CN112960699A - Heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4Electrode material and method for producing the same - Google Patents

Heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4Electrode material and method for producing the same Download PDF

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CN112960699A
CN112960699A CN202110212823.0A CN202110212823A CN112960699A CN 112960699 A CN112960699 A CN 112960699A CN 202110212823 A CN202110212823 A CN 202110212823A CN 112960699 A CN112960699 A CN 112960699A
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王海岭
李晓梅
田利英
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Yinuoxin Electric Shenzhen Co ltd
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Abstract

The invention relates to the technical field of super capacitors and discloses heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4[2,2 'of an electrode material of']Reacting-dithiophene-5, 5' -dicarbaldehyde with chitosan and serving as a cross-linking agent to generate a thiophene cross-linked chitosan derivative, activating the thiophene cross-linked chitosan derivative by using potassium hydroxide and carbonizing the thiophene cross-linked chitosan derivative at high temperature to obtain a nitrogen and sulfur double-doped porous carbon material, introducing active structures such as pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and pyridine nitrogen into the nitrogen doping, increasing the specific surface area of the porous carbon material by the sulfur doping, and synthesizing the flower-ball-shaped Fe by a hydrothermal method3O4In the process, firstly, ferroferric oxide crystal nuclei are generated and gradually grow into nanosheets, and the ferroferric oxide nanoflower is finally assembled, wherein a nitrogen and sulfur double-doped porous carbon material is used as a matrix, and flower-shaped spherical Fe3O4The nano ferroferric oxide grows in the pore channel structure in situ, and the volume expansion phenomenon of the nano ferroferric oxide is slowed down, so that the circulation stability and the rate capability of the nano ferroferric oxide electrode material are effectively improved.

