CN114758900A - Biomass porous carbon material, preparation method thereof and supercapacitor - Google Patents
Biomass porous carbon material, preparation method thereof and supercapacitor Download PDFInfo
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention relates to the technical field of supercapacitor materials, and particularly discloses a biomass porous carbon material, a preparation method thereof and a supercapacitor. Wherein the porous carbon material is prepared from canary chrysanthemum, comprises carbon and doping elements, and has a specific surface area of 1580m2/g～2100m2Per gram, average pore diameter of 2.70-3.40 nm, pore volume of 0.80cm3/g～1.10cm3Between/g. The doping elements in the biomass porous carbon material are doped in the carbon material in situ, so that the biomass porous carbon material has the characteristic of uniform distribution of the doping elements, forms a porous structure with a stable structure and has a large specific surface area, and shows excellent capacitance performance.
Description
Technical Field
The invention relates to the technical field of supercapacitor materials, in particular to a biomass porous carbon material, a preparation method thereof and a supercapacitor.
Background
The super capacitor is also called as an electrochemical capacitor, and has the advantages of high power density, high charging and discharging speed, long cycle life and the like, so that the super capacitor has wide application prospect in the field of energy storage. Carbon materials such as activated carbon, graphene, carbon nanotubes, carbon aerogel and the like are used as electrode materials of supercapacitors due to the characteristics of good electrical conductivity, large specific surface area and the like. By doping other elements, the capacitance performance of the carbon material can be effectively improved. However, the existing carbon material has the problems of high impurity element doping difficulty, uneven doped element distribution, poor doping effect, high cost and the like.
Disclosure of Invention
One of the purposes of the embodiments of the present invention is to provide a biomass porous carbon material, which aims to solve the problems of high doping difficulty, poor doping effect, high doping cost, etc. of the carbon material.
In order to achieve the above purpose, the embodiment of the present invention adopts the following technical solutions:
a biomass porous carbon material is prepared from Hypericum japonicum Kimura, comprises carbon and doping elements, and has a specific surface area of 1580m2/g～2100m2Per gram, average pore diameter of 2.70 nm-3.40 nm, pore volume of 0.80cm3/g～1.10cm3Between/g.
In one possible embodiment, the doping element comprises nitrogen and oxygen.
In one possible embodiment, the biomass porous carbon material has a mesoporous and microporous structure therein;
and/or the biomass porous carbon material has trace element imprinting.
Compared with the prior art, the biomass porous carbon material provided by the embodiment of the invention is prepared from the golden-silk chrysanthemum, on one hand, the golden-silk chrysanthemum has a porous structure, on the other hand, the golden-silk chrysanthemum contains flavone, a plurality of amino acids, vitamins and trace elements, the prepared biomass porous carbon material comprises carbon and doping elements, and the doping elements are doped in the carbon material in situ, so that the biomass porous carbon material has the characteristic of uniform distribution of the doping elements, forms a porous structure with a stable structure and has a large specific surface area, and therefore, the biomass porous carbon material shows excellent capacitance performance.
Another object of the embodiments of the present invention is to provide a method for preparing a biomass porous carbon material, which adopts the following specific technical scheme:
a preparation method of the biomass porous carbon material comprises the following steps:
carbonizing golden-silk chrysanthemum to obtain a crude carbon material;
and mixing the crude carbon material with an activating agent, and then sequentially performing activation, washing and drying treatment to obtain the biomass porous carbon material.
In a possible embodiment, the carbonization treatment comprises heating the golden filigree to 800-850 ℃ in a non-reaction atmosphere at a heating rate of 1-10 ℃/min, and keeping the temperature for 2.0-4.0 h.
In one possible embodiment, the activation treatment comprises placing the crude carbon material and the activating agent in a non-reaction atmosphere, heating to 350-550 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 0.5-1.0 h, then continuing to heat to 750-850 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 1.0-3.0 h.
In a possible embodiment, the washing treatment comprises a step of washing the product obtained by the activation with acid and deionized water in sequence.
In one possible embodiment, the acid comprises any one of hydrochloric acid, sulfuric acid, phosphoric acid.
