CN114044506B - 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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- 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
- H01G11/24—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
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- 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
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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 biomass powder to obtain a heat treatment product; PCl is put into 5 、NH 4 Cl、CS 2 Adding the mixture into a reaction kettle filled with a chlorine-containing organic solvent, stirring and reacting for 1-5 hours at the temperature of 100-200 ℃ and the pressure of 1-2MPa, adding a heat treatment product, stirring for 3-15 hours at normal temperature, centrifuging, washing, drying, and finally performing heat treatment under the protection of inert gas to obtain the polyatomic co-doped porous carbon material. The multi-atom co-doped porous carbon material is applied to super capacitors. The multi-atom co-doped porous carbon material 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 used as an electrode material of a commercial supercapacitor, has high power density, ideal long-cycle performance and fast charge and fast discharge performance, and is the most main electrode material for the current supercapacitor research. The porous carbon material undergoes ion adsorption/desorption at the surface of these electrode materials, thereby generating an electric current. At present, commercial carbon materials such as activated carbon, carbon nano tubes, carbon fibers and the like all have the characteristic of large specific surface area, however, the carbon materials with large specific surface area cannot represent the high or low specific capacitance, a large number of ineffective pores lead to the fact that ions cannot be adsorbed/desorbed, the specific capacitance of the carbon materials is reduced, meanwhile, the larger specific surface area also reduces the conductivity of the carbon materials in the electrode, a large number of commercial capacitor carbons are added, the migration rate of electrons in the super capacitor is improved, the mass specific content of the porous carbon materials in the electrode is further reduced, and the specific capacitance of the porous carbon materials is reduced.
The introduction of hetero atoms can change the electrochemical performance of a carbon material, as disclosed in patent application No. 201610132668.0, a convenient preparation method of biomass-based nitrogen-doped active carbon is disclosed, a pretreated biomass raw material is put into a reactor, mixed gas containing ammonia gas, water vapor and inert gas is introduced, the temperature is maintained at 700-900 ℃, the reaction is continued for 1-3 h, and 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, firstly, the graphene oxide is subjected to nitric acid steam pore-forming and surface activation in a high-temperature kettle, then the graphene oxide is put into an ammonium ion aqueous solution with higher concentration, a large amount of ammonium ions are adsorbed on the surface of mesoporous graphene oxide under heterogeneous self-assembly, and finally the nitrogen-doped mesoporous carbon material is prepared by heat treatment, wherein the nitrogen content is only 1-10wt%. However, the bio-based activated carbon only introduces one heteroatom, has low doping content and has limited influence on the electrochemical performance of the activated carbon material applied to the super capacitor.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a nitrogen-phosphorus-sulfur-chlorine co-doped carbon material, a preparation method thereof and application thereof in super capacitors.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a multi-atom co-doped porous carbon material is doped with nitrogen, phosphorus, sulfur and chlorine simultaneously, 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 polyatomic co-doped porous carbon material has a specific surface area of 260-1900m 2 /g。
The present invention also provides a method for preparing the polyatomic co-doped porous carbon material, which comprises the following steps:
(1) Under the protection of inert gas, carrying out heat treatment on biomass powder to obtain a heat treatment product;
(2) PCl is put into 5 、NH 4 Cl、CS 2 Adding the mixture into a reaction kettle filled with a chlorine-containing organic solvent, and stirring the mixture at 100-200 ℃ and 1-2MPa for reaction for 1-5h;
(3) Adding the heat treatment product in the step (1) into the reaction product obtained in the step (2), and stirring for 3-15h at normal temperature;
(4) Centrifuging, washing and drying the mixture obtained in the step (3), and then performing heat treatment under the protection of inert gas to obtain the polyatomic co-doped porous carbon material.
In the above preparation method, preferably, in the step (1), the temperature of the heat treatment is 600-1300 ℃, and the heat treatment time is 0.5-4h. In the heat treatment temperature range, the prepared multi-atom co-doped porous carbon material can improve the specific capacitance of the material.
The preparation method of the invention adopts the preparation method for reducing CS 2 The adsorption amount of the solvent is used, the biomass powder is subjected to pretreatment, and meanwhile, after the biomass powder is subjected to pretreatment, a certain pore can be formed, so that more active sites can be provided for doping multiple elements.
