CN114162879B - Micron-sized lithium ion battery anode material and preparation method thereof - Google Patents

Micron-sized lithium ion battery anode material and preparation method thereof Download PDF

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CN114162879B
CN114162879B CN202110833023.0A CN202110833023A CN114162879B CN 114162879 B CN114162879 B CN 114162879B CN 202110833023 A CN202110833023 A CN 202110833023A CN 114162879 B CN114162879 B CN 114162879B
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lithium
ion battery
lithium ion
positive electrode
electrode material
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CN114162879A (en
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孙全胜
孙旭
梁正
王浩
郑林
李永红
卢瑶
黄凯
吴平
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Ningxia Hanghan Graphene Technology Research Institute Co ltd
Ningxia Hanyao Lithium Technology Co ltd
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Ningxia Hanghan Graphene Technology Research Institute Co ltd
Ningxia Hanyao Lithium Technology Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The application relates to the field of lithium ion battery anode materials, in particular to a micron-sized lithium ion battery anode material and a preparation method thereof, wherein the micron-sized lithium ion battery anode material comprises a lithium source and a lithium ion battery anode material precursor, and the particle size D50 of the lithium source is 4-12 mu m. According to the application, lithium carbonate and lithium hydroxide are used as mixed lithium sources, and a eutectic is formed by heating, so that the reaction activation energy in the preparation process is reduced, the reaction temperature and reaction time in the synthesis of the positive electrode material of the lithium ion battery are reduced, the power density and capacitance of the battery are improved, meanwhile, the lithium ion battery has excellent cycling stability, higher cycling capacity retention rate and prolonged service life.

Description

Micron-sized lithium ion battery anode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to H01M4/48.
Background
Currently, the rapidly developing new energy automobile industry causes lithium ion batteries to be a hot topic. CN201310675280 is prepared into a solution through nickel sulfate, cobalt sulfate and manganese sulfate, pH is regulated, then the solution is baked and dried to obtain a precursor, then lithium carbonate, lithium fluoride and the precursor are mixed, and the ternary positive electrode material is obtained after calcination, and the positive electrode material has the characteristic of prolonging the cycle life of a battery, however, the reaction temperature is higher in the preparation process of the positive electrode material. CN201310233763 adopts nickel hydroxide, manganese carbonate, lithium hydroxide and lithium carbonate to provide a positive electrode material after sintering, and the sintering temperature of the positive electrode material is too high, so that the production efficiency is influenced and the subsequent use quality of the positive electrode material is also influenced.
Disclosure of Invention
Aiming at some problems existing in the prior art, the first aspect of the invention provides a micron-sized lithium ion battery positive electrode material, which is prepared from a lithium source and a lithium ion battery positive electrode material precursor, wherein the particle size D50 of the lithium source is 4-12 mu m.
If the lithium source is a multicomponent mixture, the particle size D50 of the lithium source in the present application is 4-12 μm, which means the D50 particle size of the lithium source after multicomponent mixing.
D50: the particle size corresponding to a cumulative particle size distribution percentage of one sample reaching 50%. Its physical meaning is that the particle size is greater than 50% of its particles and less than 50% of its particles, also called median or median particle size, D50.
The lithium ion battery positive electrode material precursors in the present application include, but are not limited to, lithium cobaltate LiCoO 2 and nickel cobalt manganese oxide Li (NixCOyMn 1-x-y)O2 and nickel cobalt aluminum oxide Li (NixCOyAl 1-x-y)O2 and nickel cobalt manganese aluminum oxide Li (NixCOyMnzAl 1-x-y-z)O2 and lithium-rich positive electrode material xLi 2MnO3·(1-x)LiMnO2, where x, y, z are any number less than 1).
In one embodiment, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate.
Preferably, the purity of the lithium carbonate is 90wt% or more, and the purity of the lithium hydroxide is 50wt% or more; more preferably, the purity of the lithium carbonate is 99.5wt% or more and the purity of the lithium hydroxide is 56wt% or more.
Preferably, the lithium source comprises lithium carbonate and lithium hydroxide, and the weight ratio of the lithium source to the lithium hydroxide is 1: (0.25-1.5); more preferably, the weight ratio of the lithium carbonate to the lithium hydroxide is 1:1.5.
In one embodiment, the lithium carbonate has a particle size D50 of 10 μm or less.
In one embodiment, the lithium hydroxide has a particle size D50 of 10 μm or less.
