CN114044506A - Polyatomic co-doped porous carbon material, preparation method thereof and application thereof in super capacitor - Google Patents
Polyatomic co-doped porous carbon material, preparation method thereof and application thereof in super capacitor 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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/84—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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A multi-atom co-doped porous carbon material is simultaneously doped with nitrogen, phosphorus, sulfur and chlorine, wherein the doping amount of nitrogen is 6-12 wt%, the doping amount of phosphorus is 1-8 wt%, the doping amount of sulfur is 5-16 wt%, and the doping amount of chlorine is 6-13 wt%. The preparation method comprises the following steps: under the protection of inert gas, carrying out heat treatment on the biomass powder to obtain a heat treatment product; mixing PCl5、NH4Cl、CS2Adding into a reaction kettle containing a chlorine-containing organic solvent, stirring and reacting at 100-200 ℃ and 1-2MPa for 1-5h, adding the heat treatment product, stirring at normal temperature for 3-15h, centrifuging, washing, drying, and finally, under the protection of inert gasAnd carrying out thermal treatment to obtain the polyatomic co-doped porous carbon material. The polyatomic co-doped porous carbon material is applied to a super capacitor. The polyatomic co-doped porous carbon material disclosed by the invention is applied to a super capacitor, and can improve the electrochemical performance of the super capacitor.
Description
Technical Field
The invention belongs to the field of preparation of carbon materials, and particularly relates to a nitrogen-phosphorus-sulfur-chlorine co-doped porous carbon material and a preparation method and application thereof.
Background
The porous carbon material is taken as an electrode material of a commercial super capacitor, has high power density, ideal long-cycle performance and fast charge and discharge performance, and is the most main electrode material of the current super capacitor research. The porous carbon material causes ion adsorption/desorption on the surface of these electrode materials, thereby generating an electric current. The carbon materials with large specific surface area, such as activated carbon, carbon nanotubes, carbon fibers and the like, cannot represent the specific capacitance, and the large number of ineffective pores cause that ions cannot be adsorbed/desorbed, so that the specific capacitance of the carbon materials is reduced, and meanwhile, the large specific surface area also reduces the electric conductivity of the carbon materials in the electrodes, so that the addition of a large amount of commercial capacitance carbon is used for increasing the migration rate of electrons in the super capacitor, further reducing the mass specific content of the porous carbon materials in the electrodes, and reducing the specific capacitance of the porous carbon materials.
Introducing heteroatoms can change the electrochemical performance of the carbon material, for example, patent application No. 201610132668.0 discloses a convenient preparation method of biomass-based nitrogen-doped activated carbon, which comprises the steps of putting a pretreated biomass raw material into a reactor, introducing mixed gas containing ammonia gas, water vapor and inert gas, maintaining the temperature at 700-900 ℃, and continuously reacting for 1-3 hours, wherein the nitrogen content is only 0.9-3 wt%. Application number 201911058018.6 discloses a preparation method and application of a nitrogen-doped mesoporous carbon material, wherein graphene oxide is used as a raw material, amine salt is used as a nitrogen source, the graphene oxide is subjected to nitric acid steam pore-forming and surface activation in a high-temperature kettle, then the graphene oxide is placed into an ammonium ion aqueous solution with high concentration, a large number of ammonium ions are adsorbed on the surface of the mesoporous graphene oxide under heterogeneous self-assembly, and finally the nitrogen-doped mesoporous carbon material is prepared through heat treatment, wherein the nitrogen content is only 1-10 wt%. However, the bio-based activated carbon only introduces one kind of heteroatom, and the doping content is low, so that the electrochemical performance of the activated carbon material applied to the super capacitor is limited.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a nitrogen-phosphorus-sulfur-chlorine co-doped carbon material, a preparation method thereof and application thereof in a super capacitor.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the multi-atom co-doped porous carbon material is doped with nitrogen, phosphorus, sulfur and chlorine at the same time, wherein the doping amount of nitrogen is 6-12 wt%, the doping amount of phosphorus is 1-8 wt%, the doping amount of sulfur is 5-16 wt%, and the doping amount of chlorine is 6-13 wt%.
Preferably, the specific surface area of the porous carbon material is 260-1900m2/g。
As a general inventive concept, the present invention also provides a preparation method of the polyatomic co-doped porous carbon material, including the following steps:
(1) under the protection of inert gas, carrying out heat treatment on the biomass powder to obtain a heat treatment product;
(2) mixing PCl5、NH4Cl、CS2Adding the mixture into a reaction kettle filled with a chlorine-containing organic solvent, and stirring and reacting for 1-5h at the temperature of 100 ℃ and 200 ℃ and under the pressure of 1-2 MPa;
(3) adding the heat treatment product in the step (1) into the reaction product after the step (2), and stirring for 3-15h at normal temperature;
(4) and (4) centrifuging, washing and drying the mixture obtained in the step (3), and then carrying out heat treatment under the protection of inert gas to obtain the polyatomic co-doped porous carbon material.
