CN112615002A - Flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material and preparation method thereof - Google Patents

Flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material and preparation method thereof Download PDF

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CN112615002A
CN112615002A CN202011488103.9A CN202011488103A CN112615002A CN 112615002 A CN112615002 A CN 112615002A CN 202011488103 A CN202011488103 A CN 202011488103A CN 112615002 A CN112615002 A CN 112615002A
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熊红梅
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Abstract

The invention relates to the technical field of lithium ion batteries, and discloses flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material, flower-like nano Fe-doped ZnCo2O4Has higher intrinsic conductivity and lithium ion diffusion coefficient and larger specific surface area, and N, P co-doped graphene and flower-shaped nano Fe-doped ZnCo2O4The composite material is used as a lithium ion battery cathode active material, the N doping can adjust the electronic arrangement of graphene, the electrochemical performance of the graphene is improved, and the N-doped pyridineThe nitrogen structure can improve the lithium storage capacity of the graphene, the P is doped in the graphene carbon layer to form structural defects, the lamellar spacing of the graphene is widened, the specific surface area is improved, and flower-shaped nano Fe is doped with ZnCo2O4Under the coating effect of N, P codoped graphene, the volume expansion is effectively relieved, the rapid capacity attenuation is avoided, and flower-shaped nano Fe is doped with ZnCo2O4The graphene-loaded negative electrode material has excellent actual specific capacity and cycling stability.

