CN111740083A - Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof - Google Patents

Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof Download PDF

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CN111740083A
CN111740083A CN202010534137.0A CN202010534137A CN111740083A CN 111740083 A CN111740083 A CN 111740083A CN 202010534137 A CN202010534137 A CN 202010534137A CN 111740083 A CN111740083 A CN 111740083A
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CN111740083B (en
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李华想
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Xiaoxian xinhuiyuan Battery Co., Ltd
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Xinchang Huafa Machinery Co ltd
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    • H—ELECTRICITY
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    • 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
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention relates to the technical field of lithium ion batteries and discloses carbon-coated porous Co3O4The microsphere lithium ion battery cathode material comprises the following formula raw materials and components: co3O4-carbon nanotube composite, resorcinol, formaldehyde, polyol phosphate. The carbon-coated porous Co3O4Lithium ion battery cathode material of microsphere, porous nanometer Co3O4The hollow microsphere has huge specific surface area, can provide more electrochemical active sites, is rich in a pore junction mesoporous structure, can provide a diffusion channel for lithium ions, and is porous and nano Co3O4The microspheres are uniformly attached to the nitrogen-doped carbon nanotubes, thereby enhancing Co3O4The conductivity of the cathode material promotes the transmission and migration of electrons, and the carbon layer doped with the cathode material can achieve the effect of carbon layer stripping, so that the carbon layer structure is widened, a large number of pores and mesoporous structures are formed, and the carbon layer is Co3O4The volume expansion of (2) provides elastic buffering, reduces stress generated by expansion, and slows down volume expansion and structural change phenomena.

Description

Carbon-coated porous Co3O4Microsphere 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 carbon-coated porous Co3O4A microsphere lithium ion battery cathode material and a preparation method thereof.
Background
The lithium ion battery is a chargeable secondary battery, in the charging and discharging process, lithium ions are inserted and extracted back and forth between a positive electrode and a negative electrode, so that the positive electrode and the negative electrode reach a lithium-rich state respectively, the lithium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm and the like, and active substances of the positive electrode material are lithium manganate, lithium cobaltate and the like generally; the electrolyte is generally carbonate solvent of lithium hexafluoropolyol phosphate ester, gel polymer electrolyte; the diaphragm is a specially formed polymer film with a microporous structure, and can allow lithium ions to freely pass through but not electrons to pass through; the negative electrode material plays an important role in the performance of the lithium ion battery.
At present, the negative electrode material of the lithium ion battery mainly comprises metal negative electrode materials such as tin-based alloy, antimony-based alloy and the like; inorganic non-metallic negative electrode materials such as carbon materials, silicon materials, and the like; transition metal oxide materials such as lithium transition oxides, tin-based composite oxides, etc., wherein Co is3O4The lithium ion battery cathode material has high theoretical specific capacity and good capacity retention rate, is an active substance of a lithium ion battery cathode material with great potential, but Co3O4Has a low conductivity, inhibits the transmission and diffusion of electrons during electrode reaction, and inhibits the progress of electrode reaction, and Co3O4During the charge and discharge process, the lithium ion extraction and insertion process can cause Co3O4The volume expansion and the change of the matrix structure of the electrode material reduce the charge-discharge reversibility and the electrochemical cycle stability of the electrode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides carbon-coated porous Co3O4The lithium ion battery cathode material of the microsphere and the preparation method thereof solve the problem of Co3O4The electrode material has a higher conductivityLow problem, and solves Co3O4In the process of charging and discharging, the phenomena of volume expansion and matrix structure change are easy to occur.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: carbon-coated porous Co3O4The microsphere lithium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 18-40 parts of Co3O4Carbon nanotube composite material, 20-26 parts of resorcinol, 32-40 parts of formaldehyde, 8-16 parts of polyhydric alcohol phosphate ester,
Preferably, said Co3O4The preparation method of the carbon nanotube composite material comprises the following steps:
(1) adding distilled water and CoCl into a reaction bottle2And a dispersant citric acid, adding urotropine and glucose after uniformly stirring, transferring the solution into a full-automatic reaction kettle, heating to 130-3O4Hollow microspheres.
