CN115818638A - Nitrogen-sulfur-doped hierarchical porous carbon and preparation method thereof - Google Patents
Nitrogen-sulfur-doped hierarchical porous carbon and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010426 asphalt Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- 238000000498 ball milling Methods 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract description 2
- 150000003841 chloride salts Chemical class 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 238000009826 distribution Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002149 hierarchical pore Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of carbon material preparation, and particularly relates to nitrogen-sulfur doped hierarchical porous carbon and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Fully mixing petroleum asphalt, a nitrogen-sulfur doped modifier, activated alkali and chloride salt to obtain a mixture; (2) Calcining the mixture obtained in the step (1) in a protective atmosphere, and cooling to room temperature after calcination to obtain a calcined material; (3) And (3) washing and filtering the calcined material obtained in the step (2), and fully drying to obtain the hierarchical porous carbon. The hierarchical porous carbon uses high-temperature petroleum asphalt and chloride as raw materials, the chloride is mixed at high temperature and melted into liquid, and a uniform reaction environment is provided for the nitrogen-sulfur doped porous carbon, so that the prepared hierarchical porous carbon has a uniform doping effect and an adjustable pore structure, and the hierarchical porous carbon is used as a positive electrode material of a lithium ion capacitor and shows good specific capacitance and circulation stability.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to nitrogen-sulfur doped hierarchical porous carbon and a preparation method thereof.
Background
The porous carbon has the characteristics of wide raw material source, high chemical stability, large specific surface area and the like, and is widely applied to the fields of energy storage, catalysis and the like. Whether the hierarchical arrangement of pores is reasonable is an important evaluation parameter for measuring the application potential of porous carbon. In electrochemical energy storage applications, micropores (< 2 nm) are mainly used as electrolyte ion storage spaces, and mesopores (2-50 nm) and macropores (> 100 nm) are used as ion transmission channels and electrolyte storage spaces. Thus, a suitable microporous-mesoporous-macroporous hierarchical configuration is key to the good electrochemical performance of porous carbon in electrochemical energy storage devices. Meanwhile, in supercapacitors, the nature of energy storage is that the surface undergoes non-faradaic reactions, which requires a large active surface area for the porous carbon.
The molten salt synthesis method is generally applied to the synthesis of inorganic materials, and has attracted wide attention because of the advantages of relatively simple process, high phase purity of the synthesized materials, relatively uniform chemical components and the like. Inert molten salts are generally classified into two groups, one is a metal or alloy melt, and the other is a compound group including oxides and ionic salts. The mixed chloride salt has the characteristics of low vapor pressure and easy hydrolysis, and is the first choice as the molten salt flux. For example, in CN107697914A, potassium chloride is used as a salt template, and nitrogen-enriched biomass is subjected to one-step high-temperature carbonization to obtain a porous carbon material with nitrogen doping property. However, it is difficult to obtain a good hierarchical pore structure only by the molten salt, and a single salt etching is not sufficient to generate a large active specific surface area, so that introduction of a more powerful pore-forming agent must be considered. Strong bases such as potassium hydroxide are widely used by researchers due to their outstanding pore-forming ability, but Kong Duowei introduced by potassium hydroxide is smaller than 1nm micropores, which are not beneficial for the entry of electrolyte ions, so that the doping ratio and pore-forming pore distribution range need to be properly controlled to obtain a better hierarchical pore structure.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, it is an object of the present invention to provide a doped porous carbon material with a rich active surface area, hierarchical pore configuration.
The technical scheme of the invention is as follows:
a preparation method of nitrogen-sulfur doped hierarchical porous carbon comprises the following steps:
s1, co-dissolving trithiocyanuric acid and asphalt in an organic non-polar solvent, stirring for 0.5-2 hours at normal temperature, heating in a water bath, stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
s2, weighing the dark brown particles obtained in the step S1 and potassium hydroxide according to the mass ratio of 1:3, mixing the dark brown particles and the potassium hydroxide with NaCl-KCl mixed inert salt, and transferring the mixture into a ball milling tank;
s3, adding ethanol serving as a ball milling dispersing agent into a ball milling tank, setting ball milling parameters, and performing ball milling for 4-8 hours to obtain a ball milling product;
s4, separating the ball-milled product, and drying in a forced air oven at 80 ℃ for one night;
s5, carbonizing the dried product separated in the step S4 in a tubular furnace, cleaning with deionized water after the carbonization is finished, and then performing suction filtration and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon.