Description

Flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to flower-shaped nano Fe-doped ZnCo2O4A graphene-loaded negative electrode material and a preparation method thereof.
Background
Compared with the traditional nickel-hydrogen battery and lead-acid battery, the lithium ion battery has the advantages of large energy density, high output voltage, long service life, relatively low manufacturing cost and the like, so that the lithium ion battery has important application in the field of energy storage, such as mobile phones, notebook computers, electric automobiles, aerospace and the like.
Transition metal oxides such as Fe3O4、Co3O4、NiCo2O4、ZnCo2O4The material has high theoretical specific capacity, rich source, low cost and easy obtaining, is widely researched in lithium ion battery cathode materials, is a cathode active material with great development prospect, but is ZnCo2O4The intrinsic conductivity and the ion diffusion coefficient are low, the transmission of charges and lithium ions is not facilitated, the rate capability and the actual specific capacity of the negative electrode material are influenced, and ZnCo2O4The negative electrode material can generate serious volume expansion in the lithium ion de-intercalation process, so that the negative electrode material is pulverized and agglomerated, the matrix structure is collapsed, and the cycle performance of the negative electrode material is reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a flower-shaped nano Fe-doped ZnCo2O4The graphene-loaded negative electrode material and the preparation method solve the problem of ZnCo2O4The rate capability and the actual specific capacity of the cathode material are not high, and the cycle performance is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material, and flower-like nano Fe doped ZnCo2O4The preparation method of the graphene-loaded negative electrode material comprises the following steps:
(1) adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea, stirring at a constant speed for 1-2h, placing the reaction bottle in a microwave reaction device, heating to 130 ℃ and 150 ℃, reacting for 30-60min, removing the solvent by suction filtration, washing with deionized water and ethanol, and drying to obtain the flower-shaped nano Fe-doped ZnCo2O4Fe doped ZnCo2O4Molecular formula of (1) is ZnFe0.15-0.35Co1.65-1.85O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10-11, adding ethylenediamine, heating to 90-110 ℃ in a nitrogen atmosphere, carrying out reflux reaction for 12-24h, filtering to remove a solvent, washing with deionized water and ethanol, and drying to prepare the amino functionalized graphene.
(3) Adding an ether solvent, amino functionalized graphene, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 12-24h in an ice water bath, adding an ethanol solvent, stirring and reacting for 24-48h at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain the cyclotriphosphazene functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment to prepare the N and P co-doped graphene.
(5) Adding deionized water, N, P co-doped graphene and flower-shaped nano Fe-doped ZnCo into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating the solution to 160-180 ℃, reacting for 6-12h, filtering and removing the solvent to prepare the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And the graphene-loaded lithium ion battery negative electrode material.
Preferably, the mass ratio of the zinc nitrate, the cobalt nitrate, the ferric nitrate and the urea in the step (1) is 1:1.65-1.85:0.15-0.35: 12-15.
Preferably, the microwave reaction device in the step (1) comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, a reaction bottle is arranged above the base, a sliding block is movably connected inside the base, and a moving plate is movably connected with the sliding block.
Preferably, the mass ratio of the graphene oxide to the ethylenediamine in the step (2) is 100: 25-60.
Preferably, the mass ratio of the amino functionalized graphene, the hexachlorocyclotriphosphazene and the pyridine in the step (3) is 10:80-120: 200-300.
Preferably, the high-temperature heat treatment in the step (4) is performed in a nitrogen atmosphere and is performed for 2-3h at 800-900 deg.C.
Preferably, in the step (5), N, P codoped graphene and flower-shaped nano Fe are doped with ZnCo2O4The mass ratio of (A) to (B) is 40-80: 10.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the flower-shaped nano Fe-doped ZnCo2O4The flower-like nano Fe-doped ZnCo negative electrode material is prepared by taking urea as a precipitator and adopting a simple and efficient microwave hydrothermal method2O4Fe doping replaces part of Co crystal lattice, which is beneficial to reducing ZnCo2O4Increasing the intrinsic conductivity thereof, and Fe doped ZnCo2O4Defects are generated in the crystal, a diffusion channel is provided for lithium ion transmission, and flower-shaped nano Fe is doped with ZnCo2O4The lithium ion battery cathode material has a unique nanometer petal-shaped appearance, a large specific surface area and abundant lithium ion de-intercalation sites, so that the cathode material has excellent electronic conductivity and lithium ion diffusion coefficient, and the rate capability and the actual specific capacity are improved.
The flower-shaped nano Fe-doped ZnCo2O4Under the promoting action of an acid-binding agent pyridine, chlorine atoms of hexachlorocyclotriphosphazene and amino groups of amino-functionalized graphene undergo nucleophilic substitution reaction, unreacted chlorine atoms are substituted by ethanol to obtain cyclotriphosphazene-grafted functionalized graphene, cyclotriphosphazene groups are highly dispersed in a graphene matrix through the connection of chemical bonds, and the cyclotriphosphazene is further carbonized at high temperature to obtain N, P co-doped graphene, and then the N, P co-doped graphene and flower-shaped nano Fe-doped ZnCo2O4The composite material is used as a negative active material of a lithium ion battery, the N doping can adjust the electronic arrangement of graphene, the electrochemical performance of the graphene is improved, the N doping forms a pyridine nitrogen structure in a graphene carbon layer matrix, the pyridine nitrogen can improve the lithium storage capacity of the graphene, the P doping forms a structural defect in the graphene carbon layer, the lamellar spacing of the graphene is widened, the specific surface area is further improved, and flower-shaped nano Fe is doped with ZnCo2O4Under the coating effect of N, P codoped graphene, the phenomenon of volume expansion is effectively relieved, the rapid capacity attenuation caused by the loss of a negative electrode material matrix is avoided, and flower-shaped nano Fe is doped with ZnCo under the synergistic effect2O4The graphene-loaded negative electrode material has excellent actual specific capacity and cycling stability.