The second aspect of the invention provides a preparation method of the micron-sized lithium ion battery anode material, which comprises the following steps:
(1) Mixing lithium carbonate and lithium hydroxide, and then mixing with a precursor of the positive electrode material of the lithium ion battery to form a precursor mixture of the positive electrode material of the lithium ion battery;
(2) And roasting the precursor mixture of the positive electrode material of the lithium ion battery to obtain the lithium ion battery.
In one embodiment, the method of mixing lithium carbonate and lithium hydroxide comprises: mixing lithium carbonate and lithium hydroxide at a rate of 600-800r/min for 10-30min using a high speed mixer.
Preferably, the method for mixing lithium carbonate and lithium hydroxide comprises the following steps: lithium carbonate and lithium hydroxide were mixed using a high speed mixer at a rate of 800r/min for 20min.
In one embodiment, the temperature of the mixture is maintained at no more than 60 ℃ during the mixing of lithium carbonate and lithium hydroxide.
In one embodiment, the step (1) includes: mixing lithium carbonate and lithium hydroxide at a speed of 600-800r/min for 10-30min by using a high-speed mixer, adding a precursor of the lithium ion cathode material, and mixing at a speed of 600-800r/min for 20-40min by using the high-speed mixer.
Preferably, the step (1) includes: lithium carbonate and lithium hydroxide were mixed at a rate of 800r/min for 20min using a high-speed mixer, and after adding the lithium ion positive electrode material precursor, mixed at a rate of 800r/min for 30min using a high-speed mixer.
In one embodiment, the firing temperature in step (2) is 800-1100 ℃.
In one embodiment, the step (2) includes: the precursor mixture of the positive electrode material of the lithium ion battery is baked for 8-11 hours at 800-950 ℃, crushed and sieved, and baked again at 750-850 ℃.
Preferably, the step (2) includes: roasting the precursor mixture of the positive electrode material of the lithium ion battery at 800-950 ℃ for 8-11 hours, crushing, sieving, roasting at 750-850 ℃ for 5-7 hours again, crushing, sieving, and obtaining the positive electrode material.
Preferably, the step (2) includes: roasting the precursor mixture of the positive electrode material of the lithium ion battery at 910 ℃ for 10 hours, crushing, sieving, roasting at 800 ℃ for 6 hours again, crushing, and sieving to obtain the lithium ion battery.
The pulverizing method in the present application is not particularly limited, and those skilled in the art can routinely select, and there may be mentioned twin roll pulverizing, jaw pulverizing, mechanical pulverizing, air flow pulverizing, and the like.
In one embodiment, the screened mesh aperture is 325 mesh.
In one embodiment, the particle size D50 is maintained between 10.5 and 12.5 μm after comminution.
Preferably, the particle diameter D50 is maintained at 11.5 μm after pulverization.
The roasting atmosphere in the application is air or oxygen.
Currently, in order to obtain a uniform crystal phase structure, a single lithium source is mostly used, however, the use of a single lithium source requires a higher temperature and a higher baking time at a later baking temperature, and the applicant has unexpectedly found that, among a plurality of lithium sources, lithium carbonate and lithium hydroxide are specifically selected while maintaining a weight ratio of 1: (0.25-1.5), in the later roasting process, roasting can be completed at a lower temperature in a shorter time, and the applicant speculates that the possible reason is that in the high-temperature roasting process, part of the mixed lithium source is melted, the reaction is carried out between solid and liquid states, the ion diffusion rate is obviously accelerated, the reaction activation energy in the preparation process is reduced, the reaction temperature and time can be effectively reduced, and the performance of the anode material is improved.