(2) Adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving hollow microspheres, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1-2h at the temperature of 40-60 ℃, adding ferrous chloride, pouring the solution into a full-automatic reaction kettle, heating to 80-120 ℃, stirring at a constant speed for reaction for 2-4h, distilling the solution under reduced pressure to remove the solvent, fully drying, placing a solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 1-5 ℃/min, calcining at the temperature of 480 ℃ for 2-4h, washing the calcined product with distilled water, and fully drying to prepare the porous nano Co-doped nano-particles, wherein the temperature of the calcined product is 480 ℃ and 520 ℃, and the calcined product is washed with distilled water and fully dried to3O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4-carbon nanotube composites.
Preferably, full-automatic reation kettle includes the cauldron body, the external fixedly connected with heat preservation of cauldron, inside and reation kettle inner bag fixed connection of heat preservation, reation kettle inner bag and air inlet fixed connection, air inlet and valve swing joint, valve swing joint has the air pump interface, agitating unit under the fixedly connected with of reation kettle inner bag below, agitating unit and lower stirring fan piece active link down, reation kettle inner bag top and reation kettle lid swing joint, agitating unit on the fixedly connected with of reation kettle lid below, go up agitating unit below and last stirring fan piece swing joint.
Preferably, the CoCl2The mass ratio of the citric acid to the urotropine to the glucose is 1:8-12:2-4: 4-6.
Preferably, the porous nano-Co3O4The mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 6-10:1:2-4: 0.04-0.1.
Preferably, the carbon-coated porous Co3O4The microsphere lithium ion battery cathode material.
(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 6-10:1, adding ammonia water to adjust the pH value of the solution to 8-10, and adding 18-40 parts of Co3O4Placing a reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-70 ℃ for 1-2h, pouring the solution into a full-automatic reaction kettle, heating to 100 ℃ and 130 ℃, stirring at constant speed for 25-30h, drying the solution in vacuum to remove the solvent, and preparing the phenolic resin nano microsphere coated Co nano microsphere3O4。
(2) Coating phenolic resin nano-microspheres with Co3O4Placing the mixture in an atmosphere resistance furnace, introducing nitrogen, calcining the mixture for 2 to 4 hours at the temperature of 500-550 ℃ at the temperature rise rate of 2 to 8 ℃/min, washing the calcined product by using distilled water, and fully drying the calcined product to prepare the carbon-coated porous Co3O4The microsphere lithium ion battery cathode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon-coated porous Co3O4A lithium ion battery cathode material of microspheres is prepared by taking carbon nano-microspheres prepared from glucose through a hydrothermal synthesis method as sacrificial templates, citric acid as a dispersing agent and urotropine as an accelerant, and removing the carbon nano-microspheres through high-temperature thermal cracking3O4Hollow structure with nano-morphology, corresponding to common Co3O4Porous nano Co3O4The hollow microspheres have huge specific surface area, can provide more electrochemical active sites, contain rich pore junction mesoporous structures, can provide diffusion channels for lithium ions, and improve the deintercalation rate of the lithium ions.
The carbon-coated porous Co3O4The microsphere lithium ion battery cathode material takes urea and melamine as a nitrogen source and a carbon source, takes ferrous chloride as a catalyst, and is prepared into a nitrogen-doped carbon nano tube by an in-situ polymerization method, wherein the electronegativity of nitrogen is larger than that of carbon, so that the transfer of electrons in carbon atoms to the nitrogen atoms is promoted, the positive charge of the carbon atoms is increased, and the carbon nano tube has more excellent electropositivity and conductivity, and the porous nano Co cathode material has the advantages of3O4The microspheres are uniformly attached to the nitrogen-doped carbon nano-tubes, so that not only can the nano Co be effectively reduced3O4The phenomenon of agglomeration and aggregation, and the nitrogen-doped carbon nanotube with excellent conductivity greatly enhances Co3O4The conductive performance of the cathode material promotes the transmission and migration of electrons, and is beneficial to the electrode reaction.