Drawings
FIG. 1 is a schematic front view of a microwave reaction apparatus;
FIG. 2 is an enlarged schematic view of the base;
FIG. 3 is a schematic view of the adjustment of the moving plate.
1-microwave reaction device; 2-a microwave emitter; 3, a motor; 4-a rotating shaft; 5-a base; 6-reaction flask; 7-a slide block; 8-moving the plate.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: flower-shaped nano Fe-doped ZnCo2O4The preparation method of the graphene-loaded negative electrode material comprises the following steps:
(1) adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, and adding zinc nitrate, cobalt nitrate, ferric nitrate and urine in a mass ratio of 1:1.65-1.85:0.15-0.35:12-15Stirring at constant speed for 1-2h, placing a reaction bottle in a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, the reaction bottle is arranged above the base, a sliding block is movably connected inside the base, the sliding block is movably connected with a moving plate, heating is carried out to 130-plus-150 ℃, reacting is carried out for 30-60min, filtering and removing a solvent, washing and drying are carried out by using deionized water and ethanol, and the flower-shaped nanometer Fe-doped ZnCo is prepared2O4Molecular formula of ZnFe0.15- 0.35Co1.65-1.85O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10-11, adding ethylenediamine, heating the solution to 90-110 ℃ in a nitrogen atmosphere at a mass ratio of 100:25-60, carrying out reflux reaction for 12-24h, filtering to remove the solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino functionalized graphene with the mass ratio of 10:80-120:200-300, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting in an ice-water bath for 12-24h, adding an ethanol solvent, stirring and reacting at room temperature for 24-48h, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to prepare the cyclotriphosphazene functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 2-3h at the temperature of 800-900 ℃ in the nitrogen atmosphere to prepare the N, P co-doped graphene.
(5) Adding deionized water, N, P co-doped graphene with mass ratio of 40-80:10 and flower-like nano Fe doped ZnCo into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating the solution to 160-180 ℃, reacting for 6-12h, filtering and removing the solvent to prepare the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And the graphene-loaded lithium ion battery negative electrode material.
Example 1
(1) Adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea with a mass ratio of 1:1.85:0.15:12, stirring at a constant speed for 1h, placing the reaction bottle into a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, the reaction bottle is arranged above the base, a sliding block is movably connected inside the base, a moving plate is movably connected with the sliding block, heating to 130 ℃, reacting for 30min, filtering to remove the solvent, washing and drying by using the deionized water and ethanol, and preparing the flower-shaped nano Fe doped ZnCo2O4Molecular formula of ZnFe0.15Co1.85O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10, adding ethylenediamine, heating the solution to 90 ℃ in a nitrogen atmosphere at a mass ratio of 100:25, carrying out reflux reaction for 12 hours, filtering to remove a solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino-functionalized graphene with a mass ratio of 10:80:200, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 12 hours in an ice water bath, adding an ethanol solvent, stirring and reacting for 24 hours at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain cyclotriphosphazene-functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 2h at 800 ℃ in a nitrogen atmosphere to prepare the N and P co-doped graphene.
(5) Adding deionized water and N, P co-doped graphene and flower-shaped graphene with the mass ratio of 40:10 into a reaction bottleNano Fe doped ZnCo2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating to 160 ℃, reacting for 6 hours, filtering to remove the solvent, and preparing the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4The graphene-loaded lithium ion battery negative electrode material 1.
Example 2
(1) Adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea with a mass ratio of 1:1.8:0.2:13, stirring at a constant speed for 2 hours, placing the reaction bottle into a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, the reaction bottle is arranged above the base, a sliding block is movably connected inside the base, a moving plate is movably connected with the sliding block, heating to 130 ℃, reacting for 60 minutes, filtering to remove the solvent, washing and drying by using the deionized water and ethanol, and preparing the flower-shaped nano Fe doped ZnCo2O4Molecular formula of ZnFe0.2Co1.8O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 11, adding ethylenediamine, heating the solution to 110 ℃ in a nitrogen atmosphere at a mass ratio of 100:35, carrying out reflux reaction for 24 hours, filtering to remove the solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino-functionalized graphene with a mass ratio of 10:95:230, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 24 hours in an ice water bath, adding an ethanol solvent, stirring and reacting for 36 hours at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain cyclotriphosphazene-functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 2h at 900 ℃ in a nitrogen atmosphere to prepare the N and P co-doped graphene.
(5) Adding deionized water, N and P co-doped graphene with the mass ratio of 50:10 and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating the solution to 180 ℃, reacting for 12 hours, filtering and removing the solvent to prepare the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And (3) a graphene-loaded lithium ion battery negative electrode material 2.
Example 3
