CN112707381A - Preparation method and application of nitrogen-rich hollow carbon sphere modified graphene positive electrode active material - Google Patents
Preparation method and application of nitrogen-rich hollow carbon sphere modified graphene positive electrode active material Download PDFInfo
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Abstract
The invention relates to the technical field of lithium-sulfur batteries, and discloses a positive active material of nitrogen-enriched hollow carbon sphere modified graphene, which takes 1,2, 3-triazole functional groups with high nitrogen content generated by alkynyl-azido reaction as a nitrogen source, and leads phenolic resin hollow microspheres to form nitrogen-enriched porous hollow carbon microspheres through potassium hydroxide high-temperature carbonization and activation, the graphene is highly distributed in pores and hollow structures of the porous hollow carbon microspheres, the unique hollow and three-dimensional hierarchical structure of the pores has good physical space confinement effect on elemental sulfur and lithium polysulfide, active sites generated by nitrogen doping are beneficial to chemical adsorption on the lithium polysulfide, the shuttle effect influence is reduced, the coating layer of the three-dimensional hierarchical structure relieves the volume expansion effect of the elemental sulfur, the capacity is prevented from being rapidly attenuated, the nitrogen-enriched porous hollow carbon microspheres modified graphene has excellent conductivity, is beneficial to promoting the transmission and migration of electrons.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a preparation method and application of a nitrogen-rich hollow carbon sphere modified graphene anode active material.
Background
Compared with the traditional lithium battery, the lithium sulfur battery takes elemental sulfur as a positive active material, the electrochemical mechanism of the lithium sulfur battery is that when discharging, lithium in the negative electrode reaction loses electrons to form lithium ions, the positive electrode reaction is that the elemental sulfur reacts with the lithium ions and the electrons to generate lithium polysulfide, the positive electrode and the negative electrode reaction generates a potential difference which is the discharge voltage of the lithium sulfur battery, the elemental sulfur has rich storage capacity, low cost, easy availability and environmental friendliness, and the theoretical specific capacity and the theoretical specific energy of the lithium sulfur battery are much higher than those of commercial lithium batteries, so the lithium sulfur battery is a lithium battery with a huge development prospect.
However, the current lithium sulfur battery is still in the research stage, and the reason that the current lithium sulfur battery is difficult to be commercially applied is that elemental sulfur in the positive electrode is easy to generate volume expansion in the continuous charging and discharging process, which leads to the loss and collapse of the positive electrode matrix structure, so that the capacity is quickly attenuated, and the cycling stability of the positive electrode material is affected, meanwhile, lithium polysulfide generated by the positive electrode reaction is easy to dissolve into the electrolyte, so that a shuttle effect is formed, which leads to the loss of positive electrode active sulfur and the attenuation of electric energy and capacity, and the conductivity of elemental sulfur is poor, which is not beneficial to the transmission and migration of electrons in the positive electrode reaction process, and affects the rate capability of the lithium sulfur battery, so that the development of a novel high-efficiency lithium sulfur battery positive electrode active material becomes a research.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of a nitrogen-rich hollow carbon sphere modified graphene anode active material, and solves the problem of poor electrochemical performance of a sulfur anode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the nitrogen-rich hollow carbon sphere modified graphene anode active material comprises the following steps:
(1) adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 12-24h at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt into an ethanol solvent, reacting for 4-8h in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with alkynyl-containing side chains.
(3) Adding phenolic resin hollow microspheres with alkynyl-containing side chains, azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, reacting at room temperature for 20-40h, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, and placing a mixed product in an atmosphere furnace for high-temperature calcination to obtain nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing the nitrogen-rich hollow carbon microsphere modified graphene and the sublimed sulfur, placing the mixture in a reaction kettle, carrying out melt reaction for 10-20h at the temperature of 150-160 ℃, and cooling to obtain the nitrogen-rich hollow carbon microsphere modified graphene anode active material which is applied to the lithium-sulfur battery anode material.