The carbon-coated porous Co3O4A lithium ion battery negative electrode material of microspheres is prepared by taking polyalcohol phosphate as a doping agent, polycondensing m-diphenol and formaldehyde into a phosphorus-doped polymer by a hot solvent method, and uniformly coating Co3O4-carbon nanotube composite material, formed by high temperature thermal cracking, phosphorus doped carbon material coated Co3O4The atomic radius of the phosphorus is much larger than that of the carbon, and the phosphorus is doped into the carbon layer structure to play a role in carbon layer stripping, so that the carbon layer structure is widened, a large number of pores and mesoporous structures are formed, and Co is used as a material for preparing the carbon-based carbon material3O4During charging and discharging, lithium ionsCan cause Co to be deintercalated and intercalated3O4Volume expansion and structural change of (a), and the pores and mesoporous structure are Co3O4The volume expansion of (A) provides an elastic buffer, reduces the stress generated by the expansion, and thus slows down Co3O4The volume expansion and the structural change phenomena enhance the electrochemical cycle stability of the cathode material, meanwhile, the phosphorus doping can improve the wettability of the carbon material, and a large number of pores and mesoporous structures can also soak the electrolyte, so that active sites can be fully contacted with the electrolyte, thereby enhancing the electrochemical performance of the electrode material.
Drawings
FIG. 1 is a schematic diagram of the front side of a kettle reaction kettle structure;
FIG. 2 is a schematic front view of a reaction vessel cover of the vessel body.
1. A kettle body; 2. a heat-insulating layer; 3. an inner container of the reaction kettle; 4. an air inlet; 5. a valve; 6. an air pump interface; 7. a lower stirring device; 8. a lower stirring fan blade; 9. a reaction kettle cover; 10. an upper stirring device; 11. and a stirring fan blade is arranged.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: carbon-coated porous Co3O4The microsphere lithium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 18-40 parts of Co3O4Carbon nanotube composite material, 20-26 parts of resorcinol, 32-40 parts of formaldehyde, 8-16 parts of polyhydric alcohol phosphate ester,
Co3O4The preparation method of the carbon nanotube composite material comprises the following steps:
(1) adding distilled water and CoCl into a reaction bottle2And citric acid serving as a dispersing agent, adding urotropine and glucose after uniformly stirring, wherein the mass ratio of urotropine to glucose is 1:8-12:2-4:4-6, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, and the valve is movably connected with an air pump to be connected with an air pumpA lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a reaction kettle cover, the lower part of the reaction kettle cover is fixedly connected with an upper stirring device, the lower part of the upper stirring device is movably connected with an upper stirring fan, the mixture is heated to 130-3O4Hollow microspheres.
(2) Adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving hollow microspheres, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1-2h at 40-60 ℃, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 80-120 ℃, uniformly stirring for reaction for 2-4h, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product in an atmosphere resistance furnace, introducing nitrogen at the heating rate of 1-5 ℃/min, calcining at the temperature of 480-520 ℃ for 2-4h, washing the calcined product with distilled water, and fully drying to prepare the porous nano Co-based catalyst, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 6-10:1:2-4:0.04-0.13O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4-carbon nanotube composites.
Carbon coated porous Co3O4The microsphere lithium ion battery cathode material.
(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 6-10:1, adding ammonia water to adjust the pH value of the solution to 8-10, and adding 18-40 parts of Co3O4Carbon nano tube composite material, 20-26 parts of resorcinol, 32-40 parts of formaldehyde and 8-16 parts of polyalcohol phosphate, placing a reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-70 ℃ for 1-2h, pouring the solution into a full-automatic reaction kettle, heating to 100 ℃ and 130 ℃, carrying out uniform stirring reaction for 25-30h, and carrying out vacuum reaction on the solutionDrying to remove the solvent, and preparing the phenolic resin nano microsphere coated Co3O4。
(2) Coating phenolic resin nano-microspheres with Co3O4Placing the mixture in an atmosphere resistance furnace, introducing nitrogen, calcining the mixture for 2 to 4 hours at the temperature of 500-550 ℃ at the temperature rise rate of 2 to 8 ℃/min, washing the calcined product by using distilled water, and fully drying the calcined product to prepare the carbon-coated porous Co3O4The microsphere lithium ion battery cathode material.