In one possible embodiment, the mass ratio of the crude carbon material to the activator charge is 1:3 to 1: 5;
and/or the activator comprises at least one of potassium hydroxide, sodium hydroxide and zinc chloride.
Compared with the prior art, the preparation method of the biomass porous carbon material provided by the embodiment of the invention has the characteristics of simple process, stable appearance, high yield, high product purity and the like of the obtained product, and the obtained biomass porous carbon material has the advantages of higher specific surface area, more stable material appearance structure, uniform distribution of doping elements, and capability of providing more electrochemical active sites and electrochemical reaction stability.
The third objective of the embodiments of the present invention is to provide a super capacitor. The technical scheme is as follows:
the supercapacitor comprises a working electrode, wherein the working electrode comprises the biomass porous carbon material or the biomass porous carbon material prepared by the preparation method of the biomass porous carbon material.
Compared with the prior art, the electrode of the supercapacitor provided by the embodiment of the invention comprises the biomass porous carbon material, and the biomass porous carbon material has a larger specific surface area, more electrochemical active sites, a uniformly distributed doping element and a more stable material morphology structure, so that the electrochemical properties such as capacitance property, rate capability, cycling stability and the like are more excellent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is an X-ray diffraction pattern of a biomass porous carbon material provided in examples 1 to 3 of the present invention;
fig. 2 is a raman spectrum characterization chart of the biomass porous carbon material provided in examples 1 to 3 of the present invention;
FIG. 3 is an SEM representation of the biomass porous carbon material provided in examples 1 and 2 of the present invention;
FIG. 4 is an EDS spectrum of a biomass porous carbon material provided in example 2 of the present invention;
fig. 5 is a nitrogen adsorption-desorption isotherm of the biomass porous carbon material provided in examples 1 to 3 of the present invention;
fig. 6 is a BJH pore size distribution diagram of a biomass porous carbon material provided in examples 1 to 3 of the present invention;
FIG. 7 is a cyclic voltammetry test curve of a supercapacitor made from the biomass porous carbon material provided in example 2 of the present invention;
fig. 8 is a constant current charge and discharge test curve of the biomass porous carbon material provided in example 2 of the present invention at different current densities;
fig. 9 is a constant current charge and discharge test curve of the biomass porous carbon material provided in embodiment 2 of the present invention at different current densities;
FIG. 10 is a rate curve of a biomass porous carbon material provided in example 2 of the present invention;
FIG. 11 is an AC impedance curve of a biomass porous carbon material provided in example 2 of the present invention;
FIG. 12 is a graph of the cycling stability of a biomass porous carbon material provided in example 2 of the present invention;
FIG. 13 is a cyclic voltammetry curve of a symmetrical supercapacitor assembled from the biomass porous carbon material provided in example 2 of the present invention;
fig. 14 is a constant current charge and discharge test curve of the biomass porous carbon nickel cobalt sulfur material provided in embodiment 2 of the present invention under different current densities;
fig. 15 is a constant current charge and discharge test curve of the biomass porous carbon material provided in example 2 of the present invention at different current densities;
FIG. 16 is a graph of energy density and power density of a symmetrical supercapacitor assembled from the biomass porous carbon material provided in example 2 of the present invention;
fig. 17 is a cycle stability diagram of a symmetrical supercapacitor assembled by the biomass porous carbon material provided in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of a biomass porous carbon material, which comprises the following steps:
(1) carbonizing the golden-silk chrysanthemum to obtain the crude carbon material.
In the step (1), the golden cypress contains flavone, a plurality of amino acids, vitamins and trace elements, and is carbonized, and nitrogen, oxygen, trace elements and the like are distributed in situ in the obtained crude carbon material. Before carbonizing the golden cypress, cleaning the golden cypress, or carbonizing the clean golden cypress so as to eliminate the influence of other impurities on the performance of the prepared biomass porous carbon material. The golden cypress can be washed by deionized water, ethanol and the like, and then dried in a forced air drying oven at the drying temperature of 50-80 ℃, so that the influence of free water, ethanol and the like on the surface of the golden cypress on carbonization can be eliminated.
