CN114751394A - Preparation of nitrogen-doped pepper residue biomass porous carbon material and application of nitrogen-doped pepper residue biomass porous carbon material as electrode material - Google Patents
Preparation of nitrogen-doped pepper residue biomass porous carbon material and application of nitrogen-doped pepper residue biomass porous carbon material as electrode material Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a preparation method of a nitrogen-doped pepper residue biomass porous carbon material, which comprises the steps of removing capsaicin from clean pepper powder, taking the pepper residue left after aliphatic hydrocarbon as a raw material, taking urea and potassium hydroxide as a nitrogen source and an activating agent respectively, preparing a biomass porous carbon material precursor through simple dipping, aging and heating, and calcining at a high temperature in a nitrogen atmosphere to obtain a final product. The physical characterization result shows that the product has ultrahigh specific surface area and abundant hierarchical porous structure. Electrochemical performance tests show that the material shows high electrochemical capacitance behavior and excellent capacitance doubling rate, and is suitable for being applied to a super capacitor as an electrode material. In addition, the porous carbon material disclosed by the invention is simple in synthetic route, the capsicum residue is used as a biomass waste, the source is wide, the cost is low, the safety and the high efficiency are realized, the environment is protected, the large-scale production can be realized, and the potential application prospect is realized.
Description
Technical Field
The invention relates to preparation of a porous carbon material, in particular to a preparation method of a nitrogen-doped pepper residue biomass porous carbon material, which is mainly used as an electrode material for preparing a supercapacitor and belongs to the technical field of biomass materials and the technical field of electrochemistry.
Background
The super capacitor is a novel energy storage device between a capacitor and a battery, and has wide application prospect in the fields of pure electric vehicles, hybrid electric vehicles, aerospace, aviation and the like due to the characteristics of high charge-discharge rate, long cycle life, wide service temperature, high specific power, cleanness and safety. The electrode material plays a decisive role in the performance of the super capacitor and is a key research object in the field of energy storage. Currently, the most common electrode materials can be classified into carbon materials (activated carbon, carbon nanotubes, graphene, onion carbon, biomass), metal oxides/hydroxides, conductive polymers, and the like. The biomass carbon usually adopts agricultural wastes as raw materials, has a series of advantages of wide sources, rich reserves, low cost and the like, shows obvious economic benefits and environmental protection advantages compared with fossil fuel energy storage materials, and is widely concerned in the field of supercapacitor electrodes.
The pepper is a perennial herb of the genus capsicum of the family solanaceae, and is mainly used as vegetables, seasonings and edible spices in life; has the efficacies of strengthening the spleen, helping digestion, warming the stomach, dispelling cold, promoting blood circulation and the like in the aspect of medicine; it also has effects of reducing blood fat and weight. The pepper residue is used as a biomass waste, has wide source and low cost, and has potential application prospect when being used for preparing materials. Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-doped pepper residue biomass porous carbon material with an ultrahigh specific surface area;
the invention also aims to research the structure and electrochemical properties of the prepared nitrogen-doped biomass porous carbon material so as to be used for preparing the electrode material of the super capacitor.
Preparation of biomass porous carbon material
The preparation method of the nitrogen-doped pepper residue biomass porous carbon material comprises the following steps:
(1) extracting clean Capsici fructus powder with ethanol at 70 deg.C, removing capsaicin and aliphatic hydrocarbon to obtain Capsici fructus residue, oven drying, and grinding into powder;
(2) soaking the pepper residues in a mixed solution of urea and potassium hydroxide, stirring and performing ultrasonic treatment, aging at room temperature for 6-8 hours, continuously stirring and evaporating at 60-80 ℃ to make the pepper residues become viscous, and finally drying at 60-80 ℃ to form a carbon precursor;
(3) Placing the carbon precursor in a tube furnace in nitrogen atmosphere at 5 deg.C for min-1Heating to 400-500 ℃ at the heating rate, keeping the temperature for 20-40 min, and then heating to 700-800 ℃ for 1-2 h; and naturally cooling to room temperature, grinding the obtained black solid into powder, washing with HCl solution to remove impurities, washing with secondary water to neutrality, performing suction filtration and collection, and drying at 60-80 ℃ to obtain the nitrogen-doped pepper residue biomass porous carbon material.