In addition, the inventors have unexpectedly found that when the particle size of the lithium source of a single component is less than 10 μm, the mixed lithium source D50 is 4 to 12 μm, and the material mixing temperature is maintained not to exceed 60 ℃ during the mixing process, and at the same time, the materials are mixed for a specific time at a rate of 600 to 800r/min by using a high-speed mixer, and after the mixing and the precursor are baked under specific conditions of the present application, the structure of the positive electrode material can realize a mixture of single crystals, quasi-single crystals and agglomerates, and the crystalline phase distribution state of the mixture is suitable, resulting in maintaining good electrical properties, especially the cycle stability at 45 ℃, in a plurality of crystalline phase structures.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the application, lithium carbonate and lithium hydroxide are used as mixed lithium sources, and a eutectic is formed through heating, so that the reaction activation energy in the preparation process is reduced, the reaction temperature and reaction time in the synthesis of the positive electrode material of the lithium ion battery are reduced, the power density and capacitance of the battery are improved, meanwhile, the lithium ion battery has excellent cycling stability, higher cycling capacity retention rate and prolonged service life of the battery;
(2) The application controls the particle size of a single lithium source to be smaller than 10 mu m, the D50 of the mixed lithium source is 4-12 mu m, the temperature of the mixed material is kept to be not higher than 60 ℃ in the mixing process, meanwhile, a high-speed mixer is used for mixing for a specific time at the speed of 600-800r/min, after the mixed material is roasted with a precursor under the specific condition of the application, the structure of the positive electrode material can realize the mixture of single crystal, quasi-single crystal and aggregate, and the crystalline phase distribution state of the mixture is proper, so that in a plurality of crystalline phase structures, the better electrical property, especially the circulation stability at 45 ℃ is maintained.
Drawings
FIGS. 1 to 4 are SEM diagrams of the positive electrode materials of lithium ion batteries obtained in examples 1 to 4, respectively;
FIG. 5 is a graph showing the first charge and discharge curves of batteries prepared from the positive electrode materials of lithium ion batteries of examples 1-4 of the present application;
FIG. 6 is a cycle charge and discharge curve of a battery prepared from the positive electrode materials of lithium ion batteries of examples 1-4 of the present application;
FIG. 7 is a DSC curve of the positive electrode material of a lithium ion battery obtained in examples 1-3 of the present application.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
The embodiment 1 of the invention provides a micron-sized lithium ion battery anode material, which is prepared by the following steps:
(1) Firstly, mixing lithium hydroxide and lithium carbonate by a high-speed mixer, wherein the mixing mass ratio of the lithium carbonate to the lithium hydroxide is 40 percent: 60%, mixing for 20 minutes by using a high-speed mixer at a mixing rate of 800r/min to form a eutectic of lithium hydroxide and lithium carbonate, keeping the temperature of the mixed materials below 60 ℃ in the mixing process, then adding a precursor of an anode material of the Lanzhou Jintong NCM523 lithium ion battery, mixing by using the high-speed mixer at the mixing rate of 800r/min for 30 minutes to form a precursor mixture of the anode material of the lithium ion battery;
(2) Roasting the precursor mixture of the positive electrode material of the lithium ion battery by a box furnace at the temperature of 910 ℃ for 10 hours to form a primary blocky material after roasting;
(3) Crushing the roasted primary block material for 2 times by a double roller, crushing by airflow, controlling the granularity D50 to be 11.5 mu m, and sieving by a 325-mesh sieve to form a primary crushed material;
(4) Roasting the primary crushed material in a box furnace at 800 ℃ for 6 hours to form a secondary block material;
(5) Crushing the baked secondary block material for 2 times by a double roller, crushing by air flow, controlling the granularity D50 to be 11.5 mu m, and sieving by a demagnetizing 325 mesh sieve to prepare the lithium ion battery anode material.
Wherein, the particle size of lithium hydroxide is 5.8 mu m, the purity is 56.5 percent, and the lithium hydroxide is purchased from Ganfeng lithium industry; the lithium carbonate had a particle size of 6.1 μm and a purity of 99.76% and was purchased from Jiangxi-Meta.
The weight ratio of the total weight of the lithium carbonate and the lithium hydroxide to the precursor of the positive electrode material of the lithium ion battery is 1:2.4.
Example 2
The embodiment 2 of the invention provides a micron-sized lithium ion battery anode material, which is prepared by the following steps:
(1) Firstly, mixing lithium carbonate and a precursor of a positive electrode material of a Rankine NCM523 lithium ion battery by a high-speed mixer at a mixing rate of 800r/min for 30 minutes to form a precursor mixture of the positive electrode material of the lithium ion battery.
(2) Roasting the precursor mixture of the positive electrode material of the lithium ion battery by a box furnace at the temperature of 910 ℃ for 10 hours to form a primary blocky material after roasting;
(3) Crushing the roasted primary block material for 2 times by a double roller, crushing by airflow, controlling the granularity D50 to be 11.5 mu m, and sieving by a 325-mesh sieve to form a primary crushed material;
(4) Roasting the primary crushed material in a box furnace at 800 ℃ for 6 hours to form a secondary block material;
(5) Crushing the baked secondary block material for 2 times by a double roller, crushing by air flow, controlling the granularity D50 to be 11.5 mu m, and sieving by a demagnetizing 325 mesh sieve to prepare the lithium ion battery anode material.
