CN112072102A - Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof - Google Patents

Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof Download PDF

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CN112072102A
CN112072102A CN202010747819.XA CN202010747819A CN112072102A CN 112072102 A CN112072102 A CN 112072102A CN 202010747819 A CN202010747819 A CN 202010747819A CN 112072102 A CN112072102 A CN 112072102A
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文永军
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Hunan Bobangshan River New Materials Co.,Ltd.
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of lithium ion battery cathode materials and discloses Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material comprises the following formula raw materials: double-layer carbon-coated Co3O4Hollow microsphere nanofiber and FeCl3Carbon nanotube, cetyl trimethyl ammonium bromide. The one kind of Fe2O3Loaded carbon coated nano Co3O4SiO as a negative electrode material for lithium ion batteries2Coating with Co-based metal-organic frameworks on N2/O2In atmospheric thermal cracking, SiO2The coating can avoid the carbon layer and O2Directly contacting to form a porous carbon structure with stable appearance, Co3O4The hollow microsphere nano-fiber shortens a lithium ion transmission path, the inner porous carbon structure promotes the permeation of electrolyte and the diffusion of lithium ions through double-layer carbon coating, the outer carbon is an N-doped carbon structure, the conductivity is excellent, a stable SEI (solid electrolyte interphase) film is favorably formed, and nano Fe is formed on the surface of a carbon layer through a hot solvent method2O3Carbon nanotubes, which provide a transport channel for charges and lithium ions.

Description

Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material and the preparation method thereof.
Background
The lithium ion battery is a chargeable secondary battery, it mainly works through the lithium ion is inserted and taken off and inserted between two electrodes to and fro, the lithium ion is taken off from the positive pole while charging, insert the negative pole through the electrolyte, the negative pole is in the state of rich lithium; lithium ions are extracted from the negative electrode during discharging, and are inserted into the positive electrode through the electrolyte, the positive electrode is in a lithium-rich state, the lithium ion battery has the advantages of high energy density, high output voltage, small self-discharge, no memory effect and the like, the lithium ion battery has excellent cycle performance, can be charged and discharged quickly, has high charging efficiency, high output power and long service life in the working process, and is an ideal green high-efficiency energy device.
At present, the negative electrode material of the lithium ion battery mainly comprises metal negative electrode materials such as tin-based alloy, aluminum-based alloy and magnesium-based alloy; inorganic non-metallic negative electrode materials such as carbon materials, silicon materials, and the like; transition metal oxide materials such as lithium titanate, tin-based composite oxides, etc., wherein Co is3O4Has higher theoretical specific capacity, is a lithium ion battery cathode material with great development potential, but the current Co3O4The cathode material has poor conductivity, reduces the transmission and migration of charges and metal ions between the cathode material and electrolyte, inhibits the electrode reaction, and is Co3O4The volume expansion phenomenon can be generated in the process of charging and discharging of the negative electrode material, and the electrochemical cycle stability of the negative electrode material is reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material and the preparation method thereof solve the problem of Co3O4The problem of poor conductivity of the anode material is solved, and Co is also solved3O4The volume expansion phenomenon is generated on the cathode material, and the electrochemical cycle stability of the cathode material is reduced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material comprises the following formula raw materials in parts by weight: 61-70 parts of double-layer carbon-coated Co3O4Hollow microsphere nano fiber and 26-32 parts of FeCl33-5 parts of carbon nano tube and 1-2 parts of hexadecyl trimethyl ammonium bromide.
Preferably, the double-layer carbon-coated Co3O4The preparation method of the hollow microsphere nanofiber comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-3:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 110-130 ℃, reacting for 15-20h, cooling the solution to room temperature, carrying out reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the Co-based metal organic framework.
(2) Adding a mixed solution of ethanol and 20-25% ammonia water in a volume ratio of 50-60:1 into a reaction bottle, adding a Co-based metal organic framework and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 40-60min, stirring at a constant speed for 1-2h, slowly dropwise adding tetraethoxysilane, stirring at a constant speed for reaction for 5-7h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water, and fully drying to prepare SiO2Coating Co-based metal organic framework.
(3) Mixing SiO2The Co-based metal-organic framework is coated and placed in an atmosphere resistance furnace, N2 is introduced,the heating rate is 2-4 ℃/min, the temperature is maintained for 2-3h at the temperature of 300-2/O2Mixed gas with the volume ratio of 1.5-2.4:1, heating to 520-540 ℃, and performing heat preservation and calcination for 3-4h, wherein the calcination product is SiO2Porous carbon coated Co3O4。
(4) Introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 4.5-5.5mol/L, adding SiO2Porous carbon coated Co3O4Placing the reaction bottle in an oil bath pan, heating to 90-100 ℃, stirring at constant speed for reaction for 3-4h to remove SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4Hollow microspheres.
(5) Adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4And polyacrylonitrile, stirring at a constant speed for 2-3h, performing ultrasonic dispersion treatment on the solution for 1-2h by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 22-30KHz, performing electrostatic spinning on the solution by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 19-21kV, the flow rate of the electrostatic spinning solution is 0.8-1.1mL/h, and the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 20-22cm, thus preparing the polyacrylonitrile-porous carbon-coated Co3O4A nanofiber composite.