In some embodiments, the carbonization treatment comprises heating the golden filigree chrysanthemum to 800-850 ℃ in a non-reaction atmosphere at a heating rate of 1-10 ℃/min, and keeping the temperature for 2.0-4.0 h. The non-reactive atmosphere referred to herein includes any atmosphere of nitrogen, argon, helium, or the like. After the constant temperature treatment, natural cooling to room temperature can be adopted, and a quenching mode can also be adopted.
(2) And mixing the crude carbon material with an activating agent, and then sequentially performing activation, washing and drying treatment to obtain the biomass porous carbon material.
In the step (2), the feeding mass ratio of the coarse carbon material to the activating agent is 1: 3-1: 5. The activating agent is excessive so as to fully activate the crude carbon material and promote the complete transformation of the crude carbon material, thereby improving the purity of the product and improving the uniformity of the morphology and the pore structure of the product. In some embodiments, the activation treatment comprises placing the crude carbon material and the activating agent in a non-reactive atmosphere to heat to 350-550 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 0.5-1.0 h, then continuing to heat to 750-850 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 1.0-3.0 h. In some embodiments, the coarse carbon material and the activating agent are mixed before activation treatment, so that the coarse carbon material and the activating agent are uniformly mixed to improve the uniformity of the activation treatment process, and the morphology of the activated material is effectively regulated. In some embodiments, the activator comprises any one of potassium hydroxide, sodium hydroxide, and zinc chloride, which have an etching, pore-forming effect on the crude carbon material to further modify the pore structure in the crude carbon material.
In some embodiments, the material obtained after the activation treatment is subjected to acid washing and water washing sequentially, and finally subjected to drying treatment. Among them, hydrochloric acid, sulfuric acid or phosphoric acid may be used for the acid washing. In some embodiments, hydrochloric acid at a mass concentration of 10% to 20% may be employed. And through acid washing, materials obtained through activation treatment are neutralized, so that the influence of alkalinity of the materials obtained through activation treatment on the target product biomass porous carbon material is avoided. The water washing can be deionized water washing and suction filtration, and the residual acid can be washed clean by the water washing, so that the target product is neutral. In the drying treatment, the target product obtained by water washing is transferred to an air-blast drying oven and dried at the temperature of 50-100 ℃. After activation treatment and washing treatment, the doped trace elements can be eluted, trace element prints are remained on the surface and inside of the target product biomass porous carbon material, and the trace element prints are beneficial to the biomass porous carbon material to exert more excellent electrochemical performance. In the invention, trace element imprinting refers to that trace elements fall off from the biomass porous carbon material after acid washing and water washing, so that three-dimensional space structures capable of accommodating the trace elements are formed on the surface and inside of the biomass porous carbon material, and the three-dimensional space structures are the same as or similar to the shapes and volumes of the trace elements.
Based on the preparation method, the biomass porous carbon material is obtained, and comprises carbon and doping elements, wherein the doping elements comprise nitrogen and oxygen, the doping elements are doped in the carbon in situ, and meanwhile, the specific surface area of the biomass porous carbon material is 1580m2/g～2100m2Per gram, average pore diameter of 2.70-3.40 nm, pore volume of 0.80cm3/g～1.10cm3Between/g, the porous structure comprises a mesoporous structure and a microporous structure, thereby being beneficial to the exertion of electrochemical performance.
Based on the obtained biomass porous carbon material, the embodiment of the invention also provides a supercapacitor.
The supercapacitor comprises a working electrode, and the working electrode comprises the biomass porous carbon material. In some embodiments, the active material of one of the working electrodes of the supercapacitor comprises the biomass porous carbon material described above, while the other working electrode is activated carbon, graphene oxide, nitrogen-doped graphene oxide, graphene, other biomass-derived carbon materials, or the like, when the resulting supercapacitor is an asymmetric supercapacitor. In some embodiments, the biomass porous carbon material is attached to the surface of nickel foam, and the nickel foam is used as a current collector. In some embodiments, the electrolyte of the supercapacitor is from 1mol/L to 6mol/L KOH.
