CN111517306A - Graphene-like/biomass carbon fiber aerogel and preparation method and application thereof - Google Patents
Graphene-like/biomass carbon fiber aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of carbon materials, and provides a graphene-like/biomass carbon fiber aerogel and a preparation method and application thereof. Mixing a nitrogen source, a carbon source, a solvent and biomass fibers, and drying to obtain a mixed solid; and then pyrolyzing the mixed solid to obtain the graphene-like/biomass carbon fiber aerogel. The graphene-like/biomass carbon fiber aerogel provided by the invention has the advantages of high specific surface area, micro-mesoporous structure, nitrogen and oxygen containing atoms, good conductivity and battery energy storage function, capability of being applied to electrochemical energy storage materials, light weight, low cost, small influence on the environment, no secondary pollution and the like, and is suitable for practical production practice.
Description
Technical Field
The invention relates to the technical field of carbon materials, and particularly relates to a graphene-like/biomass carbon fiber aerogel and a preparation method and application thereof.
Background
The carbon fiber is an inorganic polymer fiber with carbon content higher than 90%, wherein the carbon fiber with carbon content higher than 99% is called graphite fiber. The microstructure of the carbon fiber is similar to that of artificial graphite and is a turbostratic graphite structure. The spacing between the layers of carbon fiber is about
The arrangement of the individual carbon atoms between the parallel layers is not as regular as graphite and the layers are connected together by van der waals forces. The structure of carbon fibers can be seen as consisting of two-dimensional ordered crystals and pores, wherein the content, size and distribution of the pores has a large influence on the properties of the carbon fibers.
The method for doping nitrogen and oxygen atoms in the carbon material can be roughly divided into in-situ doping and post-doping, wherein the in-situ doping occurs in the preparation process of the carbon material, the post-doping is to carry out post-treatment on the prepared carbon material to introduce nitrogen, oxygen and other atoms, and the post-doping can partially change the morphology of the carbon material and even the structure of the material and has certain influence on the performance of the material, so that the in-situ doping method is generally adopted for the carbon material with a complete required structure. The nitrogen and oxygen atoms are doped, so that the surface chemical activity of the carbon material can be improved, the chemical active sites can be increased, and the electronic structure can be adjusted, so that the conductive carbon fiber containing nitrogen and oxygen atoms plays a certain role in energy storage and conversion of super capacitors, lithium ion batteries, lithium sulfur batteries and the like. However, the existing conductive carbon fiber has the problems of small specific surface area, uneven aperture matching and the like, so that the electrochemical performance is still poor, and the requirements of energy storage electrode materials such as super capacitors, lithium-sulfur batteries and the like cannot be met.
Disclosure of Invention
In view of the above, the invention provides a graphene-like/biomass carbon fiber aerogel, and a preparation method and an application thereof. The graphene-like/biomass carbon fiber aerogel provided by the invention is high in specific surface area, has a micropore-mesopore composite pore structure, is co-doped with nitrogen and oxygen atoms, and is excellent in electrochemical performance.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of graphene/biomass-like carbon fiber aerogel comprises the following steps:
(1) mixing a nitrogen source, a carbon source, a solvent and biomass fibers, and drying to obtain a mixed solid;
(2) and carrying out pyrolysis on the mixed solid to obtain the graphene-like/biomass carbon fiber aerogel.
Preferably, the nitrogen source comprises at least one of urea, thiourea, melamine, cyanuric chloride, melamine cyanurate, and cyanuric acid.
Preferably, the carbon source comprises at least one of sucrose, chitosan, glucose, starch, cellulose, fructose and cyclodextrin.
Preferably, the biomass fiber comprises at least one of cotton, catkin, dandelion, silk, bamboo, sugarcane, straw white, shaddock peel white pulp and loofah pulp.
Preferably, the solvent is water, ethanol or a mixture of water and ethanol.
Preferably, the weight ratio of the nitrogen source, the carbon source and the biomass fibers is (1-40) to 2 (0.5-2).
Preferably, the drying temperature is 90-95 ℃.
Preferably, the pyrolysis temperature is 900-1500 ℃, and the time is 1-2 h.
The invention provides the graphene-like/biomass carbon fiber aerogel prepared by the preparation method in the scheme.
The invention also provides application of the graphene-like/biomass carbon fiber aerogel in the scheme in an electrochemical energy storage material.