(6) Coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3-5 ℃/min, the heat preservation and calcination are carried out for 3-4h at the temperature of 500-520 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofibers.
Preferably, said Co (NO)3)2And the ligand 1,3, 5-triimidazolyl benzene in a molar ratio of 1: 3-4.
Preferably, the Co-based metal organic framework, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate are in a mass ratio of 2-3:1: 8-10.
Preferably, the porous carbon coating Co3O4The mass ratio of the polyacrylonitrile to the polyacrylonitrile is 1: 6-8.
Preferably, the oil bath pot comprises a shell, a supporting table is fixedly connected inside the shell, a side table is fixedly connected on the left side of the shell, a lifting cavity is formed in the top of the side table, a motor is fixedly connected inside the lifting cavity, a connecting piece is installed between the lifting cavity and the supporting table, an operating table is fixedly connected on the right side of the shell, and an oil outlet is formed in the front face of the shell.
Preferably, said Fe2O3Loaded carbon coated nano Co3O4The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding distilled water solvent and 26-32 parts of FeCl into a reaction bottle33-5 parts of carbon nano tube, placing the solution in an ultrasonic treatment instrument with the ultrasonic frequency of 25-35KHz, performing ultrasonic dispersion treatment for 2-3h at the temperature of 60-70 ℃, and then adding 61-70 parts of double-layer carbon-coated Co3O4Stirring the hollow microsphere nano fiber and 1-2 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 1-2 hours, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 160-180 ℃, reacting for 6-10 hours, cooling the solution to room temperature, removing the solvent by reduced pressure distillation, washing the solid product by using distilled water, and fully drying.
(2) Putting the solid product into an atmosphere resistance furnace, and introducing N with the volume ratio of 1.5-2.4:12/O2Mixed gas, the heating rate is 3-5 ℃/min, the mixture is subjected to heat preservation and calcination for 3-4h at 480-500 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the one kind of Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is a Co-based metal organic framework material synthesized by taking 1,3, 5-triimidazolyl benzene as an organic ligand, and a layer of SiO is coated on the surface of the Co-based metal organic framework material by an in-situ synthesis method2Layer of SiO2Coated Co radicalMetal organic framework in N2/O2In the course of atmospheric thermal cracking calcination, SiO2The coating can avoid the carbon layer and O2Direct contact to form a porous carbon structure with stable morphology, and removing SiO by etching2Layer, preparation to obtain porous carbon coated Co3O4Compounding hollow microsphere with polyacrylonitrile, preparing nanofiber by electrostatic spinning, and thermally cracking and calcining to form double-layer carbon-coated Co3O4Hollow microsphere nanofibers as the main structure of the anode material, Co3O4The hollow microsphere nanofiber shortens a transmission path of lithium ions, the hollow structure of the hollow microsphere nanofiber lightens stress generated by volume expansion in the charging and discharging process, the inner porous carbon structure promotes the permeation of electrolyte and the diffusion of the lithium ions through double-layer carbon coating, the outer carbon is an N-doped carbon structure, the hollow microsphere nanofiber has excellent conductivity, the transmission and the migration of charges are promoted, a stable SEI film is favorably formed, and the rate capability and the electrochemical cycle stability of a negative electrode material are enhanced.
The one kind of Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material uses carbon nano-tubes with huge specific surface area as Fe3+By a hot solvent method, coating Co on a double-layer carbon3O4Forming nano Fe on the surface of hollow microsphere nano fiber2O3-carbon nanotube composite, Fe2O3The carbon nanotube composite material provides a transmission channel for charges and lithium ions, promotes the migration of the lithium ions and the reaction of the negative electrode, enables the negative electrode material to have higher specific capacitance and rate capability, and improves the energy density and the cycling stability of the lithium ion battery.
Drawings
FIG. 1 is a top view of a connection structure according to the present invention;
fig. 2 is a front view of the connection structure of the present invention.
In the figure: 1-shell, 2-saddle, 3-side table, 4-lifting cavity, 5-motor, 6-connecting piece, 7-operation table, 8-oil outlet.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material comprises the following formula raw materials in parts by weight: 61-70 parts of double-layer carbon-coated Co3O4Hollow microsphere nano fiber and 26-32 parts of FeCl33-5 parts of carbon nano tube and 1-2 parts of hexadecyl trimethyl ammonium bromide.
Double-layer carbon-coated Co3O4The preparation method of the hollow microsphere nanofiber comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-3:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:3-4, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle is heated to 110-130 ℃, the reaction lasts for 15-20h, the solution is cooled to room temperature, the solvent is removed by reduced pressure distillation, the solid product is washed by distilled water and fully dried, and the Co-based metal organic framework is prepared.
(2) Adding a mixed solution of ethanol and 20-25% ammonia water in a volume ratio of 50-60:1 into a reaction bottle, adding a Co-based metal organic framework and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 40-60min, stirring at a constant speed for 1-2h, slowly dropwise adding ethyl orthosilicate, wherein the mass ratio of the Co-based metal organic framework, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate is 2-3:1:8-10, stirring at a constant speed for reaction for 5-7h, distilling the solution under reduced pressure to remove a solvent, washing a solid product with distilled water, and fully drying to obtain the SiO solid product2Coating Co-based metal organic framework.