Description

Heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4Electrode material and method for producing the same
Technical Field
The invention relates to the technical field of super capacitors, in particular to heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4The electrode material and the manufacturing method.
Background
Since the twentieth century, problems of energy consumption and environmental pollution have become more serious, and people are trying to develop and use novel energy to alleviate the speed of energy exhaustion and environmental pollution, and therefore, energy storage and conversion devices such as solar cells, lithium ion batteries, and supercapacitors have come into force, and among various energy storage and conversion devices, supercapacitors have received a great deal of attention due to the advantages of high energy density, high power density, and fast charge and discharge rates, and are gradually put into production and use.
The nano ferroferric oxide is one of transition metal oxides, has the advantages of no toxicity, low cost, large theoretical capacity, strong chemical stability and the like, has relatively wide application in the fields of magnets, pigments, telecommunication devices and the like, and researchers find that the nano ferroferric oxide has wide application prospect in the field of electrode materials along with the rapid development of the supercapacitor industry in recent years, but the nano ferroferric oxide as the electrode material has the problems of poor conductivity, low stability and poor cycle stability and rate capability caused by volume expansion in the continuous charging and discharging process, so the improvement of the nano ferroferric oxide is needed, on one hand, the nano ferroferric oxide can be started from the appearance of the nano ferroferric oxide, the surface electrochemical active sites of the nano ferroferric oxide are increased by improving the specific surface area of the nano ferroferric oxide, on the other hand, the nano ferroferric oxide can be compounded with a porous carbon material with stronger conductivity, the composite super capacitor electrode material is formed, and the electrochemical activity of the nano ferroferric oxide can be effectively improved.
The porous carbon material has a large specific surface area, and is widely applied to the fields of adsorption, catalysis, carriers and the like, however, most of the raw materials of the traditional porous carbon material depend on fossil energy, so that environmental pollution is caused, meanwhile, a certain resource waste phenomenon also exists, the biomass such as cellulose, chitosan and the like has the advantages of wide sources, low price and the like, and the biomass is gradually applied to the field of preparing the porous carbon material in recent years and is further applied to electrode materials of energy conversion devices such as lithium ion batteries, super capacitors and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4The electrode material and the preparation method solve the problem of poor electrochemical activity of the nano ferroferric oxide.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4The heteroatom doped porous carbon supported flower-like Fe3O4The preparation method of the electrode material comprises the following steps:
(1) reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:6-8 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, transferring into an oil bath pot, raising the temperature to perform Schiff base crosslinking reaction, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene crosslinked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature for pre-carbonization, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, uniformly mixing, evaporating the solvent, transferring the solvent into the tubular furnace for activation and hole making, filtering a product, repeatedly washing the product with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol into a three-necked bottle, ultrasonically stirring for 20-40min, transferring into a reaction kettle, placing into an oven, raising the temperature to perform hydrothermal reaction, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Preferably, the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarbaldehyde in the step (2) is 100: 140-320.
Preferably, the temperature of the Schiff base crosslinking reaction in the step (2) is 30-50 ℃, and the reaction is carried out for 6-12h under the constant-temperature stirring in the nitrogen atmosphere.
Preferably, the temperature of the pre-carbonization in the step (3) is 350-450 ℃, and the pre-carbonization is carried out for 2-3h in a nitrogen atmosphere.
Preferably, the mass ratio of the thiophene crosslinked chitosan derivative to the potassium hydroxide in the step (3) is 100: 40-80.
Preferably, the temperature for activating and preparing the holes in the step (3) is 750-850 ℃, and the holes are prepared for 2-3h in an argon atmosphere.
Preferably, the mass ratio of the nitrogen to the sulfur double-doped porous carbon material, the potassium ferricyanide and the glycerol in the step (4) is 100:180-240: 650-820.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 170-190 ℃, and the time is 10-20 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4[2,2 'of an electrode material of']The aldehyde group in dithiophene-5, 5' -dicarbaldehyde can perform Schiff base crosslinking reaction with the amino group in chitosan and act as a crosslinking agent to generate a thiophene crosslinked chitosan derivative, the chitosan serves as a carbon source and a nitrogen source, the thiophene serves as a sulfur source, and the thiophene is subjected to high-temperature pre-carbonization, potassium hydroxide activation and high-temperature carbonization to finally obtain a nitrogen and sulfur double-doped porous carbon material, the porous carbon material matrix contains a large number of pore channel structures, so that the carbon material provides a large specific surface area, the surface electrochemical active site and the contact area with electrolyte are increased, the electrolyte diffusion channel is shortened, the reaction is accelerated, pyridine nitrogen, pyrrole nitrogen, graphite nitrogen, pyridine nitrogen and other active structures capable of improving the electrochemical performance of the porous carbon material are introduced into the porous carbon material during nitrogen doping, wherein the pyrrole nitrogen can increase the wettability of the porous carbon material, the penetration speed of electrolyte is accelerated, the introduction of graphite nitrogen can improve the conductivity of the porous carbon material, the atomic radius of sulfur is far greater than that of carbon, the interlayer spacing of the porous carbon material is effectively enlarged, the specific surface area of the porous carbon material is further improved, more electrochemical active sites are exposed, and the electrochemical activity of the porous carbon material is further improved by introducing heteroatoms such as nitrogen and sulfur into the porous carbon material, so that the application of the porous carbon material in the field of electrode materials of supercapacitors is expanded.
The heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4Electrode material of (1), hydrothermal synthesis of hollow Fe3O4During the process of microsphere, potassium ferricyanide is decomposed to gradually generate tetraoxideForming ferroferric oxide nano-sheets by the gradual growth of the ferroferric oxide crystal nucleus, and gradually assembling the ferroferric oxide nano-sheets into the ferroferric oxide nano-flower under the action of a surfactant, namely glycerol, wherein the flower-shaped Fe nano-flower is spherical3O4Has larger specific surface area, is beneficial to exposing more electrochemical active sites on the surface of the nano ferroferric oxide, improves the electrochemical activity of the nano ferroferric oxide to a certain extent, and takes a nitrogen and sulfur double-doped porous carbon material as a matrix and flower-ball-shaped Fe3O4The nano ferroferric oxide grows in an abundant pore structure in situ, so that the phenomena of accumulation and sedimentation of the nano ferroferric oxide are avoided, and the phenomenon of volume expansion of the nano ferroferric oxide in the continuous charging and discharging process can be relieved, thereby effectively improving the cycle stability and the rate capability of the nano ferroferric oxide electrode material.
Drawings
FIG. 1 is a reaction mechanism diagram of chitosan and [2,2'] -dithiophene-5, 5' -dicarbaldehyde.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4The preparation method of the electrode material comprises the following steps:
