phosphate, carbon nano-materials and other carbon materials on the surface of the nickel-cobalt-manganese ternary material powder to obtain a precursor;
s2 spray drying and granulating, wherein the particle size is controlled to be 8-12 μm;
s3, putting the lithium ion battery into an inert gas furnace for primary sintering to obtain the lithium ion battery composite anode material with the particle size of 5-12 mu m;
further comprising step S4 of adding an adjuvant for coating, step S4 between step S1 and step S2; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
Further, in step S1, the coating is performed by a liquid phase method, and after the precursor is obtained, the adjuvant powder is added into the mixed solution and stirred for 1-4 hours to mix uniformly.
Compared with the embodiment 2, the embodiment 3 has the advantage that the step 4 is arranged between the step 1 and the step 3, only one sintering is carried out, and the production cost is lower.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.

Claims (9)

1. A lithium ion battery positive electrode material is characterized in that: the composite material comprises nickel-cobalt-manganese ternary material powder with the particle size range of 8-12 mu m and a lithium iron phosphate composite layer coated on the surface, wherein the lithium iron phosphate composite layer consists of 70-85% of lithium iron phosphate, 10-20% of carbon nano material, 0.5-3.5% of carbon nano material, 0.5-5% of other carbon material and 0.2-5% of auxiliary agent in parts by weight; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
2. The positive electrode material for a lithium ion battery according to claim 1, wherein: the particle size range of the nickel-cobalt-manganese ternary material is 2-8 mu m, the particle size range of the lithium iron phosphate is 100-500nm, the particle size range of the carbon nano material is 2-100nm, the particle size range of other carbon materials is 2-100nm, and the particle size range of the auxiliary agent is 10-500 nm; the carbon nano material is one or more of carbon nanohorn, carbon nano onion, carbon nanotube, graphene and carbon nanofiber; the specific surface area of the anode material is 0.5-3m2The compacted density of the nickel-cobalt-manganese ternary material powder is 3.4 to 3.7g/cm3The compacted density of the lithium iron phosphate is between 2.2 and 2.3g/cm3(ii) a The compacted density of the finally mixed lithium ion battery anode material is 2.8-3.2g/cm3。
3. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
s1 coating lithium iron phosphate, carbon nano-materials and other carbon materials on the surface of the nickel-cobalt-manganese ternary material powder to obtain a precursor;
s2 spray drying and granulating, wherein the particle size is controlled to be 8-12 μm;
s3, putting the lithium ion battery into an inert gas furnace for primary sintering to obtain the lithium ion battery composite anode material with the particle size of 5-12 mu m;
further comprising step S4 of adding an adjuvant for coating, step S4 after step S3 or between step S1 and step S2; the auxiliary agent consists of a pore former for reducing the specific surface area of the composite material and a proppant for keeping the structure of the material stable.
4. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: before step S1, grinding phosphoric acid source, lithium source and iron source material powder for 1-4 hours, and controlling the grinding particle size at 100-500 nm; the coating is carried out by coprecipitation, gas phase, liquid phase or solid phase.
5. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: in step S1, the coating is performed by a liquid phase method, the milled powders of the phosphoric acid source, the lithium source and the iron source are introduced into a carbon source solution dissolved or dispersed by deionized water, and then mixed uniformly, and then the nickel-cobalt-manganese ternary powder is added and stirred for 1-4 hours to obtain a precursor; the carbon source solution is a solution of carbon nano-materials and other carbon materials.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: in step S1, the coating is performed by a liquid phase method, and in step S4, between step S1 and step S2, after the precursor is obtained, the adjuvant powder is added into the mixed solution and stirred for 1-4 hours to be uniformly mixed.
7. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: step S4 after step S3, the lithium ion battery composite positive electrode material obtained by primary sintering is mixed by adding a propping agent and an auxiliary agent through a gas phase method, a liquid phase method or a solid phase method and then is sintered again, and the particle size is controlled to be 8-12um after sintering.
8. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: the other carbon material is carbon-containing organic substance such as glucose, sucrose, citric acid, asphalt, starch, acetylene black, polypropylene, phenolic resin, vitamin C, chitosan, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone;
the auxiliary agent is non-conductive, and comprises at least two of aluminum oxide, zirconium oxide, niobium oxide, tin oxide and SEI film forming agent.
9. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein: in the step S1, the nickel-cobalt-manganese ternary material powder adopts an industrialized single crystal nickel-cobalt-manganese ternary material, and the molar ratio of nickel, cobalt and manganese is 5: 2: 3 or 6: 2; the lithium iron phosphate adopts at least one phosphoric acid source selected from ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate, the lithium source is at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate, and the iron source is at least one selected from ferrous oxalate, ferrous acetate and ferrous sulfate.
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