(3) Mixing SiO2Placing the Co-based metal organic framework in an atmosphere resistance furnace, introducing N2, heating at a rate of 2-4 ℃/min, keeping the temperature at 320 ℃ for 2-3h at 300-2/O2The volume ratio of the mixed gas and the mixed gas is 1.5-2.4:1,heating to 520 ℃ and 540 ℃, and carrying out heat preservation and calcination for 3-4h, wherein the calcination product is SiO2Porous carbon coated Co3O4。
(4) Introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 4.5-5.5mol/L, adding SiO2Porous carbon coated Co3O4The reaction bottle is placed in an oil bath pot, the oil bath pot comprises a shell, a supporting platform is fixedly connected inside the shell, a side platform is fixedly connected on the left side of the shell, a lifting cavity is formed in the top of the side platform, a motor is fixedly connected inside the lifting cavity, a connecting piece is arranged between the lifting cavity and the supporting platform, an operation platform is fixedly connected on the right side of the shell, an oil outlet is arranged on the front side of the shell, the reaction bottle is heated to 90-100 ℃, and SiO is removed after uniform stirring reaction for 3-4h2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4Hollow microspheres.
(5) Adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4And polyacrylonitrile with the mass ratio of 1:6-8, stirring at constant speed for 2-3h, subjecting the solution to ultrasonic dispersion treatment for 1-2h by an ultrasonic treatment instrument with the ultrasonic frequency of 22-30KHz, subjecting the solution to electrostatic spinning by an electrostatic spinning machine with the voltage of 19-21kV, the flow rate of the electrostatic spinning solution of 0.8-1.1mL/h, and the horizontal receiving distance between an electrostatic spinning receiver and an injector needle of 20-22cm, thereby obtaining the polyacrylonitrile-porous carbon-coated Co3O4A nanofiber composite.
(6) Coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3-5 ℃/min, the heat preservation and calcination are carried out for 3-4h at the temperature of 500-520 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofibers.
Fe2O3Loaded carbon coated nano Co3O4The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding distilled water solvent and 26-32 parts of FeCl into a reaction bottle33-5 parts of carbon nano tube, placing the solution in an ultrasonic treatment instrument with the ultrasonic frequency of 25-35KHz, performing ultrasonic dispersion treatment for 2-3h at the temperature of 60-70 ℃, and then adding 61-70 parts of double-layer carbon-coated Co3O4Stirring the hollow microsphere nano fiber and 1-2 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 1-2 hours, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 160-180 ℃, reacting for 6-10 hours, cooling the solution to room temperature, removing the solvent by reduced pressure distillation, washing the solid product by using distilled water, and fully drying.
(2) Putting the solid product into an atmosphere resistance furnace, and introducing N with the volume ratio of 1.5-2.4:12/O2Mixed gas, the heating rate is 3-5 ℃/min, the mixture is subjected to heat preservation and calcination for 3-4h at 480-500 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material.
Example 1
(1) Preparation of Co-based metal-organic framework component 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:3, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle heating box is heated to 110 ℃, the reaction is carried out for 15 hours, the solution is cooled to room temperature, the solvent is removed through reduced pressure distillation, the solid product is washed through distilled water and fully dried, and the Co-based metal organic framework component 1 is prepared.
(2) Preparation of SiO2Coating Co-based metal-organic framework component 1: adding a mixed solution of ethanol and 20% ammonia water in a volume ratio of 50:1 into a reaction bottle, adding a Co-based metal organic framework component 1 and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 40min, stirring at a constant speed for 1h, slowly dropwise adding tetraethoxysilane, wherein the mass ratio of the Co-based metal organic framework, the hexadecyl trimethyl ammonium bromide and the tetraethoxysilane is 2:1:8, stirring at a constant speed for reaction for 5h, removing the solvent by reduced pressure distillation of the solution, washing a solid product by using distilled water, fully drying,preparation to obtain SiO2Coated with Co-based metal-organic framework component 1.
(3) Preparation of SiO2Porous carbon coated Co3O4Component 1: mixing SiO2Placing the Co-coated metal-organic framework component 1 in an atmosphere resistance furnace, and introducing N2Heating at 2 deg.C/min, maintaining the temperature at 300 deg.C for 2 hr, heating to 660 deg.C, maintaining the temperature, calcining for 2 hr, cooling to room temperature, introducing N2/O2Mixed gas with the volume ratio of 1.5:1, heating to 520 ℃, keeping the temperature and calcining for 3 hours, wherein the calcined product is SiO2Porous carbon coated Co3O4And (3) component 1.
(4) Preparation of porous carbon-coated Co3O4Hollow microsphere component 1: introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 4.5mol/L, adding SiO2Porous carbon coated Co3O4Component 1, arrange the reaction flask in the oil bath pot, the oil bath pot includes the casing, the inside fixedly connected with saddle of casing, the left side fixedly connected with side platform of casing, the lift chamber has been seted up at the top of side platform, the inside fixedly connected with motor in lift chamber installs the connecting piece between lift chamber and the saddle, the right side fixedly connected with operation panel of casing, the oil-out is installed in the front of casing, heat to 90 ℃, at the uniform velocity stirring reaction 3h detach SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4Component hollow microspheres 1.