Preferably, the mass ratio of the phenolic resin hollow microspheres to the m-ethynyl phenyl diazonium salt in the step (2) is 100: 60-120.
Preferably, the mass ratio of the phenolic resin hollow microspheres with alkynyl-containing side chains in the step (3), the azide functionalized graphene, the cuprous bromide and the diethylenetriamine is 8-15:100:0.02-0.05: 0.03-0.08.
Preferably, the mass ratio of the phenolic resin hollow microsphere crosslinked graphene to the potassium hydroxide in the step (4) is 10: 15-35.
Preferably, the high-temperature calcination in the step (4) is performed in a nitrogen atmosphere and is performed at 700-800 ℃ for 2-3 h.
Preferably, the mass ratio of the nitrogen-enriched hollow carbon microsphere modified graphene to the sublimed sulfur in the step (5) is 25-35: 100.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical experiment principle and beneficial technical effects:
based on a click reaction mechanism of alkyne-azide 1, 3-dipolar cycloaddition, under coordination and catalysis of cuprous bromide and diethylenetriamine, side chain alkynyl of the phenolic resin hollow microsphere and azide groups of graphene are subjected to efficient click reaction to obtain the phenolic resin hollow microsphere crosslinked graphene, and the graphene is uniformly dispersed in a matrix of the phenolic resin hollow microsphere through modification of chemical bonds, so that the agglomeration phenomenon of the graphene is reduced.
The positive active material of the nitrogen-rich hollow carbon sphere modified graphene takes 1,2, 3-triazole functional groups with high nitrogen content generated by alkynyl-azido reaction as nitrogen sources, and through high-temperature carbonization and activation of potassium hydroxide, phenolic resin hollow microspheres form nitrogen-rich porous hollow carbon microspheres with good appearance, and the graphene is highly distributed in pores and hollow structures of the porous hollow carbon microspheres, so that the agglomeration of the graphene is inhibited, the nitrogen-rich porous hollow carbon microspheres modify the graphene to form unique hollow and pore three-dimensional hierarchical structures, so that the positive active material has good physical space confinement effect on elemental sulfur and polysulfide lithium, active sites generated by nitrogen doping are favorable for improving the chemical adsorption of the porous hollow carbon microspheres on lithium polysulfide, thereby reducing the influence of shuttle effect, and the three-dimensional hierarchical structures formed by the hollow and the pores can well coat the elemental sulfur, the coating layer relieves the volume expansion effect of elemental sulfur, the stability of the matrix structure of the anode material is improved, the rapid capacity attenuation is avoided, the actual specific capacity and the cycling stability of the battery are enhanced, the nitrogen-rich porous hollow carbon microsphere modified graphene has excellent conductive performance, a three-dimensional conductive coating layer network is formed, when the anode of the lithium-sulfur battery is prepared, the conductive performance of the anode material can be greatly improved without adding traditional carbon black, acetylene black and other conductive agents, the promotion of the transmission and the migration of electrons is facilitated, and the multiplying power performance is improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a nitrogen-rich hollow carbon sphere modified graphene anode active material is prepared by the following steps:
(1) adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 12-24h at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, phenolic resin hollow microspheres and m-ethynylphenyl diazonium salt in a mass ratio of 100:60-120 into an ethanol solvent, reacting for 4-8h in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with alkynyl on side chains.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains, azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, reacting at room temperature for 20-40h, adding distilled water to precipitate, filtering and washing to obtain the phenolic resin hollow microsphere crosslinked graphene, wherein the mass ratio of the four substances is 8-15:100:0.02-0.05: 0.03-0.08.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 10:15-35 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing the mixed product in an atmosphere furnace, calcining at the high temperature of 800 ℃ for 2-3h in a nitrogen atmosphere, and obtaining the nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-rich hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 25-35:100, placing the mixture in a reaction kettle, carrying out melt reaction for 10-20h at the temperature of 150-160 ℃, and cooling to obtain the nitrogen-rich hollow carbon microsphere modified graphene anode active material applied to the lithium-sulfur battery anode material.