Furthermore, the mass ratio of the trithiocyanuric acid to the asphalt is 1:1-1:5.
Further, the organic nonpolar solvent is one of toluene, hexane, xylene, carbon disulfide and carbon tetrachloride.
Further, the water bath heating temperature is 60-90 ℃.
Further, the mixing ratio of the dark brown particles and the mixed inert salt of the potassium hydroxide and the NaCl-KCl is 1:5, 1.
Furthermore, the mass ratio of NaCl to KCl in the NaCl-KCl inert mixed salt is 1:1.
Furthermore, the ball milling parameter is 400-600 r/min, and the forward rotation and the reverse rotation are alternately operated.
Further, the adopted carbonization temperature is 700-900 ℃, the carbonization time is kept for 1-3 h, nitrogen or argon is introduced as protective gas, and the carbonization temperature rise rate is 3-8 ℃/min.
The principle of the preparation method of the invention is as follows: the inert mixed salt provides a homogeneous reaction environment, and fully disperses the dopant and the carbon source precursor. When the temperature is raised to be higher than the melting point (658 ℃), the solid mixed salt is converted into the ionic liquid, and the sulfide and the nitride generated by decomposing the cyanuric acid as the dopant are dissociated and uniformly doped in the liquid phase. And the potassium hydroxide reacts with the precursor of the carbon source to release gases such as CO2 and the like at high temperature to generate a large number of micropores, and the micropores are dissociated under the action of molten salt and aggregated into proper mesopores and macropores, so that the hierarchical porous carbon with nitrogen-sulfur doped sites is obtained.
The beneficial effects of the invention are: the method endows the porous carbon with sufficient doping sites, which is favorable for improving the wettability of the porous carbon and electrolyte and simultaneously is favorable for improving the specific capacitance of the porous carbon. The highly cross-linked hierarchical porous structure can promote the transmission of ions, and thus has excellent electrochemical performance when applied to lithium ion capacitors.
Drawings
FIG. 1 is a nitrogen isothermal adsorption and desorption curve of example 1.
FIG. 2 is a nitrogen isothermal sorption and desorption curve of example 2.
FIG. 3 is a pore volume distribution plot for example 1.
Fig. 4 is a pore volume distribution plot for example 2.
FIG. 5 is a graph of the long cycle performance of examples 1 and 2.
FIG. 6 is a transmission electron microscope photograph of example 2.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and examples.
According to the invention, high-temperature petroleum asphalt is used as a precursor of a carbon source, and the porous carbon with the hierarchical porous structure is obtained through high-temperature activation under the action of mixed molten salt. When the temperature is raised to the melting point of the mixed salt, the solid salt is melted into high-purity ionic liquid, the precursor carbon source and the dopant are uniformly reacted in a liquid environment, the uniform doping effect is realized, and the alkaline activator plays a role in enhancing pore-forming. And in the cooling stage after the reaction is finished, the inert salt is recrystallized, the salt component remained in the carbon product is solidified into a template, and a layered pore distribution structure with macropores and mesopores is remained after cleaning. The cross-linked pore structure is beneficial to the rapid transmission of ions, so that the material has excellent capacity retention capacity under high rate; on the other hand, the surface doped with a proper amount of atoms can improve the affinity with the electrolyte and improve the storage capacity of the electrolyte in the electrode.