(1) reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:6-8 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarbaldehyde in a mass ratio of 100:140 and 320, transferring the mixture into an oil bath kettle, raising the temperature to 30-50 ℃, stirring and reacting at constant temperature in a nitrogen atmosphere for 6-12h, and performing suction filtration, washing and drying after the reaction is finished to obtain a thiophene crosslinked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 350-450 ℃, pre-carbonizing for 2-3h in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, wherein the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide is 100:40-80, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at the constant temperature of 750-850 ℃ in an argon atmosphere for reaction for 2-3h, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen-sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, nitrogen and sulfur double-doped porous carbon material with the mass ratio of 100:180-3O4The electrode material of (1).
Example 1
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:6 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarbaldehyde in a mass ratio of 100:140, transferring the mixture into an oil bath pot, raising the temperature to 30 ℃, stirring and reacting at constant temperature in a nitrogen atmosphere for 6 hours, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain a thiophene crosslinked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 350 ℃, pre-carbonizing for 2 hours in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at the constant temperature of 750 ℃ in an argon atmosphere for reacting for 2 hours, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:180:650 into a three-necked bottle, ultrasonically stirring for 20min, transferring into a reaction kettle, placing into an oven, reacting for 10h at 170 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Example 2
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:7 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, wherein the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarboxaldehyde is 100:200, transferring into an oil bath pot, raising the temperature to 35 ℃, stirring and reacting at constant temperature in a nitrogen atmosphere for 8 hours, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene cross-linked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 380 ℃, pre-carbonizing for 2.5 hours in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, wherein the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide is 100:52, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at the constant temperature of 780 ℃ in an argon atmosphere for reacting for 2.5 hours, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:200:700 into a three-necked bottle, ultrasonically stirring for 25min, transferring into a reaction kettle, placing into an oven, reacting for 14h at 175 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Example 3
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:7 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, wherein the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarboxaldehyde is 100:260, transferring into an oil bath pot, raising the temperature to 30 ℃, stirring and reacting at constant temperature for 10 hours in a nitrogen atmosphere, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene cross-linked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 400 ℃, pre-carbonizing for 2.5 hours in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, wherein the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide is 100:66, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace to perform activation and hole making, stirring at the constant temperature of 800 ℃ in an argon atmosphere for reacting for 2.5 hours, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:220:760 into a three-necked bottle, ultrasonically stirring for 30min, transferring into a reaction kettle, placing into an oven, reacting for 18h at 180 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Example 4
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:8 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, wherein the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarboxaldehyde is 100:320, transferring into an oil bath pot, raising the temperature to 50 ℃, stirring and reacting at constant temperature in a nitrogen atmosphere for 12 hours, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene cross-linked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 450 ℃, pre-carbonizing for 3 hours in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, wherein the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide is 100:80, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at constant temperature of 850 ℃ in an argon atmosphere for reaction for 3 hours, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen-sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:240:820 into a three-necked bottle, ultrasonically stirring for 40min, transferring into a reaction kettle, placing into an oven, reacting for 20h at 190 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Comparative example 1
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:6 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, wherein the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarboxaldehyde is 100:60, transferring into an oil bath pot, raising the temperature to 30 ℃, stirring and reacting at constant temperature for 5 hours in a nitrogen atmosphere, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain the thiophene cross-linked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 350 ℃, pre-carbonizing for 1h in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, wherein the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide is 100:28, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at the constant temperature of 750 ℃ in an argon atmosphere for reacting for 1h, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:160:600 into a three-necked bottle, ultrasonically stirring for 10min, transferring into a reaction kettle, placing into an oven, reacting for 8h at 170 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Comparative example 2
(1) Reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding a mixed solvent of isopropanol and deionized water and chitosan in a volume ratio of 10:8 into a three-necked bottle, stirring and mixing uniformly, then continuously adding [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, wherein the mass ratio of the chitosan to the [2,2'] -dithiophene-5, 5' -dicarboxaldehyde is 100:380, transferring into an oil bath pot, raising the temperature to 50 ℃, stirring and reacting at constant temperature in a nitrogen atmosphere for 15 hours, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene cross-linked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature to 450 ℃, pre-carbonizing for 4 hours in a nitrogen atmosphere, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, uniformly mixing, evaporating the solvent, transferring the mixture into the tubular furnace for activation and hole making, stirring at constant temperature of 850 ℃ in an argon atmosphere for reacting for 4 hours, filtering a product, repeatedly washing with hydrochloric acid and deionized water, and drying to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a deionized water solvent, a nitrogen and sulfur double-doped porous carbon material, potassium ferricyanide and glycerol in a mass ratio of 100:260:880 into a three-necked bottle, ultrasonically stirring for 50min, transferring into a reaction kettle, placing into an oven, reacting for 24h at 190 ℃, cooling a product, centrifuging, repeatedly washing with ethanol and deionized water, and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
Adding prepared heteroatom doped porous carbon loaded hollow Fe with the mass ratio of 75:15:10 into 1-methyl-2-pyrrolidone solvent3O4Uniformly mixing electrode materials of microspheres, acetylene black and polyvinylidene fluoride, uniformly coating the electrode materials on foamed nickel of 1cm multiplied by 1cm, putting the foamed nickel into an oven for drying, sealing and standing the foamed nickel serving as a working electrode, a saturated calomel electrode serving as a reference electrode, a platinum electrode serving as a counter electrode and a KOH solution with 1mol/L of electrolyte to assemble a button cell, and testing the initial discharge specific capacity of the composite electrode material by using an IviumStat electrochemical workstation.
Item Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2
Current Density (A/g) 1 1 1 1 1 1
Specific capacity (F/g) 467.0 602.7 681.3 647.2 325.1 621.8
Testing of heteroatom-doped porous carbon-supported hollow Fe using IviumStat electrochemical workstation3O4The electrode material of the microsphere has specific capacity after 5000 circles of cyclic use.
Item Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2
Current Density (A/g) 1 1 1 1 1 1
Specific capacity (F/g) 396.9 482.2 545.0 453.0 286.1 315.8