Coating carbon with porous Co3O4Dissolving the microsphere lithium ion battery negative electrode material, the conductive agent acetylene black and the adhesive polyvinylidene fluoride pyrrolidone in a mass ratio of 8:1:1 in N-methyl pyrrolidone, coating the solution on copper foil, and fully drying to prepare the working electrode material of the lithium ion battery positive electrode.
Example 1
(1) Preparation of porous Nano Co3O4Hollow microsphere component 1: adding distilled water and CoCl into a reaction bottle2And citric acid as a dispersing agent, adding urotropine and glucose after uniformly stirring, wherein the mass ratio of the urotropine to the glucose is 1:8:2:4, transferring the solution into a full-automatic reaction kettle, the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, the valve is movably connected with an air pump interface, a lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a cover of the reaction kettle, an upper stirring device is fixedly connected below the cover of the reaction kettle, the lower part of the upper stirring fan is movably connected with the upper stirring fan, heating is carried out to 130 ℃, stirring reaction is carried out, placing the solid product in a resistance furnace, heating the solid product to 460 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation and calcination for 4h to prepare the porous nano Co3O4Hollow microsphere component 1.
(2) Preparation of Co3O4Carbon nanotube composite 1: adding ethanol into a reaction bottleSolvent, adding porous nano Co3O4Stirring and dissolving the hollow microsphere component 1, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1h at 40 ℃, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 80 ℃, uniformly stirring for reaction for 2 hours, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 1 ℃/min, calcining at 480 ℃ for 2 hours, washing the calcined product with distilled water, fully drying, and preparing the porous nano Co based catalyst, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 6:1:2:0.043O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4 Carbon nanotube composite 1.
(3) Preparation of phenolic resin nano-microsphere coated Co3O4Component 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 6:1, adding ammonia water to adjust the pH of the solution to be 0, and adding 40 parts of Co3O4Placing a reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 1h at 40 ℃, pouring the solution into a full-automatic reaction kettle, heating to 130 ℃, stirring at a constant speed for reaction for 25h, and performing vacuum drying on the solution to remove the solvent to prepare the phenolic resin nano microsphere coated Co composite material 1, 20 parts of resorcinol, 32 parts of formaldehyde and 8 parts of polyol phosphate3O4And (3) component 1.
(4) Preparation of carbon-coated porous Co3O4Negative electrode material of microsphere lithium ion battery 1: coating phenolic resin nano-microspheres with Co3O4Placing the component 1 in an atmosphere resistance furnace, introducing nitrogen, calcining at 500 ℃ for 2h at the heating rate of 2 ℃/min, washing the calcined product with distilled water, and fully drying to prepare the carbon-coated porous Co3O4A microsphere lithium ion battery cathode material 1.
Example 2
(1) Preparation of porous Nano Co3O4Hollow microsphere component 2: adding distilled water and CoCl into a reaction bottle2And citric acid as a dispersing agent, adding urotropine and glucose after uniformly stirring, wherein the mass ratio of the urotropine to the glucose is 1:12:2:4, transferring the solution into a full-automatic reaction kettle, the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, the valve is movably connected with an air pump interface, a lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a cover of the reaction kettle, an upper stirring device is fixedly connected below the cover of the reaction kettle, the lower part of the upper stirring fan is movably connected with the upper stirring fan, heating is carried out to 160 ℃, stirring reaction is carried out, placing the solid product in a resistance furnace, heating to 520 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation and calcination for 6h to obtain the porous nano Co3O4Hollow microsphere component 2.
(2) Preparation of Co3O4Carbon nanotube composite 2: adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving the hollow microsphere component 2, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 60 ℃ for 1h, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 120 ℃, uniformly stirring for reaction for 2 hours, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 1 ℃/min, calcining at 520 ℃ for 2 hours, washing the calcined product with distilled water, fully drying, and preparing the porous nano Co based catalyst, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 0:1:2:0.043O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4 Carbon nanotube composite 2.