Example 1
The preparation method comprises the following steps:
(1) Dissolving cyanuric acid (0 g) and asphalt (1 g) in 10mL of toluene, stirring at normal temperature for 0.5-2 hours, heating in water bath at 60 ℃ and stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
(2) Weighing the product in the step (1) and potassium hydroxide according to the mass ratio of 1:3, mixing the product with NaCl and KCl mixed inert salt according to the mass ratio of 1;
(3) Adding 20mL of ethanol serving as a ball milling dispersing agent into the mixture obtained in the step (2), setting ball milling parameters and carrying out ball milling for 4-8 h;
(4) Separating the ball-milled product after the step (3) is finished, and drying in a forced air oven at 80 ℃ for one night;
(5) And (3) carbonizing the dried product separated in the step (4) in a tubular furnace at 800 ℃, washing with deionized water after the carbonization is completed, performing suction filtration and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon, and marking the hierarchical porous carbon as NSC-0-1.
As shown in FIG. 1, the nitrogen desorption isothermal adsorption test for NSC-0-1 reflects that the pores of NSC-0-1 are mainly microporous.
As shown in FIG. 3, which is a pore volume distribution plot for NSC-0-1, it is directly confirmed that the pore distribution of NSC-0-1 is dominated by micropores.
Example 2
The preparation method comprises the following steps:
(1) Dissolving cyanuric acid (0.33 g) and asphalt (1 g) in 10mL of toluene, stirring at normal temperature for 0.5-2 hours, heating in a water bath at 60 ℃ and stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
(2) Weighing the product in the step (1) and potassium hydroxide according to the mass ratio of 1:3, mixing the product with NaCl and KCl mixed inert salt according to the mass ratio of 1;
(3) Adding 20mL of ethanol serving as a ball milling dispersing agent into the mixture obtained in the step (2), setting ball milling parameters and carrying out ball milling for 4-8 h;
(4) Separating the ball-milled product after the step (3) is finished, and drying in a forced air oven at 80 ℃ for one night;
(5) And (3) carbonizing the dried product separated in the step (4) in a tubular furnace at 800 ℃, washing with deionized water after the carbonization is completed, performing suction filtration and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon, and marking the hierarchical porous carbon as NSC-1-3.
As shown in FIG. 2, the nitrogen isothermal adsorption and desorption test for NSC-1-3 reflects the hierarchical pore structure of NSC-1-3.
As shown in FIG. 4, which is a pore volume distribution plot for NSC-1-3, it is directly confirmed that NSC-1-3 has a distinct hierarchical pore structure, i.e., a certain micro-meso-macro pore hierarchical arrangement.
As shown in FIG. 5, the long cycle performance of NSC-0-1 is compared with that of NSC-1-3, which shows that the long cycle performance is obviously improved after the doping agent is added for modification.
As shown in FIG. 6, is an image of a single carbon sheet layer of NSC-1-3 under a high resolution transmission microscope, which was directly observed to have a graded pore configuration.
Example 3
The preparation method comprises the following steps:
(1) Dissolving trithiocyanuric acid (0.2 g) and asphalt (1 g) in 10mL of toluene, stirring at normal temperature for 0.5-2 hours, heating in water bath at 60 ℃ and stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
(2) Weighing the product in the step (1) and potassium hydroxide according to the mass ratio of 1:3, mixing the product with NaCl and KCl mixed inert salt according to the mass ratio of 1;
(3) Adding 20mL of ethanol serving as a ball milling dispersing agent into the mixture obtained in the step (2), setting ball milling parameters and carrying out ball milling for 4-8 h;
(4) Separating the ball-milled product after the step (3) is finished, and drying in a forced air oven at 80 ℃ for one night;
(5) And (3) carbonizing the dried product separated in the step (4) in a tubular furnace at 800 ℃, washing with deionized water after the carbonization is completed, performing suction filtration and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon, and marking as NSC-1-5.
Example 4
The preparation method comprises the following steps:
(1) Dissolving trithiocyanuric acid (1 g) and asphalt (1 g) in 10mL of toluene, stirring at normal temperature for 0.5-2 hours, heating in water bath at 60 ℃ and stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
(2) Weighing the product in the step (1) and potassium hydroxide according to the mass ratio of 1:3, mixing the product with NaCl and KCl mixed inert salt according to the mass ratio of 1;
(3) Adding 20mL of ethanol serving as a ball milling dispersing agent into the mixture obtained in the step (2), setting ball milling parameters and carrying out ball milling for 4-8 h;
(4) Separating the ball-milled product after the step (3) is finished, and drying in a forced air oven at 80 ℃ for one night;
(5) And (5) carbonizing the dried product separated in the step (4) in a tubular furnace at 800 ℃, cleaning the carbonized product by deionized water, performing suction filtration and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon, and marking the hierarchical porous carbon as NSC-1-1.