The invention provides a preparation method of graphene/biomass-like carbon fiber aerogel, which comprises the steps of mixing a nitrogen source, a carbon source, a solvent and biomass fibers, and drying to obtain a mixed solid; and then pyrolyzing the mixed solid to obtain the graphene-like/biomass carbon fiber aerogel. The graphene-like/biomass carbon fiber aerogel is prepared by adopting an in-situ doping method, providing a skeleton structure by using biomass fibers, providing a precursor for in-situ reaction by using a carbon source, providing doped nitrogen atoms by using a nitrogen source, performing self-supporting pyrolysis on the carbon source, the nitrogen source and the biomass fibers, and preparing the graphene-like/biomass carbon fiber aerogel by a self-assembly one-step method.
The graphene-like/biomass carbon fiber aerogel prepared by the preparation method provided by the invention has the advantages of high specific surface area, micro mesoporous structure, nitrogen and oxygen heteroatom, good conductivity and battery energy storage function.
The invention also provides application of the graphene/biomass carbon fiber aerogel in the scheme in an electrochemical energy storage material. The graphene-like/biomass carbon fiber aerogel provided by the invention is applied to an electrochemical energy storage material, the performance of the electrochemical energy storage material can be obviously improved, and the graphene-like/biomass carbon fiber aerogel provided by the invention has the characteristics of light weight, low cost, small influence on the environment, no secondary pollution and the like, and is suitable for actual production practice.
Drawings
Fig. 1 is an SEM photograph of the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 1;
fig. 2 is an XPS characterization analysis chart of the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 1;
fig. 3 is a nitrogen adsorption desorption test chart of the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 1;
fig. 4 is a pore size distribution test chart of the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 1;
fig. 5 is a rate performance test chart of lithium-sulfur battery assembled by using the graphene-like/catkin-based biomass carbon fiber aerogel prepared in example 2 as a sulfur cathode carrier;
fig. 6 is a 200-cycle performance test chart of a lithium-sulfur battery assembled by using the graphene-like/silk-based biomass carbon fiber aerogel prepared in example 3 as a sulfur cathode carrier;
fig. 7 is a cyclic voltammetry performance test chart of a supercapacitor assembled by using the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 4 as an electrode material;
fig. 8 is a graph showing a relationship between the capacity and the current density of a supercapacitor assembled by using the graphene-like/loofah-based biomass carbon fiber aerogel prepared in example 5 as an electrode material;
fig. 9 is a relationship diagram of energy density and power density of a supercapacitor assembled by using the graphene-like/shaddock peel and white pulp-based biomass carbon fiber aerogel prepared in example 6 as an electrode material.
Detailed Description
The invention provides a preparation method of graphene/biomass-like carbon fiber aerogel, which comprises the following steps:
(1) mixing a nitrogen source, a carbon source, a solvent and biomass fibers, and drying to obtain a mixed solid;
(2) and carrying out pyrolysis on the mixed solid to obtain the graphene-like/biomass carbon fiber aerogel.
According to the invention, a nitrogen source, a carbon source, a solvent and biomass fibers are mixed and then dried to obtain a mixed solid. In the present invention, the nitrogen source preferably includes at least one of urea, thiourea, melamine, cyanuric chloride, melamine cyanurate, and cyanuric acid; the carbon source preferably comprises at least one of sucrose, chitosan, glucose, starch, cellulose, fructose and cyclodextrin; the biomass fiber preferably comprises at least one of cotton, catkin, dandelion, silk, bamboo, sugarcane, straw white, shaddock peel white pulp and towel gourd pulp; the straw white comprises sunflower stems and/or corn stems; the solvent is preferably water, ethanol or a mixed solution of water and ethanol; the weight ratio of the nitrogen source, the carbon source and the biomass fibers is preferably (1-40) to 2 (0.5-2), more preferably (3-35) to 2 (1-1.5); the ratio of the total mass of the nitrogen source and the carbon source to the volume of the solvent is preferably 11g to 42 g: 30mL to 100 mL.
In the embodiment of the present invention, preferably, the nitrogen source and the carbon source are first ground to a particle size of less than 400 mesh, the ground material is dissolved in the solvent under the water bath condition, and then the biomass fiber is added for standing and soaking. In the invention, the temperature of the water bath is preferably 65 ℃, the standing soaking time is preferably 6h, and the biomass fibers are enabled to adsorb the solution of the nitrogen source and the carbon source to be saturated through the standing soaking.