Further, it is preferable that the heat treatment temperature is 1100-1200 ℃, the heat treatment temperature is too high, and a part of the pore structure collapses, so that the specific surface is reduced, resulting in a reduction in the cycle stability during the cycle, and the heat treatment temperature is too low, resulting in an unstable chemical bond of the doping element, resulting in a reduction in the cycle stability.
In the above preparation method, 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 preparation method, preferably, in the step (2), PCl 5 、NH 4 Cl、CS 2 The mass ratio of the chlorine-containing organic solvent is 1: (0.5-2): (5-20): (2-20).
In the above 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 above preparation method, preferably, in the step (4), the temperature of the heat treatment is 600-1300 ℃, and the heat treatment time is 0.5-6h.
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 super capacitors as a general inventive concept.
Compared with the prior art, the invention has the advantages that:
(1) The multi-atom co-doped porous carbon material is doped with nitrogen, phosphorus, sulfur and chlorine, the nitrogen atoms and the carbon atoms have similar atomic radiuses, the nitrogen atoms are one more electron than the carbon atoms, and the doping of the nitrogen atoms can provide a free electron for the carbon material as a carrier, so that the electrochemical performance of the material is improved; the doping of phosphorus atoms causes the lattice of carbon in the carbon material to be distorted, the defect sites are increased, the increased defect sites often have higher electron cloud density, the conductivity of the carbon material is increased, and the defect sites with high electron cloud density reduce the catalytic reaction energy barrier and have higher reactivity; the doping of sulfur atoms can further adjust the structure of the carbon material to obtain pore channels and surface structures in a specific range; the specific gravity of chlorine atoms is larger, 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 when the material is applied to the supercapacitor.
(2) According to the preparation method, biomass materials are used as carbon sources, solvents and salts containing hetero atoms are creatively mixed and pre-reacted, so that hetero atom compounds are mutually and uniformly dispersed to form a certain weak chemical bond, the mixed carbon is mixed and carbonized with biomass carbon, the lattice structure of graphite is changed through doping of various hetero atoms, a large number of pores are formed through misplacement doping of atoms, and the co-doped carbon materials with high specific capacitance and high specific surface area can be prepared without adding etching agents such as acid and alkali, the doping amount of the hetero atoms can reach more than 20%, and the preparation method is simple, low in cost and beneficial to realization of scale and industrialization.
(3) The multi-atom co-doped porous carbon material is simultaneously doped with nitrogen, phosphorus, sulfur and chlorine, and the co-doped atoms improve the conductivity of the supercapacitor by changing the types and the distribution of active groups on the surface of the carbon material; and the different types of heteroatom functional groups on the carbon material can inhibit the aggregation of carbon particles, improve the wettability of electrolyte and improve the ion transmission path, so that the service life of the capacitor can be prolonged.
(4) The polyatomic co-doped porous carbon material is used as an active material of a supercapacitor, has excellent electrochemical performance, and has a specific capacitance of 113F/g under the current test condition of 1A/g.
Drawings
Fig. 1 is an SEM image of a multi-atom co-doped porous carbon material prepared in example 4 of the present invention.
FIG. 2 is a graph of pore volume versus pore diameter data for a polyatomic co-doped porous carbon material prepared in example 4 of the present invention.
FIG. 3 is a graph of cycle data for the polyatomic co-doped porous carbon materials and commercial capacitive carbon (YP 50-F) prepared in examples 4-5 of the present invention as electrode materials for supercapacitors.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms 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 be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Comparative example:
the porous carbon material of this comparative example was prepared as follows:
(1) Cleaning 300g of peanut shell product, airing, crushing and sieving with a 40-mesh sieve for standby;
(2) Under the protection of argon gas, carrying out heat treatment on the biomass powder crushed in the step (1) for 2 hours at 1000 ℃ to obtain a heat treatment product;
(3) 10g of PCl are weighed respectively 5 NH of 20g 4 Cl and 50g CS 2 Slowly adding the mixture into a beaker containing 20g of dichloromethane, and stirring the mixture at normal temperature for 4 hours to obtain a mixture;
(4) Taking 50g of the heat treatment product in the step (2), slowly adding the 50g of the heat treatment product into the mixture obtained in the step (3), and stirring the mixture for 10 hours at normal temperature;
(5) And (3) putting the mixed product obtained in the step (4) into a tube furnace, performing heat treatment at 1200 ℃ for 2 hours, and collecting a final product to obtain the porous carbon material.