In the preparation method, preferably, in the step (1), the heat treatment temperature is 600-1300 ℃, and the heat treatment time is 0.5-4 h. In the temperature range of the heat treatment, the prepared polyatomic co-doped porous carbon material can improve the specific capacitance of the material.
The preparation method of the invention adopts the technical proposal of reducing CS2For adsorption of solventsThe biomass powder is pretreated, and a certain pore can be formed after the pretreatment of the biomass powder, so that more active sites can be provided for doping multiple elements.
Further, it is preferable that the heat treatment temperature is 1100-1200 ℃, that is, too high heat treatment temperature collapses part of the pore structure to lower the specific surface area, resulting in a decrease in cycle stability during the cycle, and that too low heat treatment temperature destabilizes the chemical bond of the doping element, resulting in a decrease in cycle stability.
Preferably, in the step (2), the chlorine-containing organic solvent is one or more of chlorobenzene, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, chloroethane, chloropropane and chlorobutane.
In the above production process, preferably, in the step (2), PCl5、NH4Cl、CS2And the mass ratio of the chlorine-containing organic solvent is 1: (0.5-2): (5-20): (2-20).
In the preparation method, preferably, in the step (3), the mass ratio of the biomass powder heat treatment product to the reaction product in the step (2) is 1: (0.2-2).
In the preparation method, preferably, in the step (4), the heat treatment temperature is 600-1300 ℃, and the heat treatment time is 0.5-6 h.
As a general inventive concept, the invention also provides an application of the polyatomic co-doped porous carbon material or the polyatomic co-doped porous carbon material prepared by the preparation method in a supercapacitor.
Compared with the prior art, the invention has the advantages that:
(1) the polyatomic co-doped porous carbon material is doped with nitrogen, phosphorus, sulfur and chlorine at the same time, the nitrogen atom and the carbon atom have similar atomic radiuses, the nitrogen atom has one electron more than the carbon atom, and the doping of the nitrogen atom can provide a free electron for the carbon material to serve as a carrier, so that the electrochemical performance of the material is improved; the doping of phosphorus atoms causes the distortion of the crystal lattice of carbon in the carbon material, the number of defect sites is increased, the increased defect sites have higher electron cloud density, the conductivity of the carbon material is increased, the defect sites with high electron cloud density reduce the catalytic reaction energy barrier, and the carbon material has higher reaction activity; the structure of the carbon material can be further adjusted by doping sulfur atoms to obtain a pore channel and a surface structure in a specific range; the specific gravity of the chlorine atoms is large, so that the tap density of the carbon material can be further improved, the volume energy density of the material can be improved, and the electrochemical performance of the supercapacitor can be improved by applying the material to the supercapacitor.
(2) According to the invention, a biomass material is used as a carbon source, a solvent containing heteroatoms and salt are creatively mixed and pre-reacted, so that heteroatom compounds are uniformly dispersed and form a certain weak chemical bond, then the mixture is mixed and carbonized with biomass carbon, the graphite lattice structure is changed by doping of a plurality of different heteroatoms, a large number of pores are formed by dislocation doping of atoms, and a co-doped carbon material with high specific capacitance and high specific surface area can be prepared without adding etching agents such as acid and alkali, wherein the doping amount of the heteroatoms can reach more than 20%.
(3) The multi-atom co-doped porous carbon material is simultaneously doped with nitrogen, phosphorus, sulfur and chlorine, and the commonly doped atoms improve the conductivity of the supercapacitor by changing the types and distribution of active groups on the surface of the carbon material; besides, different heteroatom functional groups on the carbon material can inhibit agglomeration of carbon particles, improve the wettability of the electrolyte and improve an ion transmission path, so that the service life of the capacitor can be prolonged.
(4) The polyatomic co-doped porous carbon material disclosed by the invention is used as an active material of a supercapacitor, the electrochemical performance is excellent, and the specific capacitance under the current test condition of 1A/g can reach 113F/g.
Drawings
Fig. 1 is an SEM image of the polyatomic co-doped porous carbon material prepared in example 4 of the present invention.
Fig. 2 is a pore volume-pore diameter data graph of the polyatomic co-doped porous carbon material prepared in example 4 of the present invention.