(5) Preparation of Polyacrylonitrile-porous carbon-coated Co3O4Nanofiber composite component 1: adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4The mass ratio of the hollow microsphere component 1 to the polyacrylonitrile is 1:6, stirring at a constant speed for 2 hours, subjecting the solution to ultrasonic dispersion treatment for 1 hour by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 22KHz, subjecting the solution to an electrostatic spinning process by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 19kV, the flow rate of the electrostatic spinning solution is 0.8mL/h, the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 20cm, and preparing to obtain the polyacrylonitrile-porous materialCarbon coated Co3O4Nanofiber composite component 1.
(6) Preparation of double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 1: coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite component 1 in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3 ℃/min, the heat preservation and calcination are carried out for 3h at the temperature of 500 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 1.
(7) Preparation of Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery negative electrode material 1: adding distilled water solvent and 26 parts of FeCl into a reaction bottle 33 parts of carbon nano tube, placing the solution in an ultrasonic treatment instrument with the ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment for 2 hours at the temperature of 60 ℃, and then adding 70 parts of double-layer carbon-coated Co3O4Stirring the hollow microsphere nano-fiber component 1 and 1 part of hexadecyl trimethyl ammonium bromide at a constant speed for 1h, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box of the reaction kettle, heating to 160 ℃, reacting for 6h, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, introducing N with the volume ratio of 1.5:12/O2Mixed gas, the heating rate is 3 ℃/min, the mixture is subjected to heat preservation and calcination for 3h at 480 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The negative electrode material 1 for a lithium ion battery.
Example 2
(1) Preparation of Co-based metal-organic framework component 2: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:3, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle heating box is heated to 110 ℃, the reaction is carried out for 15 hours, the solution is cooled to room temperature, the solvent is removed through reduced pressure distillation, the solid product is washed through distilled water and fully dried, and the Co-based metal organic framework component 2 is prepared.
(2) Preparation of SiO2Coating Co-based metal organic framework component 2: adding a mixed solution of ethanol and 20% ammonia water in a volume ratio of 50:1 into a reaction bottle, adding a Co-based metal organic framework component 2 and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 40min, stirring at a constant speed for 1h, slowly dropwise adding ethyl orthosilicate, wherein the mass ratio of the Co-based metal organic framework component 2 to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 2:1:8, stirring at a constant speed for reaction for 7h, removing the solvent by reduced pressure distillation of the solution, washing a solid product with distilled water, and fully drying to prepare the SiO2Coated with Co-based metal-organic framework component 2.
(3) Preparation of SiO2Porous carbon coated Co3O4And (2) component: mixing SiO2Placing the Co-coated metal-organic framework component 2 in an atmosphere resistance furnace, and introducing N2Heating at 2 deg.C/min, maintaining the temperature at 300 deg.C for 2 hr, heating to 660 deg.C, maintaining the temperature, calcining for 2 hr, cooling to room temperature, introducing N2/O2Mixed gas with the volume ratio of 1.5:1, heating to 520 ℃, keeping the temperature and calcining for 3 hours, wherein the calcined product is SiO2Porous carbon coated Co3O4And (3) component 2.
(4) Preparation of porous carbon-coated Co3O4Hollow microsphere component 2: introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 4.5mol/L, adding SiO2Porous carbon coated Co3O4Component 2, place the reaction flask in the oil bath pot, heat to 90 ℃, the oil bath pot includes the casing, the inside fixedly connected with saddle of casing, the left side fixedly connected with side platform of casing, the lift chamber has been seted up at the top of side platform, the inside fixedly connected with motor in lift chamber installs the connecting piece between lift chamber and the saddle, the right side fixedly connected with operation panel of casing, the oil-out is installed in the front of casing, at the uniform velocity stirring reaction 3h detach SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4Hollow microsphere setAnd dividing into 2.
(5) Preparation of Polyacrylonitrile-porous carbon-coated Co3O4Nanofiber composite component 2: adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4The mass ratio of the hollow microsphere component 2 to the polyacrylonitrile is 1:6, stirring at a constant speed for 2 hours, subjecting the solution to ultrasonic dispersion treatment for 1 hour by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 22KHz, subjecting the solution to an electrostatic spinning process by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 19kV, the flow rate of the electrostatic spinning solution is 0.8mL/h, the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 22cm, and preparing to obtain the polyacrylonitrile-porous carbon coated Co3O4 Nanofiber composite component 2.
(6) Preparation of double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 2: coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite component 2 in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3 ℃/min, the heat preservation and calcination are carried out for 3h at the temperature of 500 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 2.
(7) Preparation of Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery negative electrode material 2: distilled water solvent and 27.3 parts of FeCl were added to a reaction flask33.5 carbon nano tube, putting the solution into an ultrasonic treatment instrument with the ultrasonic frequency of 25KHz, carrying out ultrasonic dispersion treatment for 2h at the temperature of 60 ℃, and then adding 68 parts of double-layer carbon-coated Co3O4Stirring the hollow microsphere nano-fiber component 2 and 1.2 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 1h, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a reaction kettle heating box, heating to 160 ℃, reacting for 6h, cooling the solution to room temperature, distilling under reduced pressure to remove a solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, introducing N with the volume ratio of 1.5:12/O2Mixed gas, the heating rate is 5 ℃/min, the mixture is subjected to heat preservation and calcination for 3h at 480 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The negative electrode material 2 for a lithium ion battery.