Example 1
(1) Adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 12h at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt in a mass ratio of 100:60 into an ethanol solvent, reacting for 4 hours in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with side chains containing alkynyl.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains, azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, reacting at room temperature for 20h, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene, wherein the mass ratio of the four substances is 8:100:0.02: 0.03.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 10:15 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing a mixed product in an atmosphere furnace, calcining at a high temperature of 700 ℃ for 2 hours in a nitrogen atmosphere, and thus obtaining the nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-enriched hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 25:100, placing the mixture in a reaction kettle, carrying out melt reaction for 10 hours at the temperature of 150 ℃, and cooling to obtain the nitrogen-enriched hollow carbon microsphere modified graphene anode active material.
Example 2
(1) Adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 18h at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt in a mass ratio of 100:80 into an ethanol solvent, reacting for 8 hours in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with side chains containing alkynyl.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains and azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, reacting for 40h at room temperature, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene, wherein the mass ratio of the four substances is 15:100:0.04: 0.05.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 1:2 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing the mixed product in an atmosphere furnace, calcining at 800 ℃ for 2.5 hours in a nitrogen atmosphere, and thus obtaining the nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-enriched hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 30:100, placing the mixture in a reaction kettle, carrying out melt reaction for 20 hours at 155 ℃, and cooling to obtain the nitrogen-enriched hollow carbon microsphere modified graphene anode active material.
Example 3
(1) Adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 18h at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt in a mass ratio of 100:120 into an ethanol solvent, reacting for 8 hours in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with side chains containing alkynyl.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains and azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, wherein the mass ratio of the four substances is 15:100:0.05:0.08, reacting for 40 hours at room temperature, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 10:35 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing a mixed product in an atmosphere furnace, calcining at 800 ℃ for 3h in a nitrogen atmosphere, and obtaining the nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-enriched hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 35:100, placing the mixture in a reaction kettle, carrying out melt reaction for 20 hours at 160 ℃, and cooling to obtain the nitrogen-enriched hollow carbon microsphere modified graphene anode active material.
Comparative example 1
(1) Adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 24 hours at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt in a mass ratio of 100:40 into an ethanol solvent, reacting for 6 hours in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with side chains containing alkynyl.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains and azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, reacting for 40h at room temperature, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene, wherein the mass ratio of the four substances is 6:100:0.01: 0.015.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 1:1 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing a mixed product in an atmosphere furnace, calcining at 800 ℃ for 2h in a nitrogen atmosphere, and obtaining the nitrogen-enriched hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-enriched hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 20:100, placing the mixture in a reaction kettle, carrying out melt reaction for 20 hours at the temperature of 150 ℃, and cooling to obtain the nitrogen-enriched hollow carbon microsphere modified graphene anode active material.
Comparative example 2
(1) Adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, reacting for 24 hours at room temperature, centrifugally separating to remove the solvent, and washing with distilled water and ethanol to obtain azide functionalized graphene.
(2) Adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt in a mass ratio of 100:180 into an ethanol solvent, reacting for 6 hours in an ice bath, dropwise adding dilute hydrochloric acid until a large amount of precipitates are separated out, filtering and washing to obtain the phenolic resin hollow microspheres with side chains containing alkynyl.
(3) Adding phenolic resin hollow microspheres with alkynyl side chains and azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, wherein the mass ratio of the four substances is 18:100:0.065:0.1, reacting for 30 hours at room temperature, adding distilled water to precipitate, performing suction filtration and washing to obtain the phenolic resin hollow microsphere crosslinked graphene.
(4) Dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a mass ratio of 10:45 in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, placing the mixed product in an atmosphere furnace, calcining at the high temperature of 750 ℃ for 2.5 hours in a nitrogen atmosphere, and thus obtaining the nitrogen-rich hollow carbon microsphere modified graphene.