(1) Adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea with a mass ratio of 1:1.7:0.3:14, stirring at a constant speed for 1.5h, placing the reaction bottle into a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, the reaction bottle is arranged above the base, a sliding block is movably connected inside the base, a moving plate is movably connected with the sliding block, heating is carried out to 140 ℃, reacting for 45min, filtering to remove the solvent, washing and drying by using deionized water and ethanol, and preparing the flower-shaped nano Fe-doped ZnCo2O4Molecular formula of ZnFe0.3Co1.7O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 11, adding ethylenediamine, heating the solution to 100 ℃ in a nitrogen atmosphere at a mass ratio of 100:50, carrying out reflux reaction for 18 hours, filtering to remove a solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino-functionalized graphene with a mass ratio of 10:105:260, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 18h in an ice water bath, adding an ethanol solvent, stirring and reacting for 36h at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain cyclotriphosphazene-functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 2.5h at 850 ℃ in a nitrogen atmosphere to prepare the N and P co-doped graphene.
(5) Adding deionized water, N and P co-doped graphene with the mass ratio of 65:10 and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating to 170 ℃, reacting for 10 hours, filtering to remove the solvent, and preparing the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And 3, a graphene-loaded lithium ion battery negative electrode material.
Example 4
(1) Adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea with a mass ratio of 1:1.65:0.35:15, stirring at a constant speed for 2 hours, placing the reaction bottle into a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, the reaction bottle is arranged above the base, a sliding block is movably connected inside the base, a moving plate is movably connected with the sliding block, heating to 150 ℃, reacting for 60 minutes, filtering to remove the solvent, washing and drying by using the deionized water and ethanol, and preparing the flower-shaped nano Fe doped ZnCo2O4Molecular formula of ZnFe0.35Co1.65O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 11, adding ethylenediamine, heating the solution to 110 ℃ in a nitrogen atmosphere at a mass ratio of 100:60, carrying out reflux reaction for 24 hours, filtering to remove the solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino-functionalized graphene with a mass ratio of 10:120:300, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 24 hours in an ice water bath, adding an ethanol solvent, stirring and reacting for 48 hours at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain cyclotriphosphazene-functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 3h at 900 ℃ in a nitrogen atmosphere to prepare the N and P co-doped graphene.
(5) Adding deionized water, N and P co-doped graphene with the mass ratio of 80:10 and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating the solution to 180 ℃, reacting for 12 hours, filtering and removing the solvent to prepare the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And 4, a graphene-loaded lithium ion battery negative electrode material.
Comparative example 1
(1) Adding a mixed solvent of deionized water and ethylene glycol into a reaction bottle, adding zinc nitrate, cobalt nitrate, ferric nitrate and urea in a mass ratio of 1:1.9:0.1:10, stirring at a constant speed for 2 hours, placing the reaction bottle into a microwave reaction device, wherein the microwave reaction device comprises a microwave emitter, and a motor is fixedly connected inside the microwave reaction deviceThe flower-shaped nanometer Fe-doped ZnCo is prepared by movably connecting a motor with a rotating shaft, movably connecting a base above the rotating shaft, arranging a reaction bottle above the base, movably connecting a sliding block inside the base, movably connecting the sliding block with a moving plate, heating to 130 ℃, reacting for 60min, filtering to remove a solvent, washing with deionized water and ethanol, and drying2O4Molecular formula of ZnFe0.1Co1.9O4。
(2) Adding deionized water and graphene oxide into a reaction bottle, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 11, adding ethylenediamine, heating the solution to 110 ℃ in a nitrogen atmosphere at a mass ratio of 100:15, carrying out reflux reaction for 15 hours, filtering to remove a solvent, washing with deionized water and ethanol, and drying to obtain the amino functionalized graphene.
(3) Adding an ether solvent, amino-functionalized graphene with a mass ratio of 10:60:170, hexachlorocyclotriphosphazene and pyridine into a reaction bottle, uniformly stirring and reacting for 24 hours in an ice water bath, adding an ethanol solvent, stirring and reacting for 24 hours at room temperature, carrying out reduced pressure distillation to remove the solvent, washing with deionized water and ethanol, and drying to obtain cyclotriphosphazene-functionalized graphene.
(4) And (3) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment for 3h at 860 ℃ in a nitrogen atmosphere to prepare the N and P co-doped graphene.
(5) Adding deionized water and N, P co-doped graphene and flower-like nano Fe doped ZnCo with the mass ratio of 25:10 into a reaction bottle2O4After the solution is uniformly dispersed by ultrasonic wave, pouring the solution into a reaction kettle, heating the solution to 160 ℃, reacting for 10 hours, filtering and removing the solvent to prepare the flower-shaped nano Fe-doped ZnCo2O4And loading graphene.
(6) Adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And (3) comparing the negative electrode material of the lithium ion battery loaded with graphene with 1.
The flower-shaped nano Fe in the examples and the comparative examples is doped with ZnCo2O4The graphene-loaded lithium ion battery cathode material, a lithium sheet anode material, a polypropylene diaphragm and lithium hexafluorophosphate electrolyte are assembled into a CR2025 button battery in an argon glove box, and the constant-current charge and discharge performance is detected in an Autolab PGSTAT302N type electrochemical workstation, wherein the detection standard is GB/T36276-.
Figure BDA0002839930600000101
Figure BDA0002839930600000111