To better illustrate the technical solution of the present invention, the following is further explained by a plurality of embodiments.
Example 1
A preparation method of a biomass porous carbon material comprises the following steps:
(1) the golden-silk chrysanthemum was washed with deionized water, and then transferred to a forced air drying oven for drying treatment at 60 ℃.
(2) And (2) placing the golden-silk chrysanthemum obtained in the step (1) in a tubular furnace, introducing nitrogen, heating to 800 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the temperature at 800 ℃ for 3.0h, and naturally cooling to room temperature to obtain the crude carbon material.
(3) And (3) fully grinding 0.5g of the crude carbon material obtained in the step (2) and 1.5g of potassium hydroxide to uniformly mix the crude carbon material and the potassium hydroxide to obtain a mixed material, then transferring the mixed material to a tubular furnace, introducing nitrogen, heating to 400 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, preserving heat at 400 ℃ for 0.5h, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat at 800 ℃ for 2.0h, and naturally cooling to room temperature to obtain the precursor.
(4) Soaking the precursor in a hydrochloric acid solution with the mass concentration of 20%, standing for 24h, repeatedly performing suction filtration and washing by using deionized water until the liquid obtained by suction filtration is neutral, transferring the solid matter obtained by suction filtration into a forced air drying oven, drying at 60 ℃, obtaining a sample, and collecting the sample for later use.
Example 2
A preparation method of a biomass porous carbon material comprises the following steps:
(1) the golden-silk chrysanthemum was washed with deionized water, and then transferred to a forced air drying oven, and dried at 80 ℃.
(2) And (2) placing the golden-silk chrysanthemum obtained in the step (1) in a tube furnace, introducing nitrogen, heating to 850 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat for 4.0h at 850 ℃, and then naturally cooling to room temperature to obtain the crude carbon material.
(3) And (3) fully grinding 0.5g of the crude carbon material obtained in the step (2) and 2.0g of potassium hydroxide to uniformly mix the crude carbon material and the potassium hydroxide to obtain a mixed material, then transferring the mixed material into a tubular furnace, introducing nitrogen, heating to 400 ℃ at a heating rate of 2 ℃/min in the nitrogen atmosphere, preserving heat for 0.5h at 400 ℃, heating to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 2.0h at 800 ℃, and naturally cooling to room temperature to obtain the precursor.
(4) Soaking the precursor in a hydrochloric acid solution with the mass concentration of 10%, standing for 24h, repeatedly performing suction filtration and washing by using deionized water until the liquid obtained by suction filtration is neutral, transferring the solid matter obtained by suction filtration into a forced air drying oven, drying at 60 ℃, obtaining a sample, and collecting the sample for later use.
Example 3
A preparation method of a biomass porous carbon material comprises the following steps:
(1) the golden-silk chrysanthemum was washed with deionized water, and then transferred to a forced air drying oven, and dried at 50 ℃.
(2) And (2) placing the golden-silk chrysanthemum obtained in the step (1) in a tubular furnace, introducing nitrogen, heating to 800 ℃ at the heating rate of 10 ℃/min in the nitrogen atmosphere, preserving the temperature at 800 ℃ for 3.0h, and naturally cooling to room temperature to obtain the crude carbon material.
(3) And (3) fully grinding 0.5g of the crude carbon material obtained in the step (2) and 2.5g of potassium hydroxide to uniformly mix the crude carbon material and the potassium hydroxide to obtain a mixed material, then transferring the mixed material to a tubular furnace, introducing nitrogen, heating to 400 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, preserving heat at 400 ℃ for 0.5h, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat at 800 ℃ for 2.0h, and naturally cooling to room temperature to obtain the precursor.
(4) Soaking the precursor in a hydrochloric acid solution with the mass concentration of 15%, standing for 24h, repeatedly performing suction filtration and washing by using deionized water until the liquid obtained by suction filtration is neutral, transferring the solid matter obtained by suction filtration into a forced air drying oven, drying at 60 ℃ to obtain a sample, and collecting the sample for later use.