Claims (8)

1. Heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4The electrode material of (2), characterized in that: the heteroatom-doped porous carbon-loaded flower-shaped Fe3O4The preparation method of the electrode material comprises the following steps:
(1) reacting 5,5 '-dibromo-2, 2' -bithiophene, N-formyl morpholine and N-butyllithium to obtain a compound with a molecular formula of C10H6O2S2Of [2,2']-bithiophene-5, 5' -dicarbaldehyde;
(2) adding chitosan into a mixed solvent of isopropanol and deionized water with the volume ratio of 10:6-8, stirring and mixing uniformly, continuing to add [2,2'] -dithiophene-5, 5' -dicarboxaldehyde, transferring to an oil bath pot for Schiff base crosslinking reaction, and after the reaction is finished, performing suction filtration, washing and drying to obtain a thiophene crosslinked chitosan derivative;
(3) adding a thiophene cross-linked chitosan derivative into a tubular furnace, raising the temperature for pre-carbonization, adding the thiophene cross-linked chitosan derivative into a deionized water solvent, continuously adding potassium hydroxide, uniformly mixing, evaporating the solvent, transferring the solvent into the tubular furnace for activation and hole making, and filtering, washing and drying a product to obtain a nitrogen and sulfur double-doped porous carbon material;
(4) adding a nitrogen-sulfur double-doped porous carbon material, potassium ferricyanide and glycerol into a deionized water solvent, ultrasonically stirring, transferring into a reaction kettle, placing in an oven, carrying out hydrothermal reaction, cooling a product, centrifuging, washing and drying to obtain heteroatom-doped porous carbon-loaded flower-ball-shaped Fe3O4The electrode material of (1).
2. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the chitosan and the [2,2 'in the step (2)']The mass ratio of the-bithiophene-5, 5' -dicarbaldehyde is 100: 140-320.
3. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the temperature of the Schiff base crosslinking reaction in the step (2) is 30-50 ℃, and the reaction is carried out for 6-12h under the constant-temperature stirring in the nitrogen atmosphere.
4. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the temperature of the pre-carbonization in the step (3) is 350-450 ℃, and the pre-carbonization is carried out for 2-3h in the nitrogen atmosphere.
5. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the mass ratio of the thiophene cross-linked chitosan derivative to the potassium hydroxide in the step (3) is 100: 40-80.
6. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in thatThe method comprises the following steps: the temperature for activating and preparing the holes in the step (3) is 750-850 ℃, and the holes are prepared for 2-3h in the argon atmosphere.
7. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the mass ratio of the nitrogen-sulfur double-doped porous carbon material, the potassium ferricyanide and the glycerol in the step (4) is 100:180-240: 650-820.
8. The heteroatom-doped porous carbon-supported flower-like Fe of claim 13O4The electrode material of (2), characterized in that: the temperature of the hydrothermal reaction in the step (4) is 170-190 ℃, and the time is 10-20 h.
CN202110212823.0A 2021-02-25 2021-02-25 Heteroatom-doped porous carbon-loaded flower-shaped spherical Fe3O4Electrode material and method for producing the same Withdrawn CN112960699A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114171326A (en) * 2021-12-06 2022-03-11 西北大学 Preparation method of nitrogen-doped ultrathin 2D porous carbon nanosheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114171326A (en) * 2021-12-06 2022-03-11 西北大学 Preparation method of nitrogen-doped ultrathin 2D porous carbon nanosheet

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