In the invention, the drying temperature is preferably 90-95 ℃; the invention has no special requirement on the drying time, and can completely remove the solvent in the mixture.
After the mixed solid is obtained, the invention pyrolyzes the mixed solid. In the invention, the pyrolysis temperature is preferably 900-1500 ℃, more preferably 1000-1300 ℃, the heating rate for heating to the pyrolysis temperature is preferably 5 ℃/min, and the pyrolysis time is preferably 1-2 h, more preferably 1-1.5 h; the pyrolysis time is the heat preservation time after the temperature is raised to the pyrolysis temperature; the pyrolysis is carried out under the conditions of normal pressure and no protective atmosphere; in a specific embodiment of the invention, the mixed solids are preferably placed in a muffle furnace and then warmed from room temperature to pyrolysis temperature.
In the pyrolysis process, the carbon source and the nitrogen source are converted from a solid phase to a liquid phase and then to a solid phase in the process of temperature rise. In the first stage, the carbon source and the nitrogen source which are uniformly mixed are converted from a solid phase to a solid/liquid two phase at 350-400 ℃, and a large amount of ammonia gas is released in a closed environment. In the second stage, at 550 deg.C, nitrogen source is polycondensed to produce graphite phase carbon nitride (g-C)3N4) As two-dimensional layered template, carbon source molecules are simultaneously converted into amorphous carbon with oxygen-containing functional groups, and the mixture of solid/liquid phases is gradually converted into solid phase g-C3N4Amorphous carbon. In the third stage, carbonyl groups and g-C on the amorphous carbon are reacted with the carbon-carbon mixture as the pyrolysis temperature is increased3N4Reaction of amino groups on the template by Maillard reaction at g-C3N4The defect sites or edges (rich in amino groups) of the carbon nanotubes are chemically grafted with amorphous carbon to finally produce OCN sheets (two-dimensional sheet-like nano graphene-like carbon oxynitrides). In the high-temperature oxidation process, the biomass fibers are carbonized at high temperature, the microstructure of the original fibers is kept under the protection of ammonia gas atmosphere, the original three-dimensional state of the biomass fibers is macroscopically kept, and the generated nitrogen and oxygen atom co-doped graphene-like oxygen carbon nitride can uniformly grow on the surfaces of the biomass carbon fibers in situ, so that the graphene-like/biomass carbon fiber aerogel is finally generated.
After pyrolysis is completed, the black solid obtained after pyrolysis is preferably soaked in deionized water, and then freeze-drying is carried out to obtain the graphene-like/biomass carbon fiber aerogel. In the invention, the soaking time is preferably 2 hours; the temperature of the freeze drying is preferably-40 ℃, and the time is preferably 24 h; according to the invention, inorganic salt generated in the pyrolysis period can be fully dissolved by soaking in deionized water, so that the graphene/biomass carbon fiber aerogel can be purified, and byproducts in the product can be removed.
The invention also provides the graphene-like/biomass carbon fiber aerogel prepared by the preparation method in the scheme. Structurally, the carbon fiber aerogel is formed by spirally winding and polymerizing the porous carbon fiber doped with the heteroatom, the microscopic form of the carbon fiber contains a micropore-mesopore composite pore channel structure, the average pore diameter is 2.2-6.04 nm, and the specific surface area is 81.87-1305.2 m2Per g, the pore volume of the micropores is 0.007 to 0.478cm3(ii) a resistivity of 80m Ω · cm to 1.8 Ω · cm; the carbon fiber aerogel provided by the invention is rich in heteroatoms such as nitrogen and oxygen from the aspect of element composition, wherein the chemical bond types of carbon comprise: graphitization of sp2C、sp3Hybrid C, oxygen-bridged C, heterocyclic C, said sp3The hybrid C comprises C-N or C-O, the heterocyclic ring C comprises C-N or C-O, the chemical bond of nitrogen comprises pyridine N, pyrrole N or pyridone N and graphite phase N, the content of nitrogen in the carbon fiber aerogel is 1-25 wt%, and the content of oxygen in the carbon fiber aerogel is 4-25 wt%.