According to the method, the capsicum residue powder after removing capsaicin and aliphatic hydrocarbon is fully soaked in the mixed solution of potassium hydroxide and urea, the potassium hydroxide and the urea are fully introduced into the microstructure tissues of the residue as built-in activators by absorbing water, and then the nitrogen-doped porous carbon material is prepared by simultaneously performing aging, activation, carbonization and nitrogen doping. The chemical activation of potassium hydroxide can make the material produce more micropore and mesopore structures, thereby greatly increasing the specific surface area of the material. The nitrogen atom introduced by the urea can provide a pair of lone pair electrons, and the characteristics of the carbon material electron donor and the acceptor can be effectively improved, so that pseudo-capacitance reaction is introduced, and the capacitance of the material is correspondingly improved. In addition, the surface hydrophilicity of the carbon material can be improved, so that a larger specific surface area becomes an effective specific surface area, and a larger electric double layer is formed.
Structural characterization of biomass porous carbon material
The structure of the porous carbon material prepared from the pepper residue is characterized. The morphology was characterized by a field emission scanning electron microscope (SEM; JEOL, JSM-6701F, Japan); the crystal structure is characterized by a powder X-ray diffractometer (XRD; D/Max-2400, Cu target: lambda = 1.5418A, tube voltage 40 kV, tube current 60mA, scanning rate 5 DEG/min); specific surface area and pore size distribution measurements were performed by nitrogen adsorption apparatus (BET, micromeritics ASAP 2020, America).
1. Field emission Scanning Electron Microscopy (SEM) analysis
FIG. 1 is a field emission Scanning Electron Microscope (SEM) picture of the nitrogen-doped pepper residue biomass porous carbon material prepared by the invention. As can be seen from the figure, the biomass porous carbon material is a hierarchical porous channel graphene nano-sheet structure which is cross-linked with each other.
2. X-ray diffraction Pattern (XRD) analysis
FIG. 2 is an X-ray diffraction spectrum (XRD) of the nitrogen-doped pepper residue biomass porous carbon material prepared by the invention. In fig. 2, the NPCs each have a broad diffraction peak at 22.0 degrees, corresponding to the 002 crystal plane of graphitized carbon, indicating that the material has an amorphous structure.
3、N2Adsorption and desorption analysis
FIG. 3 shows N of the nitrogen-doped pepper residue biomass porous carbon material prepared by the invention 2Adsorption and desorption curves. Is apparent N2The adsorption and desorption curves can be classified as a combination of the I and IV curves. Below relative pressure (<0.1) indicates that micropores exist in the material, the positive slope gradually increasing between 0.47 and 0.95 is the characteristic of mesopores, and the vertical tail indicates that macropores exist in the material. The specific surface area of the material can be calculated by a BET method, and the specific surface area of the NPC sample is up to 1965.5m2 g-1The increase in specific surface area may result from the gasification expansion of urea.
FIG. 4 is a pore size distribution diagram of the nitrogen-doped pepper residue biomass porous carbon material prepared by the invention. The porous structure of the biomass porous carbon material can be further confirmed by the pore size distribution curve in fig. 4. Total pore volume of NPC 1.064 cm3In terms of/g, the mean pore diameter is 2.2 nm. The micropores of the NPC are mainly and intensively distributed near 1.17 and 1.48 nm, and the mesopores and macropores are continuously distributed at 2-200 nm. The biomass porous carbon material is explained to be a multi-stage pore structure. And a specific surface area of 1965.5m as calculated by the (BET) method2(ii) in terms of/g. High specific surface areaSufficient electrode-electrolyte contact area may be provided to form an electric double layer.
Third, electrochemical performance
The electrochemical performance characterization of the nitrogen-doped capsicum residue biomass porous carbon material prepared by the invention is described in detail by the electrochemical workstation CHI 660B.
1. Preparing the electrode of the super capacitor: 4.7 mg (the mass percentages of the nitrogen-doped pepper residue biomass porous carbon material and acetylene black are 85% and 15% respectively) of mixed solid powder of the nitrogen-doped pepper residue biomass porous carbon material and acetylene black is added into 0.4 mL of Nafion solution with the mass fraction of 0.25 wt% to be subjected to ultrasonic dispersion to form a suspension. Then 6 mu L of the suspension is measured by a pipette and dropped on the surface of a glassy carbon electrode, and the glassy carbon electrode is dried at room temperature and then used for testing.