Wherein the particle size of the lithium carbonate is 6.1 μm, purchased from Jiangxi head ton.
The weight ratio of the lithium carbonate to the lithium ion battery anode material precursor is 1:2.4.
Example 3
The embodiment 3 of the invention provides a micron-sized lithium ion battery anode material, which is prepared by the following steps:
(1) Firstly, mixing lithium hydroxide and a precursor of the anode material of the Rankine NCM523 lithium ion battery by a high-speed mixer at the mixing speed of 800r/min for 30 minutes to form a precursor mixture of the anode material of the lithium ion battery.
(2) Roasting the precursor mixture of the positive electrode material of the lithium ion battery by a box furnace at the temperature of 910 ℃ for 10 hours to form a primary blocky material after roasting;
(3) Crushing the roasted primary block material for 2 times by a double roller, crushing by airflow, controlling the granularity D50 to be 11.5 mu m, and sieving by a 325-mesh sieve to form a primary crushed material;
(4) Roasting the primary crushed material in a box furnace at 800 ℃ for 6 hours to form a secondary block material;
(5) Crushing the baked secondary block material for 2 times by a double roller, crushing by air flow, controlling the granularity D50 to be 11.5 mu m, and sieving by a demagnetizing 325 mesh sieve to prepare the lithium ion battery anode material.
Wherein the particle size of the lithium hydroxide is 5.8 mu m, and the lithium hydroxide is purchased from Ganfeng lithium industry.
The weight ratio of the lithium hydroxide to the lithium ion battery positive electrode material precursor is 1:2.4.
Example 4
The embodiment 4 of the invention provides a micron-sized lithium ion battery anode material, which is prepared by the following steps:
(1) Firstly, mixing lithium hydroxide and lithium nitrate by a high-speed mixer, wherein the mixing mass ratio of the lithium nitrate to the lithium hydroxide is 40 percent: 60%, mixing for 20 minutes at a mixing rate of 800r/min to form a eutectic of lithium hydroxide and lithium nitrate, keeping the temperature of the mixed materials below 60 ℃ in the mixing process, adding a precursor of an anode material of the Rankine NCM523 lithium ion battery, mixing by a high-speed mixer at a mixing rate of 800r/min for 30 minutes to form a precursor mixture of the anode material of the lithium ion battery;
(2) Roasting the precursor mixture of the positive electrode material of the lithium ion battery by a box furnace at the temperature of 910 ℃ for 10 hours to form a primary blocky material after roasting;
(3) Crushing the roasted primary block material for 2 times by a double roller, crushing by airflow, controlling the granularity D50 to be 11.5 mu m, and sieving by a 325-mesh sieve to form a primary crushed material;
(4) Roasting the primary crushed material in a box furnace at 800 ℃ for 6 hours to form a secondary block material;
(5) Crushing the baked secondary block material for 2 times by a double roller, crushing by air flow, controlling the granularity D50 to be 11.5 mu m, and sieving by a demagnetizing 325 mesh sieve to prepare the lithium ion battery anode material.
Wherein, the particle size of lithium hydroxide is 5.8 mu m, the purity is 56.5 percent, and the lithium hydroxide is purchased from Ganfeng lithium industry; lithium nitrate was purchased from shandong chemical industry limited, battery grade, cat No. 101.
The weight ratio of the lithium nitrate to the lithium hydroxide to the lithium ion battery positive electrode material precursor is 1:2.4.
SEM images of the positive electrode materials of lithium ion batteries obtained in examples 1 to 4 are shown in FIGS. 1 to 4, respectively.
Performance evaluation
Dsc analysis: DSC analysis was performed on the positive electrode materials of the lithium ion batteries obtained in examples 1 to 3 by using a DSC thermal analyzer, respectively, wherein the temperature program of the instrument was 10deg.C/min. The DSC curves obtained are shown in FIG. 7, respectively.