Example 3
(1) Preparation of Co-based metal-organic framework component 3: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2.5:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:3.5, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle heating box is heated to 120 ℃, the reaction is carried out for 18 hours, the solution is cooled to room temperature, the solvent is removed through reduced pressure distillation, the solid product is washed by distilled water and fully dried, and the Co-based metal organic framework component 3 is prepared.
(2) Preparation of SiO2Coating Co-based metal-organic framework component 3: adding a mixed solution of ethanol and 22% ammonia water in a volume ratio of 55:1 into a reaction bottle, adding a Co-based metal organic framework component 3 and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 50min, stirring at a constant speed for 1.5h, slowly dropwise adding ethyl orthosilicate, wherein the mass ratio of the Co-based metal organic framework component 3 to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 2.5:1:9, stirring at a constant speed for reaction for 6h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water, and fully drying to obtain the SiO2Coated with a Co-based metal-organic framework component 3.
(3) Preparation of SiO2Porous carbon coated Co3O4And (3) component: mixing SiO2Placing the Co-coated metal organic framework component 3 in an atmosphere resistance furnace, and introducing N2Heating at a rate of 3 deg.C/min, maintaining at 310 deg.C for 2.5h, heating to 670 deg.C, maintaining the temperature, calcining for 2.5h, cooling to room temperature, introducing N2/O2The volume ratio of the mixed gas and the mixed gas is 2:1, the temperature is raised to 530 ℃, the heat preservation and the calcination are carried out for 3.5 hours, and the calcination product is SiO2Porous carbon coated Co3O4And (3) component.
(4) Preparation of porous carbon-coated Co3O4Hollow microsphere component 3: introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 5mol/LAdding SiO2Porous carbon coated Co3O4Component 3, place the reaction flask in the oil bath pot, heat to 95 ℃, the oil bath pot includes the casing, the inside fixedly connected with saddle of casing, the left side fixedly connected with side platform of casing, the lift chamber has been seted up at the top of side platform, the inside fixedly connected with motor in lift chamber installs the connecting piece between lift chamber and the saddle, the right side fixedly connected with operation panel of casing, the oil-out is installed in the front of casing, at the uniform velocity stirring reaction 3.5h detach SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4Hollow microsphere component 3.
(5) Preparation of Polyacrylonitrile-porous carbon-coated Co3O4Nanofiber composite component 3: adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4The mass ratio of the hollow microsphere component 3 to the polyacrylonitrile is 1:7, stirring at a constant speed for 2.5h, subjecting the solution to ultrasonic dispersion treatment for 1.5h by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 25KHz, subjecting the solution to an electrostatic spinning process by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 20kV, the flow rate of the electrostatic spinning solution is 1mL/h, the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 21cm, and preparing to obtain the polyacrylonitrile-porous carbon coated Co3O4Nanofiber composite component 3.
(6) Preparation of double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 3: coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite component 3 in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 4 ℃/min, the heat preservation and calcination are carried out for 3.5h at 510 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 3.
(7) Preparation of Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery negative electrode material 3: adding distilled water solvent and 29.5 parts of FeCl into a reaction bottle 34 parts of carbon nano tube, putting the solution into an ultrasonic treatment instrument, performing ultrasonic dispersion at the ultrasonic frequency of 30KHz and the temperature of 65 DEG CTreating for 2.5h, adding 65 parts of double-layer carbon-coated Co3O4Stirring 3 parts of hollow microsphere nano fiber component and 1.5 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 1.5 hours, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 170 ℃, reacting for 8 hours, cooling the solution to room temperature, distilling under reduced pressure to remove a solvent, washing a solid product with distilled water, fully drying, placing the solid product into an atmosphere resistance furnace, introducing N with a volume ratio of 2:12/O2Mixed gas, the heating rate is 4 ℃/min, the mixture is subjected to heat preservation and calcination at 490 ℃ for 3.5h, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The negative electrode material 3 for a lithium ion battery.
Example 4
(1) Preparation of Co-based metal-organic framework component 4: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:4, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle is heated to 130 ℃ for 20 hours, the solution is cooled to room temperature, the solvent is removed through reduced pressure distillation, the solid product is washed through distilled water and is fully dried, and the Co-based metal organic framework component 4 is prepared.
(2) Preparation of SiO2Coating Co-based metal-organic framework component 4: adding a mixed solution of ethanol and 25 mass percent ammonia water into a reaction bottle, wherein the volume ratio of the ethanol to the ammonia water is 50:1, adding a Co-based metal organic framework component 4 and hexadecyl trimethyl ammonium bromide, placing the solution into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 60min, then stirring at a constant speed for 1h, then slowly dropwise adding ethyl orthosilicate, wherein the mass ratio of the Co-based metal organic framework, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate is 3:1:10, reacting at a constant speed for 7h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare SiO2Coated with a Co-based metal-organic framework component 4.