Claims (7)

1. Flower-shaped nano Fe-doped ZnCo2O4The graphene-loaded negative electrode material is characterized in that: the flower-shaped nano Fe is doped with ZnCo2O4The preparation method of the graphene-loaded negative electrode material comprises the following steps:
(1) adding zinc nitrate, cobalt nitrate, ferric nitrate and urea into a mixed solvent of deionized water and ethylene glycol, stirring for 1-2h, placing in a microwave reaction device, heating to 130-150 ℃, and reacting for 30-60min to obtain the flower-shaped nano Fe-doped ZnCo2O4；
(2) Adding graphene oxide into deionized water, adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH of the solution to 10-11, adding ethylenediamine, heating to 90-110 ℃ in a nitrogen atmosphere, and carrying out reflux reaction for 12-24 hours to prepare amino functionalized graphene;
(3) adding amino functionalized graphene, hexachlorocyclotriphosphazene and pyridine into an ether solvent, reacting for 12-24h in an ice-water bath, adding an ethanol solvent, and stirring at room temperature for reacting for 24-48h to prepare cyclotriphosphazene functionalized graphene;
(4) placing cyclotriphosphazene modified graphene in an atmosphere furnace, and performing high-temperature heat treatment to prepare N, P co-doped graphene;
(5) adding N, P co-doped graphene and flower-like nano Fe doped ZnCo into deionized water2O4After the solution is uniformly dispersed by ultrasonic wave, the solution is poured into a reaction kettle and heated to 160-180 ℃ for reaction for 6-12h to prepare the flower-shaped nano Fe-doped ZnCo2O4Loading graphene;
(6) adding N-methyl pyrrolidone solvent and flower-shaped nano Fe doped ZnCo into a reaction bottle2O4Loading graphene, acetylene black and polyvinylidene fluoride, uniformly mixing, coating on the surface of foamed nickel, and drying to prepare the flower-shaped nano Fe-doped ZnCo2O4And the graphene-loaded lithium ion battery negative electrode material.
2. The flower-like nano Fe-doped ZnCo of claim 12O4The graphene-loaded negative electrode material is characterized in that: in the step (1), the mass ratio of the zinc nitrate, the cobalt nitrate, the ferric nitrate and the urea is 1:1.65-1.85:0.15-0.35:12-15, and the Fe is doped with ZnCo2O4Molecular formula of (1) is ZnFe0.15-0.35Co1.65-1.85O4。
3. The flower-like nano Fe-doped ZnCo of claim 12O4The graphene-loaded negative electrode material is characterized in that: the microwave reaction device in the step (1) comprises a microwave emitter, a motor is fixedly connected inside the microwave reaction device, the motor is movably connected with a rotating shaft, a base is movably connected above the rotating shaft, a reaction bottle is arranged above the base, a sliding block is movably connected inside the base, and a moving plate is movably connected with the sliding block.
4. The flower-like nano Fe-doped ZnCo of claim 12O4The graphene-loaded negative electrode material is characterized in that: the mass ratio of the graphene oxide to the ethylenediamine in the step (2) is 100: 25-60.
5. The flower-like nano Fe-doped ZnCo of claim 12O4Load stoneAn anode material of graphene, characterized in that: the mass ratio of the amino functionalized graphene, the hexachlorocyclotriphosphazene and the pyridine in the step (3) is 10:80-120: 200-300.
6. The flower-like nano Fe-doped ZnCo of claim 12O4The graphene-loaded negative electrode material is characterized in that: the high-temperature heat treatment in the step (4) is performed in a nitrogen atmosphere and is performed for 2-3h under 800-900.
7. The flower-like nano Fe-doped ZnCo of claim 12O4The graphene-loaded negative electrode material is characterized in that: in the step (5), N, P codoped graphene and flower-shaped nano Fe doped ZnCo2O4The mass ratio of (A) to (B) is 40-80: 10.
CN202011488103.9A 2020-12-16 2020-12-16 Flower-shaped nano Fe-doped ZnCo2O4Graphene-loaded negative electrode material and preparation method thereof Withdrawn CN112615002A (en)

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Cited By (2)

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CN114284082A (en) * 2021-12-30 2022-04-05 江西科技师范大学 Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nanosheet
CN114525551A (en) * 2022-03-24 2022-05-24 湖南祯晟炭素实业有限公司 Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114284082A (en) * 2021-12-30 2022-04-05 江西科技师范大学 Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nanosheet
CN114284082B (en) * 2021-12-30 2023-04-28 江西科技师范大学 Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nano-sheet
CN114525551A (en) * 2022-03-24 2022-05-24 湖南祯晟炭素实业有限公司 Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding
CN114525551B (en) * 2022-03-24 2022-10-11 湖南祯晟炭素实业有限公司 Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding

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