The invention also provides application of the graphene/biomass carbon fiber aerogel in the scheme in an electrochemical energy storage material. In the present invention, the electrochemical energy storage material preferably includes a lithium sulfur battery and a supercapacitor.
In the present invention, when the graphene-like/biomass carbon fiber aerogel is applied to a lithium sulfur battery, it is preferably used for preparing a positive electrode of the lithium sulfur battery, specifically, the carbon fiber aerogel of the present invention is used as a carrier of sulfur, and a sulfur-carbon composite material is prepared by a chemical deposition method or a mechanical grinding method. After the sulfur-carbon composite material is obtained, the invention preferably takes PVDF (polyvinylidene fluoride) as a binder, takes activated carbon (SuperP) as a conductive agent, and adopts the following steps: PVDF: mixing activated carbon (SuperP) in a ratio of 7:1:2 (mass ratio), taking N-methyl pyrrolidone (NMP) as a solvent, fully grinding to prepare electrode slurry, uniformly coating the electrode slurry on a current collector, and drying in vacuum at 60 ℃ for 12 hours to obtain the sulfur positive electrode.
After the positive electrode of the lithium-sulfur battery is obtained, the positive electrode, the negative electrode, the diaphragm and the electrolyte of the lithium-sulfur battery are processed in a glove box under the anhydrous and oxygen-free state to obtain the lithium-sulfur battery; the negative electrode is preferably metal lithium, the diaphragm is preferably Celgard2400, the solute of the electrolyte is preferably lithium bistrifluoromethanesulfonimide and lithium nitrate, the solvent is preferably a mixed solvent of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and the volume ratio of the 1, 3-dioxolane to the ethylene glycol dimethyl ether in the mixed solvent is preferably 1: 1; the concentration of lithium bis (trifluoromethanesulfonyl) imide in the electrolyte is preferably 1mol/L, and the mass percentage of lithium nitrate is preferably 1%.
The graphene-like/biomass carbon fiber aerogel provided by the invention has excellent conductivity, good chemical stability and thermal stability, large specific surface area, abundant pore structure and surface functional groups, and sulfur can be limited in micropores, defects and surface active sites of the carbon fiber aerogel by utilizing the sulfur-carbon composite material prepared by the graphene-like/biomass carbon fiber aerogel, so that the conductivity of sulfur can be effectively increased, the dissolution of polysulfide ions can be limited, the performance of a lithium-sulfur battery can be remarkably improved, and the graphene-like/biomass carbon fiber aerogel has wide potential application value.
In the invention, when the graphene/biomass-like carbon fiber aerogel is applied to a supercapacitor, the carbon fiber aerogel is preferably used as an active material of the supercapacitor electrode to prepare an aerogel electrode; the preparation method of the aerogel electrode preferably includes the steps of: mixing graphene-like/biomass carbon fiber aerogel with PVDF, and grinding with NMP (N-methyl pyrrolidone) as a solvent to obtain electrode slurry; and coating the electrode slurry on the surface of an aluminum foil current collector, cutting the aluminum foil current collector into required sizes after vacuum drying, and then soaking the cut electrode in a KOH solution to remove the aluminum foil current collector to obtain the aerogel electrode. In the invention, the mass ratio of the graphene-like/biomass carbon fiber aerogel to the PVDF is preferably 9: 1; the temperature of the vacuum drying is preferably 60 ℃, and the time is preferably 12 hours; the concentration of the KOH solution is preferably 6 mol/L; the invention has no special requirement on the soaking time, and can completely remove the aluminum current collector.
In the present invention, the electrolyte of the supercapacitor is preferably an aqueous electrolyte, and the solute of the aqueous electrolyte may specifically be potassium hydroxide, sulfuric acid, nitrate, sulfate, or the like. The method for applying the active material of the super capacitor electrode has no special requirements, and the active material can be applied according to a method well known by the technical personnel in the field.