(3) Preparation of phenolic resin nano-microsphere coated Co3O4And (2) component: 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 6:1, and addingAdding ammonia water to adjust the pH value of the solution to 10, and adding 35 parts of Co3O4Placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1h at 70 ℃, pouring the solution into a full-automatic reaction kettle, heating to 100 ℃, stirring at a constant speed for reaction for 30h, and performing vacuum drying on the solution to remove the solvent to prepare the phenolic resin nano microsphere coated Co composite material 1, 21.5 parts of resorcinol, 34 parts of formaldehyde and 9.5 parts of polyol phosphate3O4And (3) component 2.
(4) Preparation of carbon-coated porous Co3O4 Negative electrode material 2 of microspherical lithium ion battery: coating phenolic resin nano-microspheres with Co3O4Placing the component 2 in an atmosphere resistance furnace, introducing nitrogen, calcining at 500 ℃ for 4h at the heating rate of 8 ℃/min, washing the calcined product with distilled water, and fully drying to obtain the carbon-coated porous Co3O4And 2, a microsphere lithium ion battery cathode material.
Example 3
(1) Preparation of porous Nano Co3O4Hollow microsphere component 3: adding distilled water and CoCl into a reaction bottle2And citric acid as a dispersing agent, adding urotropine and glucose after uniformly stirring, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, the valve is movably connected with an air pump interface, a lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a cover of the reaction kettle, an upper stirring device is fixedly connected below the cover of the reaction kettle, the lower part of the upper stirring device is movably connected with the upper stirring fan, heating is carried out to 145 ℃, stirring reaction is carried out for 25 hours at a constant speed, the solution is dried in vacuum to remove a solvent, distilled, placing the solid product in a resistance furnace, heating to 490 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation and calcination for 5h to prepare the porous nano Co3O4Hollow microsphere component 3.
(2) System for makingPreparation of Co3O4Carbon nanotube composite 3: adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving the hollow microsphere component 3, urea and melamine, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 50 ℃ for 1.5h, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 100 ℃, uniformly stirring for reaction for 3 hours, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2 ℃/min, calcining at 500 ℃ for 3 hours, washing the calcined product with distilled water, fully drying, and preparing the porous nano Co based composite material, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 8:1:3:0.083O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4 Carbon nanotube composite 3.
(3) Preparation of phenolic resin nano-microsphere coated Co3O4And (3) component: 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 8:1, adding ammonia water to adjust the pH of the solution to 9, and adding 30 parts of Co3O4Placing a reaction bottle in an ultrasonic disperser, carrying out ultrasonic dispersion treatment for 1.5h at 55 ℃, pouring the solution into a full-automatic reaction kettle, heating to 115 ℃, stirring at a constant speed for reaction for 28h, carrying out vacuum drying on the solution to remove the solvent, and preparing the phenolic resin nano microsphere coated Co nano-microsphere3O4And (3) component.
(4) Preparation of carbon-coated porous Co3O4 Negative electrode material 3 of microspherical lithium ion battery: coating phenolic resin nano-microspheres with Co3O4Placing the component 3 in an atmosphere resistance furnace, introducing nitrogen, calcining at 520 ℃ for 3h at the heating rate of 5 ℃/min, washing the calcined product with distilled water, and fully drying to obtain the carbon-coated porous Co3O4And (3) a microsphere lithium ion battery negative electrode material.
Example 4
(1) Preparation of porous Nano Co3O4Hollow microsphere component 4: adding distilled water and CoCl into a reaction bottle2And citric acid as a dispersing agent, adding urotropine and glucose after uniformly stirring, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, the valve is movably connected with an air pump interface, a lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a cover of the reaction kettle, an upper stirring device is fixedly connected below the cover of the reaction kettle, the lower part of the upper stirring device is movably connected with the upper stirring fan, heating is carried out to 160 ℃, stirring reaction is carried out for 20 hours at a constant speed, the solution is dried in vacuum to remove a solvent, distilled, placing the solid product in a resistance furnace, heating to 520 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation and calcination for 6h to obtain the porous nano Co3O4Hollow microsphere component 4.