Characterization and electrochemical testing were performed on the samples obtained in examples 1 to 3:
the phase and the crystal structure of the sample were characterized by X-ray diffraction, as shown in fig. 1, in which the abscissa represents a 2-fold angle value (2Theta) and the ordinate represents an Intensity value (Intensity).
As is clear from fig. 1, the samples of examples 1, 2 and 3 all exhibited broad diffraction peaks at about 24 ° and 43 °, and the (002) and (101) diffraction crystal planes of graphite were identified, indicating that the samples obtained in examples 1 to 3 were all amorphous carbon.
The graphitization degree and the defects of the samples of examples 1 to 3 were characterized by Raman spectroscopy (Raman), and the results are shown in fig. 2, in which the abscissa represents Raman shift (Raman shift) and the ordinate represents Intensity value (Intensity).
As can be seen from FIG. 2, the D peak (1350 cm) for the three examples-1) Corresponding to defective graphitic or amorphous carbon, peak G (1580 cm)-1) Corresponding to the characteristics of the graphite layer, the ratio of the peak intensities of the graphite layer and the graphite layer can indirectly reflect the graphitization degree or the defect degree of the carbon material. Wherein I of the sample of example 2D/IGThe value of 0.89 indicates the highest degree of graphitization and the best conductivity.
The morphology of the samples of example 1 and example 2 was characterized by Scanning Electron Microscopy (SEM), as shown in fig. 3, wherein the left panel of fig. 2 is the characterization result of example 1 and the right panel of fig. 2 is the characterization result of example 2.
As can be seen from fig. 3, the samples obtained in examples 1 and 2 have a large number of micropores and mesopores uniformly distributed therein.
Surface elements of the sample obtained in example 2 were characterized by a Transmission Electron Microscope (TEM), and an EDS spectrum was obtained, with the results shown in fig. 4.
As can be seen from fig. 4, C, N, O elements were uniformly distributed on the surface of the sample, indicating that the sample was N, O co-doped carbon material, which was in-situ doped due to N, O elements derived from the camomile material.
From this, it can be confirmed that the samples obtained in examples 1 to 3 are biomass porous carbon materials, and are doped with nitrogen and oxygen in situ.
The specific surface area test is carried out on the confirmed biomass porous carbon material. Specifically, the nitrogen adsorption-desorption isotherm test was performed by the BET analyzer, and the results are shown in fig. 5, the abscissa represents the Relative pressure (Relative pressure) and the ordinate represents the amount of adsorption (Quantity adsorbed).
As can be seen from the view in figure 5,the samples of examples 1 to 3 all showed a classical type IV sorption-desorption isotherm, i.e. in the low pressure region (P/P)00.0-0.1) the adsorption rises rapidly and the curve is convex upward, indicating that the sample has abundant micropores while in the middle pressure zone (P/P)00.3-0.8) and high pressure zone (P/P)00.9-1.0) a clear hysteresis loop of H4 type appeared, and the curve did not show an adsorption termination plateau, indicating that the sample had a large number of mesopores. The specific surface areas of the samples of examples 1 to 3 were calculated to be 1580.70m by the BET model, respectively2/g、2062.58m2/g、2099.44m2And the catalyst provides more active sites and is beneficial to improving the electrochemical performance of the material.
The results of the BJH Pore size distribution test are shown in FIG. 6, in which the abscissa represents the Pore width (Pore width) and the ordinate represents the Pore volume distribution (dV/dP).
As can be seen from FIG. 6, the pore size distribution and pore structure characteristics of the sample are reflected, and it can be seen that the pore size of the material is microporous and mesoporous, the average pore size is 2.70 nm-3.40 nm, and the pore volume is 0.80cm3/g～1.10cm3The ratio of the carbon atoms to the carbon atoms is between/g.
The biomass porous carbon material obtained in example 2 was used as a positive electrode material, and electrochemical performance test was performed according to the following experimental procedures.
The preparation method of the working electrode comprises the following steps:
(1) cutting the 110-mesh foamed nickel into sheets of 1.0cm × 1.5cm × 0.1cm, sequentially ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10min, and vacuum drying for later use.