As can be seen from fig. 7, the positive electrode material for lithium ion battery obtained in example 1 has an absorption peak before 100 ℃, which is generated by evaporation of water, and the peak has a small left shift in the DSC curve of the positive electrode material for lithium ion in comparative example 3, and the peak has a large left shift in the DSC curve of the positive electrode material for lithium ion in comparative example 2. Meanwhile, the positive electrode material of the lithium ion battery obtained in example 1 has an absorption peak at about 420 ℃, the peak is a decomposition absorption peak of the positive electrode material of the lithium ion battery obtained in example 1, the peak has a small left shift in comparison with the DSC curve of the positive electrode material of the lithium ion battery in example 3, and the peak has a large left shift in comparison with the DSC curve of the positive electrode material of the lithium ion battery in example 2, and the peak is different by about 90 ℃. The lithium ion positive electrode material in example 1 has an absorption peak at about 715 ℃, which is a chemical reaction absorption peak, the lithium ion positive electrode material in comparative example 3 has a DSC curve where an obvious absorption peak is present, and the lithium ion positive electrode material in comparative example 2 has a DSC curve where the peak shifts left by a small margin.
From this, it can be seen that the lithium ion positive electrode material of example 1 relatively produced a leftwards shift phenomenon at the moisture volatilization absorption peak, the substance decomposition absorption peak and the chemical reaction absorption peak, compared with the single component, and reduced the absorption peak production temperature, so that the reaction can be carried out at a relatively low temperature.
2. And (3) testing electrical properties: the positive electrode materials of the lithium ion batteries in examples 1 to 4 were prepared into batteries, respectively, by the following methods: uniformly mixing the material or blank sample obtained in the embodiment, conductive carbon black and polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to the weight ratio of 8:1:1, and coating the aluminum foil to form a pole piece; and (5) drying the prepared pole piece in a vacuum drying oven at 110 ℃ for 5 hours for standby. And rolling the pole piece on a rolling machine, and punching the rolled pole piece into a round pole piece. The cell assembly was performed in an argon filled glove box with electrolyte 1MLiPF6 and solvent EC: DEC: dmc=1:1:1 (volume ratio), the metallic lithium sheet is the counter electrode. Capacity testing was performed on a blue CT2001A tester. And respectively carrying out charge and discharge tests on the prepared battery, wherein the test voltage is 3.0-4.3V, the cycle test condition is 0.5CC/1.0CD, the battery is cycled for 50 circles, the last discharge capacity is respectively recorded, and the cycle retention rate is obtained by dividing the last cycle discharge capacity.
The first charge and discharge curves of the battery prepared from the positive electrode material of the lithium ion battery of example 1 are shown in fig. 5, and the cyclic charge and discharge curves are shown in fig. 6.
The first charge-discharge capacity and the cyclic charge-discharge capacity retention rate are shown in table 1.
TABLE 1

Claims (1)

1. The preparation method of the micron-sized lithium ion battery cathode material is characterized in that the preparation raw materials comprise a lithium source and a lithium ion battery cathode material precursor, wherein the lithium source comprises lithium carbonate and lithium hydroxide, and the weight ratio of the lithium carbonate to the lithium hydroxide is 1:1.5, wherein the purity of the lithium carbonate is greater than or equal to 99.5wt%, the purity of the lithium hydroxide is greater than or equal to 56wt%, the particle size D50 of a mixed lithium source is 4-12 mu m, the particle size D50 of the lithium carbonate is less than or equal to 10 mu m, and the particle size D50 of the lithium hydroxide is less than or equal to 10 mu m;
the preparation method of the micron-sized lithium ion battery anode material comprises the following steps:
(1) Mixing lithium carbonate and lithium hydroxide, and then mixing with a precursor of the positive electrode material of the lithium ion battery to form a precursor mixture of the positive electrode material of the lithium ion battery;
(2) Roasting the precursor mixture of the positive electrode material of the lithium ion battery to obtain the lithium ion battery;
in the mixing process of lithium carbonate and lithium hydroxide, keeping the temperature of the mixed materials not to exceed 60 ℃;
The step (1) comprises: mixing lithium carbonate and lithium hydroxide at a rate of 800 r/min for 20min by using a high-speed mixer, adding a lithium ion positive electrode material precursor, and mixing at a rate of 800 r/min for 30min by using the high-speed mixer;
the step (2) comprises: roasting the precursor mixture of the positive electrode material of the lithium ion battery at 910 ℃ for 10 hours, crushing, sieving, roasting at 800 ℃ for 6 hours again, crushing, and sieving to obtain the lithium ion battery.
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