Under the condition of aqueous electrolyte, in a three-electrode and two-electrode test, the native spiral pore structure, the large specific surface area, the micro-mesoporous structure, the specific functional group and the good conductivity and wettability of the material of the carbon fiber aerogel material are reflected in the supercapacitor, and the spiral structure, the large specific surface area and the mesoporous structure can effectively promote the transmission and diffusion of ions; the doping of nitrogen oxygen atom, its peculiar functional group show certain pseudo-capacitance nature in electrochemistry, the effectual electric capacity that improves ultracapacitor system, and carbon fiber aerogel's quality is light, and then can effectively improve the energy density and the power density of condenser.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Weighing 20g of urea and 2g of glucose, mixing the urea and the glucose in an agate mortar, grinding the mixture in a ball mill for about 2 hours until the granularity is less than 400 meshes, dissolving the mixture in 60mL of mixed solution of ethanol and water in a hot water bath at 65 ℃, stirring the mixture for 2 hours, weighing 2g of biomass cotton, soaking the cotton in the solution, standing the solution for 6 hours, pouring the mixture into a corundum reaction kettle after the mixture is completely soaked and saturated, drying the mixture in a waterless oven at 90 ℃ for 3 days, placing the dried mixture in a muffle furnace, and heating the mixture to 1200 ℃ at the speed of 5 ℃/min for pyrolysis, wherein the pyrolysis time is 1.5 hours. Weighing the pyrolyzed black solid, soaking in 200mL of deionized water for 2h, then carrying out freeze drying to prepare graphene/cotton-like-based biomass carbon fiber aerogel, and respectively carrying out SEM (scanning Electron microscope), XPS (XPS), specific surface area and pore size distribution tests on the obtained carbon fiber aerogel.
Fig. 1 is an SEM photograph of the obtained graphene/cotton-like biomass carbon fiber aerogel. As can be seen from fig. 1, the cotton fiber after high temperature treatment not only maintains its original skeleton, but also coats a certain amount of graphene-like material on its outer surface.
Fig. 2 is an XPS characterization analysis diagram of the obtained graphene/cotton-based biomass carbon fiber aerogel. As can be seen from fig. 2, the material is rich in carbon, nitrogen and oxygen elements.
Fig. 3 is a nitrogen adsorption and desorption test chart of the obtained graphene/cotton-based biomass carbon fiber aerogel. According to the nitrogen adsorption and desorption test curve test, the specific surface area of the graphene-like/cotton-based biomass carbon fiber aerogel prepared in example 1 is 157.93m2/g。
Fig. 4 is a graphene-like/cotton-based biomass carbon fiber aerogel, pore size distribution test chart. The pore size distribution curve shows that the graphene/cotton-based biomass carbon fiber aerogel prepared in example 1 has a micro-mesoporous structure, wherein micropores are mainly concentrated at about 1nm, and mesopores are mainly concentrated at 3.3nm and 5.3 nm.
Example 2
Weighing 15g of melamine and 2g of cellulose, mixing the melamine and the cellulose in an agate mortar, grinding the mixture in a ball mill for about 2 hours until the granularity is less than 400 meshes, carrying out hot water bath at 65 ℃, dissolving the mixture in 60mL of aqueous solution, stirring the mixture for 2 hours, weighing 1g of biomass catkin, soaking the catkin in the solution, standing the solution for 6 hours, pouring the mixture into a corundum reaction kettle after the mixture is completely soaked and saturated, drying the mixture for 3 days in a 95 ℃ anhydrous oven, placing the dried mixture in a muffle furnace, heating the mixture to 1100 ℃ at the speed of 5 ℃/min, and carrying out pyrolysis for 1.5 hours. And weighing the pyrolyzed black solid, soaking the black solid in 200mL of deionized water for 2h, and performing freeze drying and freeze drying to prepare the graphene/catkin-based biomass carbon fiber aerogel.
The graphene-like/catkin-based biomass carbon fiber aerogel is used as a sulfur carrier and applied to a lithium-sulfur battery. Preparing a sulfur-carbon composite material by a grinding method, wherein the sulfur-carbon composite material comprises the following steps: PVDF: mixing activated carbon (SuperP) in a ratio of 7:1:2 (mass ratio), taking N-methyl pyrrolidone (NMP) as a solvent, fully grinding to prepare electrode slurry, uniformly coating the electrode slurry on an aluminum foil current collector, and drying in vacuum at 60 ℃ for 12 hours to obtain the sulfur positive electrode. The sulfur loading of the positive electrode was 1.2mg/cm2Celgard2400 as separator, lithium plate as negative electrode (diameter: 15.6mm, thickness: 450 μm), electrolyte: LITFSI was dissolved in a mixed solvent of DME and DOL at a volume ratio of 1:1, the concentration of LITFSI was 1mol/L, and 1 wt% LiNO was added3. The lithium-sulfur battery was processed in a glove box in the anhydrous and oxygen-free state.