Example 1:
the preparation method of the multi-atom co-doped porous carbon material comprises the following steps:
(1) Cleaning 300g of peanut shell product, airing, crushing and sieving with a 40-mesh sieve for standby;
(2) Under the protection of argon gas, carrying out heat treatment on the biomass powder crushed in the step (1) for 2 hours at 1000 ℃ to obtain a heat treatment product;
(3) Respectively weighing 10g PCl 5 、20g NH 4 Cl and 50g CS 2 Slowly adding the mixture into a high-pressure stainless steel kettle containing 20g of dichloromethane, stirring for 4 hours at 120 ℃ and 2MPa, adding 50g of the heat treatment product in the step (2), and stirring for 10 hours at normal temperature;
(4) Collecting the mixture obtained in the step (3) into a centrifuge tube, centrifuging for 5min at 5000r/min, sucking away the upper 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 at 80 ℃ for 6h to obtain the solid product;
(5) And (3) under the protection of argon, placing the solid product obtained in the step (4) into a tubular furnace, performing heat treatment at 800 ℃ for 5 hours, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-800.
Example 2:
the preparation method of the polyatomic co-doped porous carbon material of this embodiment is basically the same as that of embodiment 1, except that the heat treatment conditions of step (5) are different, and the preparation process of step (5) is as follows: and (3) under the protection of argon, placing the solid product prepared in the step (4) into a tubular furnace, performing heat treatment for 4 hours at 900 ℃, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-900.
Example 3:
the preparation method of the polyatomic co-doped porous carbon material of this embodiment is basically the same as that of embodiment 1, except that the heat treatment conditions of step (5) are different, and the preparation process of step (5) is as follows: and (3) under the protection of argon, placing the solid product prepared in the step (4) into a tubular furnace, performing heat treatment at 1000 ℃ for 4 hours, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-1000.
Example 4:
the preparation method of the polyatomic co-doped porous carbon material of this embodiment is basically the same as that of embodiment 1, except that the heat treatment conditions of step (5) are different, and the preparation process of step (5) is as follows: and (3) placing the solid product prepared in the step (4) into a tube furnace under the protection of argon, performing heat treatment at 1100 ℃ for 3 hours, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-1100.
As shown in FIG. 1, the SEM image of the porous carbon material prepared in this example shows that the particle size of the multi-atom co-doped porous carbon material is relatively uniform, about 0.5-1 μm, and the morphology is mostly spherical.
The pore volume-pore diameter data graph of the porous carbon prepared in this example is shown in fig. 2. As can be seen from FIG. 2, the pore size of CCI is concentrated in the range of 0.8-2 nm and 2.8-5.5 nm, and this pore size range is just the effective pore size for ion adsorption/desorption, thus bringing about excellent specific capacitance performance of the material.
Example 5:
the preparation method of the polyatomic co-doped porous carbon material of this embodiment is basically the same as that of embodiment 1, except that the heat treatment conditions of step (5) are different, and the preparation process of step (5) is as follows: and (3) under the protection of argon, placing the solid product prepared in the step (4) into a tube furnace, performing heat treatment at 1200 ℃ for 2 hours, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-1200.
Example 6:
the preparation method of the polyatomic co-doped porous carbon material of this embodiment is basically the same as that of embodiment 1, except that the heat treatment conditions of step (5) are different, and the preparation process of step (5) is as follows: and (3) under the protection of argon, placing the solid product prepared in the step (4) into a tubular furnace, performing heat treatment at 1300 ℃ for 1h, and collecting the final product to obtain the N/P/S/Cl co-doped porous carbon material, which is named CCl-1300.
The N/P/S/Cl co-doped porous carbon materials prepared in examples 1 to 6 and the porous carbon materials prepared in comparative examples were subjected to a carbon chlorine sulfur phosphorus element ratio test elemental analyzer (EDX 4500P) and a specific surface area test (JB-1), and the results are shown in Table 1 below.