(3) Preparation of SiO2Porous carbon coated Co3O4Components4: mixing SiO2Placing the Co-based metal organic framework component 4 in an atmosphere resistance furnace, introducing N2, heating at a rate of 4 ℃/min, keeping the temperature at 320 ℃ for 3h, heating to 660 ℃, keeping the temperature and calcining for 3h, cooling the atmosphere resistance furnace to room temperature, introducing N2/O2Mixed gas with the volume ratio of 1.5:1, heating to 520 ℃, keeping the temperature and calcining for 4 hours, wherein the calcined product is SiO2Porous carbon coated Co3O4And (4) component.
(4) Preparation of porous carbon-coated Co3O4Hollow microsphere component 4: introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 5.5mol/L, adding SiO2Porous carbon coated Co3O4Component 4, place the reaction flask in the oil bath pot, heat to 90 ℃, the oil bath pot includes the casing, the inside fixedly connected with saddle of casing, the left side fixedly connected with side platform of casing, the lift chamber has been seted up at the top of side platform, the inside fixedly connected with motor in lift chamber installs the connecting piece between lift chamber and the saddle, the right side fixedly connected with operation panel of casing, the oil-out is installed in the front of casing, at the uniform velocity stirring reaction 4h detach SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4A hollow microsphere component 4.
(5) Preparation of Polyacrylonitrile-porous carbon-coated Co3O4Nanofiber composite component 4: adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4The mass ratio of the hollow microsphere component 4 to the polyacrylonitrile is 1:8, stirring at a constant speed for 2 hours, subjecting the solution to ultrasonic dispersion treatment for 1 hour by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 22KHz, subjecting the solution to an electrostatic spinning process by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 21kV, the flow rate of the electrostatic spinning solution is 1.1mL/h, the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 22cm, and preparing to obtain the polyacrylonitrile-porous carbon coated Co3O4Nanofiber composite component 4.
(6) Preparation of double-layer carbon-coated Co3O4Hollow microsphere nanofiber component4: coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite component 4 in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3 ℃/min, the heat preservation and calcination are carried out for 3h at the temperature of 520 ℃, and the calcination product is double-layer carbon-coated Co3O4A hollow microsphere nanofiber component 4.
(7) Preparation of Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery negative electrode material 4: adding distilled water solvent and 30.8 parts of FeCl into a reaction bottle34.5 parts of carbon nano tube, placing the solution in an ultrasonic treatment instrument with the ultrasonic frequency of 25KHz, performing ultrasonic dispersion treatment for 2 hours at the temperature of 70 ℃, and then adding 63 parts of double-layer carbon-coated Co3O4Stirring 4 parts of hollow microsphere nanofiber component and 1.7 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 2 hours, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a reaction kettle heating box, heating to 180 ℃, reacting for 6 hours, cooling the solution to room temperature, distilling under reduced pressure to remove a solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, introducing N with the volume ratio of 2.4:12/O2Mixed gas, the heating rate is 5 ℃/min, the mixture is subjected to heat preservation and calcination for 3h at 480 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The negative electrode material 4 for a lithium ion battery.
Example 5
(1) Preparation of Co-based metal-organic framework component 5: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3:1, and adding Co (NO)3)2And ligand 1,3, 5-triimidazolyl benzene, wherein the mass molar ratio of the two substances is 1:4, the solution is transferred into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a reaction kettle heating box, the reaction kettle is heated to 130 ℃ for 20 hours, the solution is cooled to room temperature, the solvent is removed through reduced pressure distillation, the solid product is washed through distilled water and fully dried, and the Co-based metal organic framework component 5 is prepared.
(2) Preparation of SiO2Coating Co-based metal-organic framework component 5: adding a mixed solution of ethanol and 25 mass percent ammonia water into a reaction bottleAdding a Co-based metal organic framework component 5 and hexadecyl trimethyl ammonium bromide into the solution at a volume ratio of 60:1, placing the solution into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 60min, stirring at a constant speed for 2h, slowly dropwise adding ethyl orthosilicate, wherein the mass ratio of the Co-based metal organic framework to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 3:1:10, stirring at a constant speed for reaction for 6h, carrying out reduced pressure distillation on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare SiO2Coated with a Co-based metal-organic framework component 5.
(3) Preparation of SiO2Porous carbon coated Co3O4And (5) component: mixing SiO2Placing the Co-coated metal-organic framework component 5 in an atmosphere resistance furnace, and introducing N2Heating at a rate of 4 ℃/min, keeping the temperature of 320 ℃ for 3h, heating to 680 ℃, keeping the temperature, calcining for 3h, cooling the atmosphere resistance furnace to room temperature, and introducing N2/O2Mixed gas with the volume ratio of 2.4:1, the temperature is raised to 540 ℃, the temperature is preserved and calcined for 3.5 hours, and the calcined product is SiO2Porous carbon coated Co3O4And (5) component.
(4) Preparation of porous carbon-coated Co3O4Hollow microsphere component 5: introducing N into the reaction bottle2Adding sodium hydroxide solution with the mass concentration of 5.5mol/L, adding SiO2Porous carbon coated Co3O4Component 5, place the reaction flask in the oil bath pot, heat to 100 ℃, the oil bath pot includes the casing, the inside fixedly connected with saddle of casing, the left side fixedly connected with side platform of casing, the lift chamber has been seted up at the top of side platform, the inside fixedly connected with motor in lift chamber installs the connecting piece between lift chamber and the saddle, the right side fixedly connected with operation panel of casing, the oil-out is installed in the front of casing, at the uniform velocity stirring reaction 3.5h detach SiO2Filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the porous carbon-coated Co3O4A hollow microsphere component 5.