The rate performance test was performed on the lithium sulfur battery, and the obtained results are shown in fig. 5. Fig. 5 is a rate performance test chart of a lithium-sulfur battery assembled by graphene-like/catkin-based biomass carbon fiber aerogel serving as a sulfur cathode carrier. According to fig. 5, it is possible that the obtained lithium-sulfur battery can release 1386.7mAh/g of capacity under the condition of 0.1C of low rate, and the release capacity is 870.1mAh/g under the condition of 2C of high rate, the capacity retention rate is as high as 62.74%, and the battery shows excellent electrochemical energy storage performance.
Example 3
Weighing 30g of thiourea and 2g of cyclodextrin, mixing the thiourea and the cyclodextrin in an agate mortar, grinding the mixture in a ball mill for about 2 hours until the granularity is less than 400 meshes, carrying out hot water bath at 65 ℃, dissolving the mixture in 50mL of mixed solution of ethanol and water, stirring the mixture for 2 hours, weighing 0.5g of silk, soaking the silk in the solution, standing the solution for 6 hours, pouring the mixture into a corundum reaction kettle after the silk is completely soaked and saturated, drying the mixture in a 95 ℃ anhydrous oven for 3 days, placing the dried mixture in a muffle furnace, heating the mixture to 1000 ℃ at the speed of 5 ℃/min, and carrying out pyrolysis for 2 hours. And weighing the pyrolyzed black solid, soaking the black solid in 200mL of deionized water for 2h, and performing freeze drying and freeze drying to prepare the graphene/silk-like-based biomass carbon fiber aerogel.
The graphene-like/silk-based biomass carbon fiber aerogel is used as a sulfur carrier and applied to a lithium-sulfur battery. The preparation method of the sulfur positive electrode is consistent with that of the example 2, and the sulfur loading of the positive electrode is 1.2mg/cm2Celgard2400 as separator, lithium plate as negative electrode (diameter: 15.6mm, thickness: 450 μm), electrolyte: LITFSI was dissolved in a mixed solvent of DME and DOL at a volume ratio of 1:1, the concentration of LITFSI was 1mol/L, and 1 wt% LiNO was added3. The lithium-sulfur battery was processed in a glove box in the anhydrous and oxygen-free state.
The cycle performance test was performed on the lithium sulfur battery, and the results are shown in fig. 6. Fig. 6 is a 200-cycle performance test chart of the obtained lithium sulfur battery. According to fig. 3, the graphene-like/silk-based biomass carbon fiber aerogel is used as the positive electrode material of the lithium-sulfur battery, and under the multiplying power of 0.5C, the capacity of the battery still maintains 997.1mAh/g after 200 cycles, and the capacity retention rate is as high as 76.18%.
Example 4
Weighing 15g of urea and 2g of cellulose, mixing the urea and the cellulose in an agate mortar, grinding the mixture for 2h by a ball mill until the granularity is less than 400 meshes, carrying out hot water bath at 65 ℃, dissolving the mixture in 60mL of aqueous solution, stirring the solution for 2h, weighing 1g of biomass cotton, soaking the cotton in the solution, standing the solution for 6h, completely soaking the cotton until the mixture is saturated, pouring the mixture into a corundum reaction kettle, drying the mixture for 3 days in a 95 ℃ anhydrous oven, placing the dried mixture in a muffle furnace, and heating the mixture to 1000 ℃ at the speed of 5 ℃/min for pyrolysis, wherein the pyrolysis time is 2 h. And weighing the pyrolyzed black solid, soaking the black solid in 200mL of deionized water for 2h, and performing freeze drying and freeze drying to prepare the graphene/cotton-like biomass carbon fiber aerogel.
The graphene/cotton-like biomass carbon fiber aerogel material is applied to a super capacitor as an electrode active material. The prepared carbon fiber aerogel is used as an active material and is uniformly mixed with PVDF according to the mass ratio of 9:1, NMP is used as a solvent to be fully ground to prepare electrode slurry, the electrode slurry is uniformly coated on the surface of an aluminum foil current collector, vacuum drying is carried out at the temperature of 60 ℃ for 12h, and the dried electrode slice is cut into spare electrodes with equal size and equal mass. And weighing the mass, and soaking in 6mol/L KOH solution to remove an aluminum current collector, so as to serve as the graphene/cotton-based biomass carbon fiber aerogel electrode. Two electrodes (1mg) with equal size and equal mass are weighed as a working electrode and a counter electrode of the supercapacitor, NKK cellulose diaphragm paper is used as a diaphragm, 6mol/L KOH is used as electrolyte, and cyclic voltammetry curves at different scanning rates are tested, and the obtained result is shown in FIG. 7.