(2) Preparation of Co3O4Carbon nanotube composite 4: adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving the hollow microsphere component 4, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 40 ℃ for 1h, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 120 ℃, uniformly stirring for reaction for 4 hours, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, calcining at 520 ℃ for 2 hours, washing the calcined product with distilled water, fully drying, and preparing the porous nano Co based composite material, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 10:1:2:0.043O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4 Carbon nanotube composite 4.
(3) Preparation of phenolic resin nano-microsphere coated Co3O4And (4) component: 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 10:1, adding ammonia water to adjust the pH value of the solution to be 8, and adding 23 parts of Co3O44 parts of carbon nano tube composite material, 25 parts of resorcinol, 38 parts of formaldehyde and 14 parts of polyol phosphate, placing a reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 2 hours at 40 ℃, pouring the solution into a full-automatic reaction kettle, heating to 130 ℃, stirring at a constant speed for reaction for 25 hours, and carrying out vacuum drying on the solution to remove the solvent to prepare the phenolic resin nano microsphere coated Co3O4And (4) component.
(4) Preparation of carbon-coated porous Co3O4 Negative electrode material 4 of lithium ion battery of microsphere: coating phenolic resin nano-microspheres with Co3O4Placing the component 4 in an atmosphere resistance furnace, introducing nitrogen, calcining at 500 ℃ for 4h at the temperature rise rate of 2 ℃/min, washing the calcined product with distilled water, and fully drying to obtain the carbon-coated porous Co3O4And (4) a microsphere lithium ion battery negative electrode material.
Example 5
(1) Preparation of porous Nano Co3O4Hollow microsphere component 5: adding distilled water and CoCl into a reaction bottle2And citric acid as a dispersing agent, adding urotropine and glucose after uniformly stirring, transferring the solution into a full-automatic reaction kettle, wherein the full-automatic reaction kettle comprises a kettle body, a heat insulation layer is fixedly connected outside the kettle body, the interior of the heat insulation layer is fixedly connected with an inner container of the reaction kettle, the inner container of the reaction kettle is fixedly connected with an air inlet, the air inlet is movably connected with a valve, the valve is movably connected with an air pump interface, a lower stirring device is fixedly connected below the inner container of the reaction kettle, the lower stirring device is movably connected with a lower stirring fan, the upper part of the inner container of the reaction kettle is movably connected with a cover of the reaction kettle, an upper stirring device is fixedly connected below the cover of the reaction kettle, the lower part of the upper stirring device is movably connected with the upper stirring fan, heating is carried out to 160 ℃, stirring reaction is carried out for 30 hours at a constant speed, the solution is dried in vacuum to remove a solvent, distilled, placing the solid product in a resistance furnace, heating to 520 ℃ at the heating rate of 8 ℃/min, and carrying out heat preservation and calcination for 6h to obtain the porous nano-particlesRice Co3O4A hollow microsphere component 5.
(2) Preparation of Co3O4Carbon nanotube composite 5: adding ethanol solvent into a reaction bottle, and adding porous nano Co3O4Stirring and dissolving the hollow microsphere component 5, urea and melamine, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 60 ℃ for 2 hours, and adding ferrous chloride, wherein the porous nano Co is3O4Pouring the solution into a full-automatic reaction kettle, heating to 120 ℃, uniformly stirring for reaction for 4 hours, distilling the solution under reduced pressure to remove the solvent, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, calcining at 520 ℃ for 4 hours, washing the calcined product with distilled water, fully drying, and preparing the porous nano Co based composite material, wherein the mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 10:1:4:0.13O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4 Carbon nanotube composite 5.