2. Electrochemical Performance test
A three-electrode system is formed by taking a nitrogen-doped pepper residue biomass porous carbon material as a working electrode, a platinum net as a counter electrode and a saturated calomel electrode as a reference electrode. With 1 mol L-1 H2SO4The solution is used as an electrolyte solution, and the potential window range is-1 to 0V.
FIG. 5 is a cycle Curve (CV) of NPC at different scan rates. It can be seen that the CV curve is a very regular bi-layer rectangular-like shape, with the integrated area and peak current of the CV curve increasing gradually as the scan rate increases, but as the scan rate increases to 200 mV s-1Even to 500 mV s-1The shape of the curve remains substantially unchanged, indicating that the electrode material has a very good volume-doubling rate, a fast response and low polarization in the electrochemical process.
FIG. 6 is the specific capacitance of NPC at different current densities. The specific capacitances of the porous carbon materials were calculated to be 358F/g, 345F/g, 336F/g, 323F/g, 320F/g and 316F/g at current densities of 1A/g, 2A/g, 3A/g, 5A/g, 7A/g and 10A/g, respectively. The material has higher specific capacitance and wide potential window, has potential of being used as an electrode material of a super capacitor, and is consistent with the test result of the cyclic voltammetry curve.
FIG. 7 is an alternating current impedance diagram of the nitrogen-doped pepper residue biomass porous carbon material prepared by the invention, wherein the frequency range is 100 kHz-0.2 Hz. It can be seen that, in the high-frequency region, the impedance represented by the intercept of the impedance spectrum on the real axis, i.e. the equivalent series internal resistance, is composed of the resistance of the electrolyte, the contact resistances among the activated carbon particles and between the electrode active material and the current collector; the impedance 45-degree curve of the intermediate frequency region represents the characteristic of Warburg diffusion impedance, namely semi-infinite diffusion of ions to a pore structure of a porous biomass carbon material-electrolyte interface; in a low-frequency area, a more vertical curve is approximately parallel to a virtual axis, the lower equivalent series resistance of the nitrogen-doped capsicum residue biomass porous carbon material is shown, and the nitrogen-doped capsicum residue biomass porous carbon material has good capacitance characteristics, so that the electrochemical energy storage performance and the conductivity of the electrode material are improved by nitrogen doping.
In conclusion, the invention takes the capsicum residue as the raw material, urea and potassium hydroxide as the nitrogen source and the activating agent respectively, the biomass porous carbon material precursor is prepared through impregnation, aging and heating, and then the nitrogen-doped capsicum residue biomass porous carbon material is obtained through high-temperature calcination in the nitrogen atmosphere, and the material shows higher specific capacitance and excellent volume-doubling rate, so the material can be used as the electrode material of the supercapacitor. The nitrogen-doped pepper residue biomass porous carbon material disclosed by the invention is simple in preparation route, easy to operate, low in cost, safe, efficient, green and environment-friendly, can realize large-scale production, and has potential application prospects as a supercapacitor electrode material.
Drawings
FIG. 1 is a field emission scanning electron microscope picture of the biomass porous carbon material prepared by the invention.
FIG. 2 is an X-ray diffraction spectrum of the biomass porous carbon material prepared by the invention.
FIG. 3 shows N of the biomass porous carbon material prepared by the invention2The attached drawing is sucked and removed.
FIG. 4 is a pore size distribution diagram of a biomass porous carbon material prepared by the present invention.
FIG. 5 shows that the electrode of the biomass porous carbon material prepared by the invention is 1 mol L-1 H2SO4At different scanning rates in the electrolyte solutionCyclic voltammogram.
FIG. 6 shows that the electrode of the biomass porous carbon material prepared by the invention is 1 mol L-1 H2SO4Constant current charge and discharge curve diagram under different current density in electrolyte solution.
FIG. 7 is an AC impedance diagram of a biomass porous carbon material prepared by the present invention.
Detailed Description
The preparation of the biomass porous carbon material and the preparation and electrochemical properties of the electrode material thereof are further described in detail by specific examples.
Instruments and reagents used: CHI660B electrochemical workstation (shanghai chenhua instruments) for electrochemical performance testing; an electronic balance (beijing sidoris instruments ltd) for weighing the medicine; SEM (Ultra Plus, CarlZeiss, Germany) field emission scanning electron microscopy was used for morphology characterization of materials; urea (Tianjin far chemical reagent Co., Ltd.), potassium hydroxide (national drug group chemical reagent), acetylene black (Sa Yang Tan Sha graphite factory, Hunan province), paprika (purchased from Gancu county, Gansu province), glassy carbon electrode (Shanghai Zhongwei New materials Co., Ltd.). The water used in the experiment process is secondary distilled water, and the reagents used in the experiment are analytically pure.