Fig. 7 is a cyclic voltammetry performance test chart of a supercapacitor assembled by using the obtained graphene/cotton-based biomass carbon fiber aerogel as an electrode material. According to the graph in FIG. 7, the cyclic voltammetry curves (10mV/s to 100mV/s) tested at different scanning rates of a super capacitor assembled by using the graphene-like/cotton-based biomass carbon fiber aerogel as an electrode material can keep a complete rectangular-like shape under the environment of 6mol/LKOH as an electrolyte, and the super capacitor shows excellent electrochemical energy storage performance.
Example 5
Weighing 30g of urea and 2g of cyclodextrin, mixing the urea and the cyclodextrin in an agate mortar, grinding the urea and the cyclodextrin in a ball mill for about 2 hours until the granularity is less than 400 meshes, carrying out hot water bath at 65 ℃, dissolving the urea and the cyclodextrin in 30mL of mixed solution of ethanol and water, stirring the mixed solution for 2 hours, weighing 2g of dried vegetable sponge, cutting the vegetable sponge into small segments, gradually soaking the small segments in the solution, standing the small segments for 10 hours, pouring the mixture into a corundum reaction kettle, drying the mixture in an anhydrous oven at 95 ℃ for 3 days, placing the dried mixture in a muffle furnace, heating the mixture to 900 ℃ at the speed of 5 ℃/min, and carrying out pyrolysis for 2 hours. And weighing the pyrolyzed black solid, soaking the black solid in 200mL of deionized water for 2h, and freeze-drying to prepare the graphene/vegetable sponge-like biomass carbon fiber aerogel.
The graphene-like/loofah-based biomass carbon fiber aerogel material is applied to a super capacitor as an electrode active material. The graphene/loofah-like biomass carbon fiber aerogel electrode is prepared by the same method as in example 4, two electrodes (1mg) with equal size and equal mass are weighed as a working electrode and a counter electrode of a supercapacitor, NKK cellulose diaphragm paper is a diaphragm, 6mol/L KOH is electrolyte, and specific capacities under different current densities are tested, and the obtained result is shown in FIG. 8.
Fig. 8 is a relation graph of specific capacity and current density of a supercapacitor assembled by using the obtained graphene/loofah-based biomass carbon fiber aerogel as an electrode material. According to fig. 8, the graphene-like/loofah-based biomass carbon fiber aerogel is used as the electrode material of the supercapacitor, the electrode material can release 463.4F/g specific capacity in an environment with 6mol/LKOH as an electrolyte and at a current density of 0.5A/g, the capacity can still maintain 287.5F/g under a high current density condition of 100A/g, the retention rate is as high as 62.0%, and the super capacitor has excellent rate capability and extremely high specific capacity.
Example 6
Weighing 40g of urea and 2g of cyclodextrin, mixing the urea and the cyclodextrin in an agate mortar, grinding the mixture for about 2h by a ball mill until the granularity is less than 400 meshes, carrying out hot water bath at 65 ℃, dissolving the mixture in 30mL of mixed solution of ethanol and water, stirring the mixture for 2h, weighing 2g of dried white pulp of shaddock peel, cutting the white pulp of the shaddock peel into small blocks, gradually soaking the small blocks into the solution, standing the solution for 10h, pouring the mixture into a corundum reaction kettle integrally, drying the mixture for 2 days in a 95 ℃ anhydrous oven, placing the dried mixture in a muffle furnace, heating the mixture to 1300 ℃ at the speed of 5 ℃/min, and carrying out pyrolysis for 1 h. And weighing the pyrolyzed black solid, soaking the black solid in 200mL of deionized water for 2h, and freeze-drying to prepare the graphene/shaddock peel white pulp-based biomass carbon fiber aerogel.