Mixing the prepared biomass porous carbon material with Ketjen black and Polytetrafluoroethylene (PVDF) according to the mass ratio of 8:1:1, preparing to form slurry by taking N-methyl pyrrolidone as a solvent, and stirring for 2 hours in a stirrer to uniformly mix the slurry. Coating the slurry on a foamed nickel current collector of 1.0cm multiplied by 1.5cm, drying the sample at 60 ℃ for 24h, and tabletting under the pressure of 10MPa to obtain the working electrode.
The test system adopts a three-electrode test system, the reference electrode is Hg/HgO, the counter electrode is a platinum sheet, the electrolyte is 6M/L KOH, and the test is carried out by adopting a CHI660E type electrochemical workstation.
The Cyclic Voltammetry (CV) test is performed at-1.0-0.0V, the CV curve is scanned at a rate of 10 mV/s-500 mV/s, and the test result is shown in FIG. 7, wherein the abscissa represents voltage (Potential) and the ordinate represents specific capacity (Current sensitivity).
As is evident from FIG. 7, the CV curve profile shape remained essentially unchanged as the scan rate increased until the CV curve profile remained quasi-rectangular in shape as the scan rate increased to 500mV/s, indicating that the electrodes prepared had good rate capability.
The constant current charge and discharge test is performed at different current densities, and the test results are shown in fig. 8 and fig. 9, in which the abscissa represents Time (Time) and the ordinate represents voltage (Potential).
From fig. 8 and 9, it can be seen that the constant current charge and discharge curve is in a quasi-triangular shape, and when the current density is increased to 50A/g, the sample shows extremely small voltage drop, which proves that the sample has good reversibility and tiny internal resistance, and still has highly reversible charge and discharge capacity under high current density.
Specific capacities at different currents were calculated from fig. 8 and 9, and a rate graph was plotted, and the result is shown in fig. 10, in which the abscissa represents the Current density (Current density) and the ordinate represents the Specific capacitance (Specific capacitance).
As can be seen from FIG. 10, the calculated specific capacitances were 322F/g, 294F/g, 231F/g, 222F/g, 208F/g, 195F/g, and 180F/g at current densities of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g, 30A/g, and 50A/g, respectively. The current density is increased from 1A/g to 20A/g, the specific capacitance is kept to be 69%, and the material has good rate performance.
To obtain more electrochemical properties for the sample of example 2, 10-2Hz～10-5Alternating current impedance (EIS) characterization was performed at Hz frequency and the results are shown in fig. 11.
As can be seen from FIG. 11, it is apparent that the sample exhibits an extremely small internal resistance (R) in the high frequency region of the samples0.52 Ω), indicating that the sample has excellent conductivity; arc radius pole of sampleSmall, indicating that the sample has a low charge transfer resistance RctAnd the electron transfer rate is effectively ensured. In the low frequency region, the curve is nearly parallel to the Y-axis, indicating that it has a small ion diffusion impedance.
In order to verify the Cycle stability of the biomass porous carbon material obtained in example 2, after the symmetrical supercapacitor was assembled, a Cycle stability test was performed at a current density of 10A/g, and the result is shown in fig. 12, in which the abscissa represents the number of cycles (Cycle number) and the ordinate represents the Specific capacitance (Specific capacitance).
As can be seen from fig. 12, after 5500 cycles, the specific capacity was 99.6% of the initial specific capacity, indicating excellent cycling stability.
To verify the practical application performance of the sample obtained in example 2, the sample obtained in example 2 was used as a working electrode, Ag/AgCl was used as a reference electrode, a platinum sheet was used as a counter electrode, and 1mol/L Na was used2SO4For the electrolyte, a supercapacitor was assembled and tested using an electrochemical workstation model CHI 660E.
The cyclic voltammetry test is performed at 0-1.8V, the CV curve is performed at a scan rate of 10-500 m V/s, and the test result is shown in FIG. 13.
As can be seen from fig. 13, the CV curve profile shape remains substantially constant as the scan rate increases.
