CN111430692A - Lithium ion battery cathode material and preparation method thereof - Google Patents

Lithium ion battery cathode material and preparation method thereof Download PDF

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CN111430692A
CN111430692A CN202010244312.2A CN202010244312A CN111430692A CN 111430692 A CN111430692 A CN 111430692A CN 202010244312 A CN202010244312 A CN 202010244312A CN 111430692 A CN111430692 A CN 111430692A
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lithium ion
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CN111430692B (en
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王胜彬
张超
张臻
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Beijing WeLion New Energy 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative 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
    • 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 lithium ion battery cathode material and a preparation method thereof, belonging to the technical field of lithium ion batteries. The lithium ion battery cathode material is internally provided with a three-dimensional carbon material conductive network, is externally provided with a uniform carbon material coating layer and is SiOxThe nano particles are uniformly dispersed in the three-dimensional carbon material conductive network. By mixing SiOxThe material, the solvent, the metal compound and the carbon source are uniformly mixed and mechanically crushed to obtain slurry, the slurry is subjected to spray drying and then to a fluidized bed coating process to obtain powder containing a coating layer, and finally the powder is sintered at high temperature in an inert atmosphere to obtain the material. The lithium ion battery cathode material has high conductivity, long cycle life and high first efficiencyThe preparation method has the advantages of simple and convenient operation, high repeatability, easy industrialization and the like.

Description

Lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery cathode material and a preparation method thereof.
Background
The theoretical capacity of the graphite cathode material is 372mAh/g, and the graphite cathode material cannot meet the requirement of a novel materialAlthough silicon has the highest theoretical specific capacity of 4200mAh/g, the problem of excessive volume expansion (more than or equal to 300%) in the lithium intercalation process of silicon materials causes serious cycle attenuation of the silicon materials2O and L i4SiO4The inactive phase can well play a role in inhibiting and buffering the volume expansion of the material, so that the cycle performance is more advantageous. However, the formation of the inactive phase consumes a part of lithium, resulting in a problem that the silica material has a low first efficiency.
CN108493438A discloses SiO for lithium ion batteryxThe material is disproportionated to generate silicate, so that L i of silicon oxide pair in the process of lithium intercalation for the first time is avoided+The irreversible consumption of the energy-saving power source improves the first coulomb efficiency. But the high-temperature sintering is carried out twice in the preparation process, so that the energy consumption is high and the cost is high; meanwhile, the outer carbon coating mode of the sol-gel method is not beneficial to generating uniform coating layers, and the improvement effect on the cycle performance is not obvious.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a lithium ion battery cathode material and a preparation method thereof.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiOxUniformly mixing a material, a solvent, a metal compound and a carbon source, and mechanically crushing until the median particle size of SiOx is 0.1-3 um to obtain slurry;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas to keep the powder in a suspended state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
and S4, heating the powder obtained in the step S3 to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an inert atmosphere, and carrying out constant-temperature heat treatment for 1-6 h to obtain the cathode material.
In a preferred embodiment of the present invention, the SiO in step S1xThe material is SiOxParticles, or a mixture of Si and SiO, wherein 0.5. ltoreq. x.ltoreq.1.5.
In a preferred embodiment of the present invention, the solvent and SiO in step S1xThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanol.
As a preferred embodiment of the present invention, in the metal compound in step S1, the metal element M is one of aluminum, magnesium, lithium and calcium; the compound is at least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the metal element M; wherein, the metal elements M and SiOxThe mass ratio of the materials is 1: 1 to 12.
As a preferred embodiment of the present invention, the carbon source and SiO in step S1xThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
In a preferred embodiment of the present invention, the fluidizing gas in step S2 is one of air and nitrogen.
As a preferred embodiment of the present invention, the organic carbon source and SiO of step S3xThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin.
In a preferred embodiment of the present invention, the mass ratio of the organic carbon source to the solvent in the organic carbon source-containing solution in step S3 is 0.1 to 0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol.
In a preferred embodiment of the present invention, the reaction time of the organic carbon source-containing solution in step S3 is 1 to 4 hours.
As a preferred embodiment of the present invention, the mechanical crushing in the step S1 is planetary ball milling or high energy ball milling or sand milling.
As a preferred embodiment of the present invention, the inert atmosphere in step S4 is nitrogen or argon.