The graphene-like/shaddock peel and white pulp-based biomass carbon fiber aerogel material is applied to a super capacitor as an electrode active material. The graphene/loofah-like biomass carbon fiber aerogel electrode is prepared by the same method as in example 4, two electrodes (1mg) with equal size and equal mass are weighed as a working electrode and a counter electrode of a supercapacitor, NKK cellulose diaphragm paper is a diaphragm, 6mol/L KOH is electrolyte, and the energy density and power density performance which can be output by the electrode are tested, and the obtained result is shown in FIG. 9.
Fig. 9 is a relation diagram of energy density and power density of a supercapacitor assembled by using the obtained graphene-like/shaddock peel and white pulp-based biomass carbon fiber aerogel as an electrode material. According to the figure 9, the graphene-like/shaddock peel and pulp-based biomass carbon fiber aerogel is used as the electrode material of the supercapacitor, and under the environment that 6mol/LKOH is used as an electrolyte, the energy density of 16.0Wh/kg and the power density of 24880W/kg can be released to the maximum extent. The electrochemical energy storage performance is excellent.
SEM and XPS tests are carried out on the graphene-like/biomass carbon fiber aerogel obtained in the embodiments 1-6, and SEM results show that the surfaces of the obtained carbon fibers are all coated with graphene-like structures; the XPS results showed that the resulting carbon fiber aerogel was rich in heteroatoms such as nitrogen, oxygen, etc., wherein the chemical bond types of carbon include: graphitization of sp2C、sp3Hybrid C, oxygen-bridged C, heterocyclic C, said sp3The hybrid C comprises C-N or C-O, the heterocyclic ring C comprises C-N or C-O, the chemical bond of nitrogen comprises pyridine N, pyrrole N or pyridone N and graphite phase N, the content of nitrogen in the carbon fiber aerogel is 1-25 wt%, and the content of oxygen in the carbon fiber aerogel is 4-25 wt%.
Specific surface area and pore size distribution tests were performed on the graphene-like/biomass carbon fiber aerogels obtained in examples 1 to 6, and the results are listed in table 1. The pore size distribution test result shows that the microscopic morphology of the graphene-like/biomass carbon fiber aerogel is a micropore-mesopore composite pore channel structure, and the average pore size is 2.2 nm-6.04 nm; the specific surface area test results show that: the specific surface area of the material is 81.87-1305.2 m2Per g, the pore volume of the micropores is 0.007 to 0.478cm3/g；
Resistivity tests are carried out on the graphene-like/biomass carbon fiber aerogels prepared in examples 1 to 6, and the results are listed in table 1, and the results show that the resistivity range of the material is 80m Ω · cm to 1.8 Ω · cm, which indicates that the graphene-like/biomass carbon fiber aerogels prepared by the invention have good conductivity.
Table 1 results of pore size distribution and resistivity test of graphene-like/biomass carbon fiber aerogel obtained in examples 1 to 6
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the graphene/biomass-like carbon fiber aerogel is characterized by comprising the following steps of:
(1) mixing a nitrogen source, a carbon source, a solvent and biomass fibers, and drying to obtain a mixed solid;
(2) and carrying out pyrolysis on the mixed solid to obtain the graphene-like/biomass carbon fiber aerogel.
2. The method according to claim 1, wherein the nitrogen source comprises at least one of urea, thiourea, melamine, cyanuric chloride, melamine cyanurate, and cyanuric acid.
3. The method of claim 1, wherein the carbon source comprises at least one of sucrose, chitosan, glucose, starch, cellulose, fructose, and cyclodextrin.
4. The method of claim 1, wherein the biomass fiber comprises at least one of cotton, catkin, dandelion, silk, bamboo, sugarcane, straw white, grapefruit peel white pulp, and loofah pulp.
5. The method according to claim 1, wherein the solvent is water, ethanol, or a mixture of water and ethanol.
6. The method according to claim 1, wherein the weight ratio of the nitrogen source, the carbon source and the biomass fibers is (1-40): 2 (0.5-2).
7. The method according to claim 1, wherein the drying temperature is 90 to 95 ℃.
8. The preparation method according to claim 1, wherein the pyrolysis temperature is 900-1500 ℃ and the time is 1-2 h.
9. The graphene-like/biomass carbon fiber aerogel prepared by the preparation method of any one of claims 1 to 8.
10. Use of the graphene-like/biomass carbon fiber aerogel according to claim 9 in an electrochemical energy storage material.
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