FIG. 3 is a graph of cycle data for polyatomic co-doped porous carbon material and commercial capacitive carbon (YP50-F) prepared in examples 4-5 of the present invention as electrode materials for supercapacitors.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Comparative example:
the porous carbon material of this comparative example was prepared as follows:
(1) cleaning, airing and crushing 300g of peanut shell product, and sieving the crushed product with a 40-mesh sieve for later use;
(2) under the protection of argon gas, carrying out heat treatment on the pulverized biomass powder obtained in the step (1) at 1000 ℃ for 2 hours to obtain a heat-treated product;
(3) 10g of PCl were weighed out separately520g of NH4Cl and 50g of CS2Slowly adding into a beaker filled with 20g of dichloromethane, and stirring for 4 hours at normal temperature to obtain a mixture;
(4) taking 50g of the heat treatment product in the step (2), slowly adding the heat treatment product into the mixture obtained in the step (3), and stirring for 10 hours at normal temperature;
(5) and (4) putting the mixed product obtained in the step (4) into a tubular furnace, carrying out heat treatment at 1200 ℃ for 2h, and collecting the final product to obtain the porous carbon material.
Example 1:
the preparation method of the polyatomic co-doped porous carbon material comprises the following steps:
(1) cleaning, airing and crushing 300g of peanut shell product, and sieving the crushed product with a 40-mesh sieve for later use;
(2) under the protection of argon gas, carrying out heat treatment on the pulverized biomass powder obtained in the step (1) at 1000 ℃ for 2 hours to obtain a heat-treated product;
(3) 10g of PCl were weighed out separately5、20g NH4Cl and 50g CS2Slowly adding into a high-pressure stainless steel kettle containing 20g of dichloromethane, stirring at 120 ℃ and 2MPa for 4h, adding 50g of the heat treatment product in the step (2), and stirring at normal temperature for 10 h;
(4) collecting the mixture obtained in the step (3) into a centrifuge tube, centrifuging for 5min at 5000r/min, sucking away the upper layer liquid, adding deionized water into the centrifuge tube, repeatedly washing for 10 times, discarding the supernatant, collecting the solid product in the centrifuge tube, and vacuum-drying the solid product at 80 ℃ for 6h to obtain the solid product;
(5) and (3) under the protection of argon, putting the solid product obtained in the step (4) into a tube furnace, carrying out heat treatment at 800 ℃ for 5h, and collecting a final product to obtain the N/P/S/Cl co-doped porous carbon material, which is marked as CCl-800.
Example 2:
the preparation method of the polyatomic co-doped porous carbon material in this embodiment is substantially the same as that in embodiment 1, except that the heat treatment conditions in step (5) are different, and the preparation process in step (5) is as follows: and (3) under the protection of argon, putting the solid product prepared in the step (4) into a tube furnace, carrying out heat treatment at 900 ℃ for 4h, and collecting a final product to obtain the N/P/S/Cl co-doped porous carbon material, which is marked as CCl-900.
Example 3:
the preparation method of the polyatomic co-doped porous carbon material in this embodiment is substantially the same as that in embodiment 1, except that the heat treatment conditions in step (5) are different, and the preparation process in step (5) is as follows: and (3) under the protection of argon, putting the solid product prepared in the step (4) into a tube furnace, carrying out heat treatment at 1000 ℃ for 4h, and collecting a final product to obtain the N/P/S/Cl-codoped porous carbon material, which is marked as CCl-1000.
Example 4:
the preparation method of the polyatomic co-doped porous carbon material in this embodiment is substantially the same as that in embodiment 1, except that the heat treatment conditions in step (5) are different, and the preparation process in step (5) is as follows: and (3) under the protection of argon, putting the solid product prepared in the step (4) into a tube furnace, carrying out heat treatment at 1100 ℃ for 3h, and collecting a final product to obtain the N/P/S/Cl-codoped porous carbon material, which is marked as CCl-1100.
As shown in fig. 1 of the SEM image of the porous carbon material prepared in this embodiment, as can be seen from fig. 1, the particle size of the polyatomic co-doped porous carbon material is relatively uniform, about 0.5 to 1 μm, and most of the porous carbon material is spherical particles.
The pore volume-pore diameter data of the porous carbon prepared in this example is shown in fig. 2. As can be seen from FIG. 2, the pore diameter of CCI is concentrated in the range of 0.8-2 nm and 2.8-5.5 nm, which is the effective pore diameter for ion generation and adsorption/desorption, thereby providing the material with excellent specific capacitance performance.
Example 5:
the preparation method of the polyatomic co-doped porous carbon material in this embodiment is substantially the same as that in embodiment 1, except that the heat treatment conditions in step (5) are different, and the preparation process in step (5) is as follows: and (3) under the protection of argon, putting the solid product prepared in the step (4) into a tube furnace, carrying out heat treatment at 1200 ℃ for 2h, and collecting a final product to obtain the N/P/S/Cl-codoped porous carbon material, which is marked as CCl-1200.
Example 6:
the preparation method of the polyatomic co-doped porous carbon material in this embodiment is substantially the same as that in embodiment 1, except that the heat treatment conditions in step (5) are different, and the preparation process in step (5) is as follows: and (3) under the protection of argon, putting the solid product prepared in the step (4) into a tube furnace, carrying out heat treatment at 1300 ℃ for 1h, and collecting a final product to obtain the N/P/S/Cl-codoped porous carbon material, which is marked as CCl-1300.