The invention also provides the lithium ion battery cathode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the lithium ion battery cathode material provided by the invention has a three-dimensional carbon material conductive network inside, a uniform carbon material coating layer outside, and SiOxThe nano particles are uniformly dispersed in the three-dimensional carbon material conductive network. The invention improves the electronic conductivity of the cathode material by constructing an internal three-dimensional carbon material conductive network, and combines the characteristic of high stability of the structure with the nano SiOxThe function of inhibiting volume expansion is achieved; by adding metal salts or oxides to SiOxHigh temperature disproportionation of product reaction to avoid or mitigate irreversible L i+Consumption, and the first coulombic efficiency of the negative electrode material is improved; the dynamic and continuous coating of the fluidized bed is utilized to enable the coating to continuously exist on the surface of the material, and a compact and uniform coating layer is obtained through heat treatment, so that the electrochemical performance of the cathode material is obviously improved; and the traditional multiple sintering process is reduced to single sintering, so that the process is simplified and the cost is reduced. In conclusion, the lithium ion battery cathode material has the advantages of high conductivity, long cycle life and high first-effect, and the preparation method has the advantages of simplicity and convenience in operation, high repeatability, easiness in industrialization and the like.
Drawings
FIG. 1 is a schematic structural diagram of a three-dimensional carbon material conductive network provided by the present invention;
FIG. 2 is a schematic structural diagram of a negative electrode material for a lithium ion battery provided by the present invention;
fig. 3 is a scanning electron microscope image of the negative electrode material of the lithium ion battery with the three-dimensional carbon material conductive network in example 5 of the present invention.
FIG. 4 is a transmission electron microscope image of the lithium ion battery cathode material of example 5 after SiO is etched away.
The reference numbers illustrate: 1. a three-dimensional carbon material conductive network; 2. a carbon material coating layer; 3. SiOx nanoparticles.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiOxUniformly mixing a material, a solvent, a metal compound and a carbon source, and mechanically crushing the mixture in a planetary ball milling or high-energy ball milling or sanding mode until the median particle size of SiOx is 0.1-3 um to obtain slurry; wherein, SiOxThe material is SiOxParticles or a mixture of Si and SiO, and x is 0.5-1.5;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas air or nitrogen to keep the powder in a suspension state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
and S4, heating the powder obtained in the step S3 to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an inert atmosphere of nitrogen or argon, and carrying out constant-temperature heat treatment for 1-6 h to obtain the cathode material.
In step S1, the solvent and SiOxThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanol. The metal element M in the metal compound is one of aluminum, magnesium, lithium and calcium; the compound being a metal elementAt least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the element M; wherein, the metal elements M and SiOxThe mass ratio of the materials is 1: 1 to 12. Carbon source and SiOxThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
In step S3, the organic carbon source is mixed with SiOxThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin. The mass ratio of the organic carbon source to the solvent in the solution containing the organic carbon source is 0.1-0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol. The reaction time of the solution containing the organic carbon source is 1-4 h.
Referring to fig. 1 and 2, the lithium ion battery negative electrode material of the present invention has a three-dimensional carbon material conductive network 1 inside, a uniform carbon material coating layer 2 outside, and SiOx nanoparticles 3 uniformly dispersed in the three-dimensional carbon material conductive network. The invention improves the electronic conductivity of the cathode material by constructing an internal three-dimensional carbon material conductive network, and combines the characteristic of high stability of the structure with the nano SiOxPlays a role in inhibiting volume expansion.
Example 1:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, magnesium oxide, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with a median particle size of 0.1-3 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of magnesium oxide to SiO is 1: 2, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the ethanol solution of the phenolic resin into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 1 hour, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Example 2:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing Si particles, SiO particles, isopropanol, aluminum chloride, graphene and sodium carboxymethyl cellulose, and grinding and crushing the mixture to obtain slurry with a median particle size of 0.1 um; wherein the mass ratio of Si to SiO is 1: 1, the mass ratio of the isopropanol to the Si-containing material is 5: 1, the mass ratio of aluminum element in the alumina to Si-containing material is 1: 12, the mass ratio of the graphene to the Si-containing material is 0.01: 1, the mass ratio of the sodium carboxymethyl cellulose to the Si-containing material is 0.04: 1;
s2, spray drying the slurry to obtain powder with the median particle size of 20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized air to keep the powder in a suspended state;
s3, spraying the deionized water solution of glucose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 4 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the glucose to the Si-containing material is 0.05: 1, the mass ratio of glucose to deionized water is 0.1: 1;
and S4, heating the powder obtained in the step S3 to 1000 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 1h to obtain the cathode material.