(3) Preparation of phenolic resin nano-microsphere coated Co3O4And (5) component: 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 10:1, adding ammonia water to adjust the pH value of the solution to 10, and adding 18 parts of Co3O4Placing a reaction bottle in an ultrasonic disperser, carrying out ultrasonic dispersion treatment for 2h at 70 ℃, pouring the solution into a full-automatic reaction kettle, heating to 130 ℃, stirring at a constant speed for reaction for 30h, carrying out vacuum drying on the solution to remove the solvent, and preparing the phenolic resin nano microsphere coated Co composite material3O4And (5) component.
(4) Preparation of carbon-coated porous Co3O4 Negative electrode material 5 of microspherical lithium ion battery: coating phenolic resin nano-microspheres with Co3O4Placing the component 5 in an atmosphere resistance furnace, introducing nitrogen, calcining at 550 ℃ for 4h at the heating rate of 8 ℃/min, washing the calcined product with distilled water, and fully drying to prepare the carbon-coated porous Co3O4And (3) a microsphere lithium ion battery negative electrode material 5.
The carbon-coated porous Co of examples 1-5 were separately prepared3O4Adding an N-methyl pyrrolidone solvent into a lithium ion battery cathode material of the microsphere, then adding polyvinylidene fluoride and acetylene black, uniformly coating slurry on the surface of a copper foil and drying to obtain a cathode electrode material, taking a lithium sheet as a counter electrode, taking a 1mol/L solution of lithium hexafluorophosphate and diethyl carbonate as an electrolyte and dimethyl carbonate to assemble a CR2032 button battery, and testing the electrochemical performance of the cathode electrode material by using a CHI660D electrochemical workstation, wherein the test standard is GB/T36276-2018.
Figure BDA0002536447690000121
Figure BDA0002536447690000131
In summary, the carbon-coated porous Co3O4A lithium ion battery cathode material of microspheres is prepared by taking carbon nano-microspheres prepared from glucose through a hydrothermal synthesis method as sacrificial templates, citric acid as a dispersing agent and urotropine as an accelerant, and removing the carbon nano-microspheres through high-temperature thermal cracking3O4Hollow structure with nano-morphology, corresponding to common Co3O4Porous nano Co3O4The hollow microspheres have huge specific surface area, can provide more electrochemical active sites, contain rich pore junction mesoporous structures, can provide diffusion channels for lithium ions, and improve the deintercalation rate of the lithium ions.
Urea and melamine are used as a nitrogen source and a carbon source, ferrous chloride is used as a catalyst, the nitrogen-doped carbon nanotube is prepared by an in-situ polymerization method, the electronegativity of nitrogen is larger than that of carbon, the electron transfer in carbon atoms to the nitrogen atoms is promoted, the positive charge of the carbon atoms is increased, and therefore the carbon nanotube has more excellent electropositivity and conductivity, and the porous nano Co is used as a catalyst3O4The microspheres are uniformly attached to the nitrogen-doped carbon nano-tubes, so that not only can the nano Co be effectively reduced3O4The phenomenon of agglomeration and aggregation, and the nitrogen-doped carbon nanotube with excellent conductivity greatly enhances Co3O4The conductive performance of the cathode material promotes the transmission and migration of electrons, and is beneficial to the electrode reaction.
Polyol phosphate is used as dopant, and is polycondensed with m-diphenol and formaldehyde to form phosphorus doped polymer through hot solvent process to coat Co homogeneously3O4-carbon nanotube composite material, formed by high temperature thermal cracking, phosphorus doped carbon material coated Co3O4The atomic radius of the phosphorus is much larger than that of the carbon, and the phosphorus is doped into the carbon layer structure to play a role in carbon layer stripping, so that the carbon layer structure is widened, a large number of pores and mesoporous structures are formed, and Co is used as a material for preparing the carbon-based carbon material3O4During the charging and discharging process, the lithium ion is extracted and inserted, which causes Co3O4Volume expansion and structural change of (a), and the pores and mesoporous structure are Co3O4The volume expansion of (A) provides an elastic buffer, reduces the stress generated by the expansion, and thus slows down Co3O4The volume expansion and the structural change phenomena enhance the electrochemical cycle stability of the cathode material, meanwhile, the phosphorus doping can improve the wettability of the carbon material, and a large number of pores and mesoporous structures can also soak the electrolyte, so that active sites can be fully contacted with the electrolyte, thereby enhancing the electrochemical performance of the electrode material.