Claims (9)
1. The preparation method of the nitrogen-sulfur-doped hierarchical porous carbon is characterized by comprising the following steps of:
s1, co-dissolving trithiocyanuric acid and asphalt in an organic nonpolar solvent, stirring for 0.5-2 hours at normal temperature, heating in a water bath, stirring for 10-30 min until the solvent is completely volatilized, and separating out dark brown particles;
s2, weighing the dark brown particles obtained in the step S1 and potassium hydroxide according to the mass ratio of 1:3, mixing the dark brown particles and the potassium hydroxide with a NaCl-KCl mixed inert salt, and transferring the mixture into a ball milling tank;
s3, adding ethanol serving as a ball milling dispersing agent into a ball milling tank, setting ball milling parameters, and performing ball milling for 4-8 hours to obtain a ball milling product;
s4, separating the ball-milled product, and drying in a forced air oven at 80 ℃ for one night;
s5, carbonizing the dried product separated in the step S4 in a tubular furnace, washing with deionized water after the carbonization is completed, filtering, and drying to obtain the nitrogen-sulfur doped hierarchical porous carbon.
2. The method for preparing nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the mass ratio of the trithiocyanuric acid to the pitch is 1:1-1:5.
3. The method of claim 1, wherein the organic non-polar solvent is one of toluene, hexane, xylene, carbon disulfide, and carbon tetrachloride.
4. The preparation method of the nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the water bath heating temperature is 60-90 ℃.
5. The preparation method of nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the mass ratio of the dark brown particles to the potassium hydroxide mixed with the NaCl-KCl mixed inert salt is one of 1:5, 1, 10, 1, 15, 1.
6. The method for preparing the nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the mass ratio of NaCl to KCl in the NaCl-KCl inert mixed salt is 1:1.
7. The method for preparing nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the ball milling parameter is 400-600 r/min, and forward rotation and reverse rotation are alternately performed.
8. The preparation method of the nitrogen-sulfur-doped hierarchical porous carbon according to claim 1, wherein the carbonization temperature is 700-900 ℃, the carbonization time is kept for 1-3 h, nitrogen or argon is introduced as a protective gas, and the carbonization temperature rise rate is 3-8 ℃/min.
9. Nitrogen-sulfur-doped hierarchical porous carbon, characterized in that it is prepared by the method of preparation of nitrogen-sulfur-doped hierarchical porous carbon according to any one of claims 1 to 8.
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Cited By (2)
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| CN116199223A (en) * | 2023-03-24 | 2023-06-02 | 河北省科学院能源研究所 | Preparation method of hard porous carbon for sodium ion battery |
| CN116239100A (en) * | 2023-03-27 | 2023-06-09 | 四川大学 | Rosin-based nitrogen-doped porous hard carbon material and preparation method and application thereof |
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| CN111825074A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method and application of sulfur-nitrogen co-doped three-dimensional porous carbon nanosheet |
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| CN111825074A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method and application of sulfur-nitrogen co-doped three-dimensional porous carbon nanosheet |
Non-Patent Citations (1)
| Title |
|---|
| LEI PAN ET AL.: "3D interconnected honeycomb-like and high rate performance porous carbons from petroleum asphalt for supercapacitors", 《APPLIED SURFACE SCIENCE》, vol. 444, pages 739 - 746 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116199223A (en) * | 2023-03-24 | 2023-06-02 | 河北省科学院能源研究所 | Preparation method of hard porous carbon for sodium ion battery |
| CN116239100A (en) * | 2023-03-27 | 2023-06-09 | 四川大学 | Rosin-based nitrogen-doped porous hard carbon material and preparation method and application thereof |
| CN116239100B (en) * | 2023-03-27 | 2023-10-27 | 四川大学 | Rosin-based nitrogen-doped porous hard carbon material and preparation method and application thereof |
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