Example 3:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO0.5Particles, and particlesUniformly mixing propanol, aluminum chloride, graphene and sodium carboxymethylcellulose, and grinding by using a high-energy ball mill until the median particle size is 0.1 um; wherein, isopropanol and SiO0.5The mass ratio of (A) to (B) is 5: 1, aluminum element and SiO in alumina0.5The mass ratio of (1): 12, graphene and SiO0.5Is 0.01: 1, sodium carboxymethylcellulose and SiO0.5Is 0.04: 1;
s2, spray drying the slurry to obtain powder with the median particle size of 20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the deionized water solution of glucose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 4 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the glucose and SiO0.5Is 0.05: 1, the mass ratio of glucose to deionized water is 0.1: 1;
and S4, heating the powder obtained in the step S3 to 1000 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 1h to obtain the cathode material.
Example 4:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO1.5Uniformly mixing the particles, ethanol, lithium hydroxide and polyethylene glycol, and carrying out planetary ball milling and crushing to obtain slurry with a median particle size of 3 um; wherein, ethanol and SiO1.5The mass ratio of (A) to (B) is 3: 1, lithium element and SiO in lithium carbonate1.5The mass ratio of (1): 1, polyethylene glycol and SiO1.5Is 0.1: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 15 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the deionized water solution of the sucrose into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be sprayed within 2 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature;wherein the sucrose is in contact with SiO1.5Is 0.1: 1, the mass ratio of the sucrose to the deionized water is 0.2: 1;
and S4, heating the powder obtained in the step S3 to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 3h to obtain the cathode material.
Example 5:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, methanol, calcium carbonate and phenolic resin, and carrying out planetary ball milling and crushing to obtain slurry with the median particle size of 1 um; wherein the mass ratio of methanol to SiO is 2: 1, the mass ratio of aluminum nitrate to SiO is 1: 3, the mass ratio of the phenolic resin to the SiO is 0.2: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 10 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized air to keep the powder in a suspended state;
s3, spraying a methanol solution of polyethylene glycol and polyvinylpyrrolidone into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 2 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of polyethylene glycol to SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.1: 1, the mass ratio of the organic carbon source to the methanol is 0.4: 1;
and S4, heating the powder obtained in the step S3 to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 4h to obtain the cathode material.
Fig. 3 is a scanning electron microscope image of the lithium ion battery anode material of the present embodiment; fig. 4 is a transmission electron microscope photograph of the residual three-dimensional carbon material conductive network after the SiO is etched away from the lithium ion battery negative electrode material of this embodiment. As can be seen from fig. 3 and 4, in the lithium ion battery negative electrode material prepared in the embodiment, the SiO nanoparticles are uniformly dispersed in the three-dimensional carbon material conductive network, the three-dimensional carbon material conductive network has a highly stable structure and higher electronic conductivity, and can inhibit volume expansion of the material in the charging and discharging processes, thereby significantly improving the electrochemical performance of the negative electrode material.
Example 6:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, mixing SiO0.8Uniformly mixing particles, deionized water, magnesium nitrate, polyvinylpyrrolidone and glucose, and carrying out planetary ball milling and crushing to obtain slurry with the median particle size of 2 um; wherein, the deionized water and SiO0.8The mass ratio of (A) to (B) is 4: 1, magnesium nitrate and SiO0.8The mass ratio of (1): 2, polyvinylpyrrolidone and SiO0.8Is 0.1: 1, glucose and SiO0.8Is 0.1: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 12 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying a methanol solution of polyethylene glycol into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 3 hours, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the polyethylene glycol and SiO0.8Is 0.1: 1, the mass ratio of polyethylene glycol to methanol is 0.2: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, and carrying out constant-temperature heat treatment for 4h to obtain the cathode material.
Comparative example 1:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with the median particle size of 1 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heating fluidized nitrogen to keep the powder in a suspension state;
s3, spraying the ethanol solution of the phenolic resin into the cavity of the fluidized bed reactor, controlling the spraying speed of the solution to be finished within 1 hour, and obtaining powder containing a coating layer after the temperature of the cavity of the fluidized bed is reduced to room temperature; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S4, heating the powder obtained in the step S3 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Comparative example 2:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, uniformly mixing SiO particles, deionized water, magnesium oxide, carbon nanotubes and polyvinylpyrrolidone, and carrying out planetary ball milling and crushing to obtain SiO slurry with the median particle size of 1 um; wherein the mass ratio of the deionized water to the SiO is 1: 1, the mass ratio of magnesium oxide to SiO is 1: 2, the mass ratio of the carbon nano tube to the SiO is 0.1: 1, the mass ratio of polyvinylpyrrolidone to SiO is 0.4: 1;
s2, spray drying the slurry to obtain powder with a median particle size of 5 um;
s3, heating the powder obtained in the step S2 to 700 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and carrying out constant-temperature heat treatment for 2h to obtain black powder;
s4, adding the black powder obtained in the step S3 into an ethanol solution of phenolic resin, stirring and evaporating to dryness to obtain powder containing a coating layer; wherein the mass ratio of the phenolic resin to the SiO is 0.2: 1, the mass ratio of the phenolic resin to the ethanol is 0.5: 1;
and S5, heating the powder containing the coating layer obtained in the step S4 to 700 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and carrying out constant-temperature heat treatment for 6h to obtain the cathode material.