Claims (6)

1. Carbon-coated porous Co3O4The microsphere lithium ion battery cathode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 18-40 parts of Co3O4Carbon nanotube composite material, 20-26 parts of resorcinol, 32-40 parts of formaldehyde and 8-16 parts of polyhydric alcohol phosphate.
2. The carbon-coated porous Co of claim 13O4The microsphere lithium ion battery cathode material is characterized in that: the Co3O4The preparation method of the carbon nanotube composite material comprises the following steps:
(1) to fully automatic reactionAdding distilled water solvent and CoCl into the kettle2Heating the dispersing agents citric acid, urotropine and glucose to 160 ℃ for reaction for 20-30h, removing the solvent from the solution, washing and drying the solid product, placing the solid product in a resistance furnace, heating the solid product to 520 ℃ at the heating rate of 2-8 ℃/min, keeping the temperature and calcining for 4-6h, and obtaining the porous nano Co3O4Hollow microspheres.
(2) Adding porous nano Co into ethanol solvent3O4Stirring and dissolving hollow microspheres, urea and melamine, performing ultrasonic dispersion treatment on the solution at 40-60 ℃ for 1-2h, adding ferrous chloride, pouring the solution into a full-automatic reaction kettle, heating to 80-120 ℃, reacting for 2-4h, removing the solvent from the solution, drying, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 1-5 ℃/min, calcining at the temperature of 480-520 ℃ for 2-4h, washing the calcined product with distilled water, and fully drying to prepare the porous nano Co-based catalyst3O4The hollow microsphere is loaded with nitrogen-doped carbon nano-tubes, namely Co3O4-carbon nanotube composites.
3. The carbon-coated porous Co of claim 23O4The microsphere lithium ion battery cathode material is characterized in that: full-automatic reation kettle includes the cauldron body, the external fixedly connected with heat preservation of cauldron, inside and reation kettle inner bag fixed connection of heat preservation, reation kettle inner bag and air inlet fixed connection, air inlet and valve swing joint, valve swing joint has the air pump interface, agitating unit under the reation kettle inner bag below fixedly connected with, agitating unit and stirring fan piece active link down, reation kettle inner bag top and reation kettle lid swing joint, agitating unit on the fixedly connected with of reation kettle lid below, go up agitating unit below and last stirring fan piece swing joint.
4. The carbon-coated porous Co of claim 23O4The microsphere lithium ion battery cathode material is characterized in that: the CoCl2The mass ratio of the citric acid to the urotropine to the glucose is 1:8-12:2-4: 4-6.
5. The carbon-coated porous Co of claim 23O4The microsphere lithium ion battery cathode material is characterized in that: the porous nano Co3O4The mass ratio of the hollow microspheres to the urea to the melamine to the ferrous chloride is 6-10:1:2-4: 0.04-0.1.
6. The carbon-coated porous Co of claim 13O4The microsphere lithium ion battery cathode material is characterized in that: the carbon-coated porous Co3O4The microsphere lithium ion battery cathode material.
(1) Adding ammonia water into a mixed solvent of distilled water and ethanol with the volume ratio of 6-10:1 to adjust the pH of the solution to 8-10, and adding 18-40 parts of Co3O4Carrying out ultrasonic dispersion treatment on the solution at 40-70 ℃ for 1-2h, pouring the solution into a full-automatic reaction kettle, heating to 100-130 ℃, reacting for 25-30h, removing the solvent from the solution, and preparing the phenolic resin nano microsphere coated Co nano microsphere3O4；
(2) Coating phenolic resin nano-microspheres with Co3O4Placing the mixture in an atmosphere resistance furnace, introducing nitrogen, calcining the mixture for 2 to 4 hours at the temperature of 500-550 ℃ at the temperature rise rate of 2 to 8 ℃/min, washing the calcined product by using distilled water, and fully drying the calcined product to prepare the carbon-coated porous Co3O4The microsphere lithium ion battery cathode material.
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