The constant current charge and discharge tests were performed at different current densities, and the test results are shown in fig. 14 and 15.
As can be seen from the constant current charge and discharge curves of fig. 14 and 15, the sample has a very small voltage drop, and also demonstrates good reversibility and slight internal resistance.
Fig. 16 is a graph of Energy density (Energy density) versus power density (power density) for a symmetrical supercapacitor made from the sample of example 2.
According to the graph 16, a high energy density of 25.3Wh/kg is obtained when the power density is 225W/kg, which shows that the biomass porous carbon material obtained in the embodiment has a relatively excellent energy density, and is beneficial to large-scale application of a supercapacitor by using the biomass porous carbon material as a working electrode of the supercapacitor.
FIG. 17 is a graph of constant current charging and discharging performance 40000 times at a high current density of 5A/g for the symmetrical supercapacitor made from the sample of example 2, wherein the abscissa represents the number of cycles (Cycle number), the ordinate represents capacity retention (capacity retention) on the left axis, and the ordinate represents coulombic efficiency (coulombic efficiency) on the right axis.
As can be seen from fig. 17, the device remained 96.9% of the initial capacity after 40000 cycles, and the coulombic efficiency was close to 98.5%, indicating that the device had excellent cycling stability.
According to the performance tests of the embodiments 1 to 3, the biomass porous carbon material obtained by activating the golden filigree is found to have excellent capacitance performance, and the biomass porous carbon material has potential application potential in the field of electrochemical energy storage.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the equivalent modifications or substitutions within the technical scope of the present invention, and these modifications or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The biomass porous carbon material is characterized by being prepared from golden-silk chrysanthemum, comprising carbon and doping elements, and having a specific surface area of 1580m2/g～2100m2Per gram, average pore diameter of 2.70-3.40 nm, pore volume of 0.80cm3/g～1.10cm3Between/g.
2. The biomass porous carbon material of claim 1, wherein the doping element comprises nitrogen and oxygen.
3. The biomass porous carbon material according to any one of claims 1 to 2, wherein the biomass porous carbon material has a mesoporous and microporous structure therein;
and/or the biomass porous carbon material has trace element imprinting.
4. A method for producing a biomass porous carbon material according to any one of claims 1 to 3, comprising the steps of:
carbonizing golden-silk chrysanthemum to obtain a crude carbon material;
and mixing the crude carbon material with an activating agent, and then sequentially performing activation, washing and drying treatment to obtain the biomass porous carbon material.
5. The method for preparing the biomass porous carbon material according to claim 4, wherein the carbonization treatment comprises heating the golden filigree to 800-850 ℃ at a heating rate of 1-10 ℃/min in a non-reactive atmosphere, and keeping the temperature for 2.0-4.0 h.
6. The method for producing a biomass porous carbon material according to claim 4, wherein the activation treatment comprises heating the crude carbon material and the activating agent in a non-reactive atmosphere at a heating rate of 1 ℃/min to 10 ℃/min to 350 ℃ to 550 ℃ for a constant temperature of 0.5h to 1.0h, and then continuing to heat at a heating rate of 1 ℃/min to 10 ℃/min to 750 ℃ to 850 ℃ for a constant temperature of 1.0h to 3.0 h.
7. The method for producing a biomass porous carbon material according to claim 4, wherein the washing treatment comprises a step of washing the product obtained by the activation with an acid and deionized water in this order.
8. The method for producing a biomass porous carbon material according to claim 7, wherein the acid comprises any one of hydrochloric acid, sulfuric acid, and phosphoric acid.
9. The method for preparing a biomass porous carbon material according to any one of claims 4 to 8, wherein the mass ratio of the crude carbon material to the activator charge is 1:3 to 1: 5;
and/or the activator comprises at least one of potassium hydroxide, sodium hydroxide and zinc chloride.
10. A supercapacitor comprising a working electrode, wherein the working electrode comprises the biomass porous carbon material according to any one of claims 1 to 3, or the biomass porous carbon material prepared by the method for preparing the biomass porous carbon material according to any one of claims 4 to 9.
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