Examples
(1) Preparing a nitrogen-doped pepper residue biomass porous carbon material: 5g of the pepper residue was soaked in 120 mL of a solution containing 5g of urea and 2.5 g of potassium hydroxide, and the mixture was continuously stirred for 30 min, further sonicated for 4 h, and then aged at room temperature for 8 h. Then the mixed liquid is put into an oil bath and continuously stirred and evaporated at 70 ℃ to become viscous, and then dried in an oven at 70 ℃ to form a carbon precursor. Then the carbon precursor is put into a tube furnace and is put in a nitrogen atmosphere for 5 ℃ min -1The temperature rise rate of (2) is increased to 450 ℃ and kept for 30 min, and then increased to 750 ℃ and kept for 2 h. After natural cooling to room temperature, the obtained black solid was ground into powder and washed with 1M HCl solution to remove impurities, then washed with secondary water to neutrality, collected by suction filtration, and dried at 70 ℃.
(2) Preparing a nitrogen-doped pepper residue biomass porous carbon electrode: : 4.7 mg (85 percent and 15 percent respectively by mass) of mixed solid powder of the nitrogen-doped pepper residue biomass porous carbon material and acetylene black is added into 0.4 mL of Nafion solution with the mass fraction of 0.25 wt% to be ultrasonically dispersed to form suspension. Then 6. mu.L of the suspension was dropped on the surface of a glassy carbon electrode by using a pipette gun, and the suspension was dried at room temperature and used for testing.
(3) And (3) electrochemical performance testing: a three-electrode system is formed by taking a nitrogen-doped pepper residue biomass porous carbon material as a working electrode, a platinum net as a counter electrode and a saturated calomel electrode as a reference electrode. With 1 mol L-1 H2SO4The solution is used as an electrolyte solution, and the potential window range is-1-0V. Origin 8.0 software was used for mapping. The constant current test result shows that when the current density is 1A/g, the specific capacitance of the electrode material can reach 358F/g, which indicates that the material has higher specific capacitance and wide potential window and has the potential of being used as a capacitor electrode material.
Claims (5)
1. A preparation method of a nitrogen-doped pepper residue biomass porous carbon material comprises the following steps:
(1) extracting clean Capsici fructus powder with ethanol at 70 deg.C, removing capsaicin and aliphatic hydrocarbon to obtain Capsici fructus residue, oven drying, and grinding into powder;
(2) soaking the pepper residues in a mixed solution of urea and potassium hydroxide, stirring and performing ultrasonic treatment, aging at room temperature for 6-8 hours, continuously stirring and evaporating at 60-80 ℃ to make the pepper residues become viscous, and drying to form a carbon precursor;
(3) placing the carbon precursor in a tube furnace in nitrogen atmosphere at 5 deg.C for min-1Heating to 400-500 ℃ at the heating rate, keeping the temperature for 20-40 min, and then heating to 700-800 ℃ for 1-2 h; and naturally cooling to room temperature, grinding the obtained black solid into powder, washing the powder with HCl solution, washing the powder with secondary water to be neutral, performing suction filtration, collecting and drying to obtain the nitrogen-doped pepper residue biomass porous carbon material.
2. The method for preparing a nitrogen-doped capsicum residue biomass porous carbon material according to claim 1, wherein the method comprises the following steps: in the step (1), the drying temperature is 60-80 ℃.
3. The method for preparing a nitrogen-doped capsicum residue biomass porous carbon material according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the capsicum residue to the urea to the potassium hydroxide is 1:1: 0.5.
4. The method for preparing a nitrogen-doped capsicum residue biomass porous carbon material according to claim 1, wherein the method comprises the following steps: in the step (2), the drying temperature is 60-80 ℃.
5. The use of the nitrogen-doped capsicum residue biomass porous carbon material prepared by the method as claimed in claim 1 as an electrode material of a supercapacitor.
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| CN202210479619.XA CN114751394A (en) | 2022-05-05 | 2022-05-05 | Preparation of nitrogen-doped pepper residue biomass porous carbon material and application of nitrogen-doped pepper residue biomass porous carbon material as electrode material |
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