(5) Uniformly mixing nitrogen-enriched hollow carbon microsphere modified graphene and sublimed sulfur in a mass ratio of 40:100, placing the mixture in a reaction kettle, carrying out melt reaction for 15 hours at 160 ℃, and cooling to obtain the nitrogen-enriched hollow carbon microsphere modified graphene anode active material.
Uniformly mixing a positive active material of nitrogen-enriched hollow carbon sphere modified graphene, a binding agent polyvinylidene fluoride and N-methylpyrrolidone, coating the mixture on the surface of an aluminum foil, drying, cutting and tabletting to obtain a lithium-sulfur battery positive material, assembling a CR2025 button battery in a glove box by using a lithium sheet as a negative electrode, a Celgard porous membrane as a diaphragm and 1mol/L lithium bistrifluoromethanesulfonylimide solution as an electrolyte, performing cyclic voltammetry test by using a CHI760E electrochemical workstation, and performing constant current charge and discharge test in a CT-4008 battery test system.
Claims (6)
1. A positive active material of nitrogen-rich hollow carbon sphere modified graphene is characterized in that: the preparation method of the nitrogen-enriched hollow carbon sphere modified graphene anode active material comprises the following steps:
(1) adding aminated graphene, 5-azido valeric acid and a condensing agent O-benzotriazole-tetramethylurea hexafluorophosphate into a dimethyl sulfoxide solvent, and reacting to obtain azide functionalized graphene;
(2) adding a sodium hydroxide solution, the phenolic resin hollow microspheres and m-ethynyl phenyl diazonium salt into an ethanol solvent, and reacting for 4-8h in an ice bath to obtain the phenolic resin hollow microspheres with alkynyl-containing side chains;
(3) adding phenolic resin hollow microspheres with alkynyl side chains and azide functionalized graphene, cuprous bromide and diethylenetriamine into an N, N-dimethylformamide solution, and reacting at room temperature for 20-40h to obtain phenolic resin hollow microsphere crosslinked graphene;
(4) dissolving phenolic resin hollow microsphere crosslinked graphene and potassium hydroxide in a distilled water solvent, performing ultrasonic dispersion uniformly, performing vacuum drying, and placing a mixed product in an atmosphere furnace for high-temperature calcination to obtain nitrogen-enriched hollow carbon microsphere modified graphene;
(5) uniformly mixing the nitrogen-rich hollow carbon microsphere modified graphene and the sublimed sulfur, placing the mixture in a reaction kettle, carrying out melt reaction for 10-20h at the temperature of 150-160 ℃, and cooling to obtain the nitrogen-rich hollow carbon microsphere modified graphene anode active material which is applied to the lithium-sulfur battery anode material.
2. The positive active material of nitrogen-enriched hollow carbon sphere modified graphene according to claim 1, wherein: the mass ratio of the phenolic resin hollow microspheres to the m-ethynyl phenyl diazonium salt in the step (2) is 100: 60-120.
3. The positive active material of nitrogen-enriched hollow carbon sphere modified graphene according to claim 1, wherein: the mass ratio of the phenolic resin hollow microspheres with alkynyl-containing side chains in the step (3), the azide functionalized graphene, the cuprous bromide and the diethylenetriamine is 8-15:100:0.02-0.05: 0.03-0.08.
4. The positive active material of nitrogen-enriched hollow carbon sphere modified graphene according to claim 1, wherein: the mass ratio of the phenolic resin hollow microsphere crosslinked graphene to the potassium hydroxide in the step (4) is 10: 15-35.
5. The positive active material of nitrogen-enriched hollow carbon sphere modified graphene according to claim 1, wherein: the high-temperature calcination in the step (4) is performed in a nitrogen atmosphere and is performed for 2-3h at the temperature of 700-800 ℃.
6. The positive active material of nitrogen-enriched hollow carbon sphere modified graphene according to claim 1, wherein: the mass ratio of the nitrogen-enriched hollow carbon microsphere modified graphene to the sublimed sulfur in the step (5) is 25-35: 100.
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