The N/P/S/Cl-codoped porous carbon materials prepared in examples 1 to 6 and the porous carbon material prepared in comparative example were subjected to an element analyzer for the Phosphorus carboniclosus element ratio test (EDX4500P), a specific surface area test (JB-1), and the results are shown in Table 1 below.
Table 1: the mass percentages of carbon, chlorine, sulfur and phosphorus in the carbon-phosphorus-sulfur-chlorine porous carbon material at different heat treatment temperatures
As can be seen from the comparative example, the doping ratio of nitrogen, sulfur and phosphorus elements is obviously lower than that of other examples, and chlorine elements are not successfully doped, which shows that the stirring reaction at 100-200 ℃ and 1-2MPa is helpful for doping nitrogen, sulfur, chlorine and other atoms, especially chlorine atoms in the carbon material.
The N/P/S/Cl-codoped porous carbon material prepared in examples 1 to 6 and commercial capacitance carbon (YP-50F) were added to the electrode material of the supercapacitor, respectively, in amounts of 90% of the total mass of the electrode material, and prepared into a supercapacitor, and specific capacitances measured using a three-electrode method at a current density of 1A/g were as shown in Table 1. The measured cycle performance data for the capacitors made from example 4, example 5 and commercial capacitance carbon (YP50-F) is shown in fig. 3.
As can be seen from the specific capacitance data in Table 1, the specific capacitance of the commercial capacitor carbon (YP-50F) was 85.67F/g, and the specific capacitances of example 3(CCl-1000) -example 6(CCl-1300) were all superior to that of the commercial capacitor carbon (YP-50F), with the specific capacitance of example 5 reaching 114F/g.
As can be seen from fig. 3, after the nitrogen, phosphorus, sulfur and chlorine co-doped porous carbon materials of example 4(CCl-1100) and example 5(CCl-1200) are subjected to high temperature treatment, the porous carbon materials have stable pore structures, excellent specific surface areas and stable chemical bonds, and the cycling performance of the porous carbon materials is obviously better than that of the commercial capacitance carbon (YP-50F) while the porous carbon materials have high specific capacitance, and especially, the supercapacitor prepared from the porous carbon material of example 5(CCl-1200) still maintains more than 90% of capacity after 1000 cycles.
Claims (9)
1. The polyatomic co-doped porous carbon material is characterized in that nitrogen, phosphorus, sulfur and chlorine are doped in the porous carbon material at the same time, wherein the doping amount of nitrogen is 6 wt% -12 wt%, the doping amount of phosphorus is 1 wt% -8 wt%, the doping amount of sulfur is 5 wt% -16 wt%, and the doping amount of chlorine is 6 wt% -13 wt%.
2. The polyatomic co-doped porous carbon material of claim 1, wherein the specific surface area of the porous carbon material is 260-1900m2/g。
3. The preparation method of the polyatomic co-doped porous carbon material according to claim 1 or 2, comprising the following steps:
(1) under the protection of inert gas, carrying out heat treatment on the biomass powder to obtain a heat treatment product;
(2) mixing PCl5、NH4Cl、CS2Adding the mixture into a reaction kettle filled with a chlorine-containing organic solvent, and stirring and reacting for 1-5h at the temperature of 100 ℃ and 200 ℃ and under the pressure of 1-2 MPa;
(3) adding the heat treatment product in the step (1) into the reaction product after the step (2), and stirring for 3-15h at normal temperature;
(4) and (4) centrifuging, washing and drying the mixture obtained in the step (3), and then carrying out heat treatment under the protection of inert gas to obtain the polyatomic co-doped porous carbon material.
4. The method as set forth in claim 3, wherein the heat treatment temperature in step (1) is 600 ℃ and 1300 ℃, and the heat treatment time is 0.5-4 h.
5. The preparation method according to claim 3, wherein in the step (2), the chlorine-containing organic solvent is one or more of chlorobenzene, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, chloroethane, chloropropane and chlorobutane.
6. The method according to claim 3, wherein in the step (2), PCl5、NH4Cl、CS2And the mass ratio of the chlorine-containing organic solvent is 1: (0.5-2): (5-20): (2-20).
7. The method according to claim 3, wherein in the step (3), the mass ratio of the heat-treated product of the biomass powder to the reaction product of the step (2) is 1: (0.2-2).
8. The method according to any one of claims 3-7, wherein in step (4), the heat treatment temperature is 600-1300 ℃, and the heat treatment time is 0.5-6 h.
9. Use of the polyatomic co-doped porous carbon material according to any one of claims 1 to 2 or the polyatomic co-doped porous carbon material prepared by the preparation method according to any one of claims 3 to 8 in a supercapacitor.
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