(5) Preparation of Polyacrylonitrile-porous carbon-coated Co3O4Nanofiber composite component 5: into N, N-dimethylformamide solventAdding porous carbon coated Co3O4The mass ratio of the hollow microsphere component 5 to the polyacrylonitrile is 1:8, stirring at a constant speed for 3 hours, subjecting the solution to ultrasonic dispersion treatment for 1.5 hours by an ultrasonic treatment instrument, wherein the ultrasonic frequency is 30KHz, subjecting the solution to an electrostatic spinning process by an electrostatic spinning machine, the voltage of the electrostatic spinning machine is 21kV, the flow rate of the electrostatic spinning solution is 1.1mL/h, the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 22cm, and preparing to obtain the polyacrylonitrile-porous carbon coated Co3O4Nanofiber composite component 5.
(6) Preparation of double-layer carbon-coated Co3O4Hollow microsphere nanofiber component 5: coating polyacrylonitrile-porous carbon with Co3O4The nanofiber composite component 5 was placed in an atmospheric resistance furnace and N was passed through2The temperature rise rate is 5 ℃/min, the heat preservation and calcination are carried out for 4h at the temperature of 520 ℃, and the calcination product is double-layer carbon-coated Co3O4A hollow microsphere nanofiber component 5.
(7) Preparation of Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery negative electrode material 5: adding distilled water solvent and 32 parts of FeCl into a reaction bottle 35 parts of carbon nano tube, placing the solution in an ultrasonic treatment instrument with the ultrasonic frequency of 35KHz, performing ultrasonic dispersion treatment for 3 hours at the temperature of 70 ℃, and then adding 61 parts of double-layer carbon-coated Co3O4Stirring 5 parts of hollow microsphere nano fiber component and 2 parts of hexadecyl trimethyl ammonium bromide at a constant speed for 2 hours, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 180 ℃, reacting for 10 hours, cooling the solution to room temperature, distilling under reduced pressure to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, introducing N with the volume ratio of 2.4:12/O2Mixed gas, the heating rate is 5 ℃/min, the mixture is subjected to heat preservation and calcination for 4h at the temperature of 500 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The negative electrode material 5 for a lithium ion battery.
Fe in examples 1 to 52O3Loaded carbon coated nano Co3O4Lithium ion ofThe method comprises the steps of respectively placing a sub-battery negative electrode material in an N-methylpyrrolidone solvent, adding polyvinylidene fluoride and acetylene black, uniformly dispersing, uniformly coating slurry on the surface of copper foil, drying, preparing to obtain a negative working electrode, assembling a CR2032 button battery by taking a lithium sheet as a counter electrode, taking Celgard 2400 as a diaphragm and taking 1mol/L LiPF6+ dimethyl carbonate + ethylene carbonate + diethyl carbonate solution as electrolyte in an argon atmosphere, and testing the electrochemical performance in a CT-4000T-5V6A battery detection system, wherein the test standard is GB/T36276-2018.
Figure BDA0002608940950000171
In summary, the one kind of Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is a Co-based metal organic framework material synthesized by taking 1,3, 5-triimidazolyl benzene as an organic ligand, and a layer of SiO is coated on the surface of the Co-based metal organic framework material by an in-situ synthesis method2Layer of SiO2Coating with Co-based metal-organic frameworks on N2/O2In the course of atmospheric thermal cracking calcination, SiO2The coating can avoid the carbon layer and O2Direct contact to form a porous carbon structure with stable morphology, and removing SiO by etching2Layer, preparation to obtain porous carbon coated Co3O4Compounding hollow microsphere with polyacrylonitrile, preparing nanofiber by electrostatic spinning, and thermally cracking and calcining to form double-layer carbon-coated Co3O4Hollow microsphere nanofibers as the main structure of the anode material, Co3O4The hollow microsphere nanofiber shortens a transmission path of lithium ions, the hollow structure of the hollow microsphere nanofiber lightens stress generated by volume expansion in the charging and discharging process, the inner porous carbon structure promotes the permeation of electrolyte and the diffusion of the lithium ions through double-layer carbon coating, the outer carbon is an N-doped carbon structure, the hollow microsphere nanofiber has excellent conductivity, the transmission and the migration of charges are promoted, a stable SEI film is favorably formed, and the rate capability and the electrochemical cycle stability of a negative electrode material are enhanced.
Using specific surface areaGiant carbon nanotubes as Fe3+By a hot solvent method, coating Co on a double-layer carbon3O4Forming nano Fe on the surface of hollow microsphere nano fiber2O3-carbon nanotube composite, Fe2O3The carbon nanotube composite material provides a transmission channel for charges and lithium ions, promotes the migration of the lithium ions and the reaction of the negative electrode, enables the negative electrode material to have higher specific capacitance and rate capability, and improves the energy density and the cycling stability of the lithium ion battery.