Performance comparison experiment:
the materials prepared in the above examples and comparative examples were respectively prepared into pole pieces as working electrodes, L iPF6The button cell is assembled by using/DMC + EC + DEC (1: 1: 1) as electrolyte, and the charging and discharging cut-off voltage is 0.005-1.5V, and the constant electricity of 150mA/gThe results of charging and discharging are shown in Table 1.
TABLE 1 comparison of initial specific charge capacity, initial coulombic efficiency, 50 cycle retention
Specific capacity for first charge (mAh/g) First coulombic efficiency (%) 50-week cycle maintenance (%)
Example 1 1265 76 89
Example 2 1647 83 75
Example 3 1592 81 72
Example 4 581 68 94
Example 5 1318 74 86
Example 6 1506 80 78
Comparative example 1 1053 59 79
Comparative example 2 1229 75 65
As can be seen from Table 1, example 1 is comparable to comparative example 1 in that it is compatible with SiO by additionxHigh temperature disproportionation product SiO2Compared with the traditional drying coating method of the comparative example 2, the fluidized bed coating process of the embodiment 1 has the effects of reducing high-temperature sintering steps, simplifying operation flow and improving the cycle performance of the silicon-based composite cathode, and the reason is that the coating process of the fluidized bed can realize uniform coating of the particle surface, avoid the contact of a silicon-based material and an electrolyte, and reduce the occurrence of side reactions and structural degradation.
In conclusion, the lithium ion battery cathode material has the advantages of high conductivity, long cycle life and high first-effect, and the preparation method has the advantages of simplicity and convenience in operation, high repeatability, easiness in industrialization and the like.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. A preparation method of a lithium ion battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing SiOxUniformly mixing the material, the solvent, the metal compound and the carbon source, mechanically crushing the mixture until the mixture is SiOxThe median particle size of the slurry is 0.1-3 um to obtain slurry;
s2, spray drying the slurry to obtain powder with a median particle size of 5-20 um; placing the powder in a cavity of a fluidized bed reactor, and introducing heated fluidized gas to keep the powder in a suspended state;
s3, spraying the solution containing the organic carbon source into the cavity of the fluidized bed reactor, and cooling after the solution containing the organic carbon source completely reacts to obtain powder containing a coating layer;
and S4, heating the powder obtained in the step S3 to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an inert atmosphere, and carrying out constant-temperature heat treatment for 1-6 h to obtain the cathode material.
2. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: SiO of the step S1xThe material is SiOxParticles, or a mixture of Si and SiO, wherein 0.5. ltoreq. x.ltoreq.1.5.
3. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the solvent and SiO in the step S1xThe mass ratio of the materials is 1-5: 1; the solvent is at least one of deionized water, ethanol, methanol and isopropanol.
4. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the metal element M in the metal compound in step S1 is one of aluminum, magnesium, lithium, and calcium; compound (I)Is at least one of nitrate, sulfate, carbonate, chloride, hydroxide and oxide of the metal element M; wherein, the metal elements M and SiOxThe mass ratio of the materials is 1: 1 to 12.
5. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the carbon source and SiO in the step S1xThe mass ratio of the materials is 0.05-0.5: 1; the carbon source is at least one of carbon nano tube, graphene, glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone, phenolic resin and sodium carboxymethylcellulose.
6. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the organic carbon source and SiO of step S3xThe mass ratio of the materials is 0.05-0.2: 1; wherein the organic carbon source is at least one of glucose, sucrose, polyethylene glycol, polyvinylpyrrolidone and phenolic resin.
7. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the mass ratio of the organic carbon source to the solvent in the organic carbon source-containing solution in the step S3 is 0.1-0.5: 1; wherein the solvent is at least one of deionized water, ethanol and methanol.
8. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the reaction time of the solution containing the organic carbon source in the step S3 is 1-4 h.
9. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, characterized in that: the mechanical crushing in the step S1 is planetary ball milling or high-energy ball milling or sand milling.
10. The lithium ion battery negative electrode material prepared by the preparation method of any one of claims 1 to 9.
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