Table 1: carbon, chlorine, sulfur and phosphorus content in mass percent in carbon-phosphorus-sulfur-chlorine porous carbon material at different heat treatment temperatures
As can be seen from the comparison example, the doping proportion of nitrogen, sulfur, phosphorus and chlorine is obviously lower than that of other examples, and chlorine is not successfully doped, which shows that the stirring reaction at the high pressure of 1-2MPa at the temperature of 100-200 ℃ is favorable for doping atoms such as nitrogen, sulfur, phosphorus, chlorine and the like, especially for doping chlorine atoms in a carbon material.
The N/P/S/Cl co-doped porous carbon materials prepared in examples 1 to 6 and commercial capacitive carbon (YP-50F) were added to the electrode materials of the super capacitor in an amount of 90% of the total mass of the electrode materials, respectively, and prepared into super capacitors, and specific capacitances were measured using a three electrode method at a current density of 1A/g as shown in Table 1. The cyclic performance data for the capacitors prepared in example 4, example 5, and commercial capacitive carbon (YP 50-F) were measured and are shown in fig. 3.
As can be seen from the specific capacitance data of Table 1, the specific capacitance of commercial capacitive carbon (YP-50F) was 85.67F/g, and the specific capacitances of examples 3 (CCl-1000) -6 (CCl-1300) were all superior to the specific capacitance of commercial capacitive carbon (YP-50F), wherein the specific capacitance of example 5 reached 114F/g.
As can be seen from fig. 3, the porous carbon materials co-doped with nitrogen, phosphorus, sulfur and chlorine of example 4 (CCl-1100) and example 5 (CCl-1200) have stable pore structure, excellent specific surface area and stable chemical bond after high temperature treatment, and the cycling performance is obviously superior to that of commercial capacitor carbon (YP-50F) while the high specific capacitance is possessed, and in particular, the super capacitor prepared from the porous carbon material of example 5 (CCl-1200) still maintains more than 90% of capacity after 1000 cycles.
Claims (7)
1. The preparation method of the polyatomic co-doped porous carbon material is characterized in that the porous carbon material is doped with nitrogen, phosphorus, sulfur and chlorine at the same time, wherein the doping amount of the nitrogen is 6-12 wt%, the doping amount of the phosphorus is 1-8 wt%, the doping amount of the sulfur is 5-16 wt%, and the doping amount of the chlorine is 6-13 wt%;
the preparation method comprises the following steps:
(1) Under the protection of inert gas, carrying out heat treatment on biomass powder to obtain a heat treatment product; the heat treatment temperature is 600-1300 ℃, and the heat treatment time is 0.5-4h;
(2) PCl is put into 5 、NH 4 Cl、CS 2 Adding the mixture into a reaction kettle filled with a chlorine-containing organic solvent, and stirring the mixture at 100-200 ℃ and 1-2MPa for reaction for 1-5h;
(3) Adding the heat treatment product in the step (1) into the reaction product obtained in the step (2), and stirring for 3-15h at normal temperature;
(4) Centrifuging, washing and drying the mixture obtained in the step (3), and then performing heat treatment under the protection of inert gas to obtain the polyatomic co-doped porous carbon material.
2. The method according to claim 1, wherein in the step (2), the chlorine-containing organic solvent is one or more of chlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane, chloroethane, chloropropane, and chlorobutane.
3. The process according to claim 1, wherein in step (2), PCl 5 、NH 4 Cl、CS 2 The mass ratio of the chlorine-containing organic solvent is 1: (0.5-2): (5-20): (2-20).
4. The method according to claim 1, wherein in the step (3), the mass ratio of the biomass powder heat-treated product to the reaction product of the step (2) is 1: (0.2-2).
5. The process according to any one of claims 1 to 4, wherein in the step (4), the heat treatment is carried out at a temperature of 600 to 1300℃for a time of 0.5 to 6 hours.
6. The method according to claim 1, wherein the porous carbon material has a specific surface area of 260 to 1900m 2 /g。
7. Use of a polyatomic co-doped porous carbon material prepared by the preparation method of any one of claims 1-6 in a supercapacitor.
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