Claims (7)

1. Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material comprises the following formula raw materials in parts by weight, and is characterized in that: 61-70 parts of double-layer carbon-coated Co3O4Hollow microsphere nano fiber and 26-32 parts of FeCl33-5 parts of carbon nano tube and 1-2 parts of hexadecyl trimethyl ammonium bromide.
2. Fe according to claim 12O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: the double-layer carbon coated Co3O4The preparation method of the hollow microsphere nanofiber comprises the following steps:
(1) adding Co (NO) into a mixed solvent of distilled water and ethanol with a volume ratio of 2-3:13)2And ligand 1,3, 5-triimidazolyl benzene, transferring the solution into a hydrothermal reaction kettle, heating to 110 ℃ and 130 ℃, reacting for 15-20h, removing the solvent from the solution, washing the solid product, and drying to prepare the Co-based metal organic framework.
(2) Adding a Co-based metal organic framework and hexadecyl trimethyl ammonium bromide into a mixed solution of ethanol and ammonia water with the mass fraction of 20-25% in a volume ratio of 50-60:1, performing ultrasonic dispersion treatment on the solution for 40-60min, stirring at a constant speed for 1-2h, slowly dropwise adding ethyl orthosilicate, reacting for 5-7h, removing the solvent from the solution, washing a solid product, drying, and preparing to obtain SiO2Coating Co-based metal organic framework.
(3) Mixing SiO2Placing the Co-based metal organic framework in an atmosphere resistance furnace, introducing N2, heating at a rate of 2-4 ℃/min, keeping the temperature at 320 ℃ for 2-3h at 300-2/O2Mixed gas with the volume ratio of 1.5-2.4:1, heating to 520-540 ℃, and performing heat preservation and calcination for 3-4h, wherein the calcination product is SiO2Porous carbon coated Co3O4。
(4) Adding SiO into sodium hydroxide solution with the mass concentration of 4.5-5.5mol/L2Porous carbon coated Co3O4Adding the solution in N2In the atmosphere, placing the mixture in an oil bath pot, heating the mixture to 90-100 ℃, and reacting for 3-4h to remove SiO2Layer, removing solvent from the solution, washing the solid product, drying to obtain the porous carbon coated Co3O4Hollow microspheres.
(5) Adding porous carbon-coated Co into N, N-dimethylformamide solvent3O4And polyacrylonitrile, stirring at a constant speed for 2-3h, performing ultrasonic dispersion treatment on the solution for 1-2h at an ultrasonic frequency of 22-30KHz, performing electrostatic spinning on the solution by using an electrostatic spinning machine at a voltage of 19-21kV and a flow rate of 0.8-1.1mL/h, wherein the horizontal receiving distance between a receiver of the electrostatic spinning and a syringe needle is 20-22cm, and thus obtaining the polyacrylonitrile-porous carbon-coated Co3O4A nanofiber composite.
(6) Coating polyacrylonitrile-porous carbon with Co3O4Placing the nanofiber composite in an atmosphere resistance furnace, and introducing N2The temperature rise rate is 3-5 ℃/min, the heat preservation and calcination are carried out for 3-4h at the temperature of 500-520 ℃, and the calcination product is double-layer carbon-coated Co3O4Hollow microsphere nanofibers.
3. Fe according to claim 22O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: the Co (NO)3)2And the ligand 1,3, 5-triimidazolyl benzene in a molar ratio of 1: 3-4.
4. Fe according to claim 22O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: the Co-based metal organic framework, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate are in a mass ratio of 2-3:1: 8-10.
5. Fe according to claim 22O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: the porous carbon coated Co3O4The mass ratio of the polyacrylonitrile to the polyacrylonitrile is 1: 6-8.
6. Fe according to claim 22O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: the oil bath pot comprises a shell (1), a supporting platform (2) fixedly connected with the inside of the shell (1), a side platform (3) fixedly connected with the left side of the shell (1), a lifting cavity (4) is formed in the top of the side platform (3), a motor (5) fixedly connected with the inside of the lifting cavity (4), a connecting piece (6) is installed between the lifting cavity (4) and the supporting platform (2), an operating platform (7) fixedly connected with the right side of the shell (1), and an oil outlet (8) is installed in the front of the shell (1).
7. Fe according to claim 12O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material is characterized in that: said Fe2O3Loaded carbon coated nano Co3O4The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding 26-32 parts of FeCl into distilled water solvent33-5 parts of carbon nano tube, performing ultrasonic dispersion treatment on the solution at the temperature of 60-70 ℃ for 2-3h, wherein the ultrasonic frequency is 25-35KHz, and then adding 61-70 parts of double-layer carbon-coated Co3O4Mixing hollow microsphere nano fiber and 1-2 parts of hexadecyl trimethyl ammonium bromide at constant speed for 1-2hTransferring the solution into a hydrothermal reaction kettle, heating to 160-180 ℃, reacting for 6-10h, removing the solvent from the solution, washing the solid product, and drying.
(2) Putting the solid product into an atmosphere resistance furnace, and introducing N with the volume ratio of 1.5-2.4:12/O2Mixed gas, the heating rate is 3-5 ℃/min, the mixture is subjected to heat preservation and calcination for 3-4h at 480-500 ℃, and the calcination product is Fe2O3Loaded carbon coated nano Co3O4The lithium ion battery cathode material.
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