CN108288547B - Preparation method of nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material - Google Patents
Preparation method of nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material, relates to a preparation method of a nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material, and aims to solve the problem that the capacitance performance of the mesoporous carbon material is improved to a limited extent by doping of a single heteroatom in the prior art. Firstly, preparing an ordered mesoporous silica template (KIT-6); the mixed solution of sucrose, phosphoric acid and thiosemicarbazide and KIT-6 dispersion liquid are stirred and aged for 10 to 14 hours at the temperature of between 40 and 60 ℃ by a nano perfusion method. And drying the obtained pasty compound in a drying oven at 70-90 ℃ for 10-14 h, and finally, putting the pasty compound in a tubular furnace to be pyrolyzed for 1-3 h at 700-900 ℃ under high-purity nitrogen (the nitrogen flow rate is 50 mL/s), wherein the heating rate is 2 ℃/min. And immersing the carbonized composite material in HF solution, stirring to remove the silicon dioxide template, performing suction filtration, washing with ultrapure water and ethanol respectively, and drying to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material (NPS-OMC). According to the invention, the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material is prepared by adopting nano perfusion through the template, and the specific capacitance of the material electrode can reach 343F/g.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material.
Background
With the rapid development of global economy, environmental problems and the increasing deterioration of energy crisis have seriously threatened human survival and social progress. Therefore, environmental pollution and energy supply become two of the most urgent problems to be solved in the world today. The two fields of environmental pollution and energy supply are closely connected, and the development of renewable new energy sources to replace fossil fuels through sustainable and environment-friendly technology is a brand-new solution.
In order to obtain new energy sources that are safe and renewable and to reduce the emission of greenhouse gases, scientists have developed new materials and methods for storing energy. Supercapacitors and advanced battery systems have been identified as very promising energy storage devices that can both store renewable energy and reduce the demand for fossil fuels. In particular, super capacitors have become efficient, practical, and environmentally friendly energy storage devices due to their fast charge and discharge processes, high specific capacity, long cycle life, simple principles, high power density, high energy density, and the like. At present, the super capacitor is mainly applied to the fields of portable electronic equipment, hybrid electric vehicles, computer terminals, aerospace and the like. It is well known that the electrode material of a supercapacitor plays a decisive role in its capacitive properties, and mainly includes three types: transition metal compounds, conductive polymers, and porous carbon materials. Among them, porous carbon materials have been widely used in commercial supercapacitors as advanced electrode materials with their long cycle life, high power density, wide operating potential window and low cost. However, the specific capacitance of the pure carbon-based supercapacitor is low, generally less than 150F/g, and the requirement of human for energy density is difficult to meet. Therefore, it is still a significant subject to synthesize an electrode material with high energy density, high power density, long cycle stability, economy and environmental protection.
Carbon-based electrode materials are dominated by the creation of electric double layer capacitance. Currently, the most studied carbon-based super-electrode materials mainly include Activated Carbon (ACs), Graphene (Graphene), Carbon Nanotubes (CNTs), Carbon Nanofibers (CNFs), Ordered Mesoporous Carbon (OMC), and the like. Among various carbon materials, the ordered mesoporous carbon has high power density and good cycle stability due to uniform pore diameter and special pore channels, and is considered to be a super capacitor electrode material with great application potential. Many studies have demonstrated that: the pore size distribution of the porous carbon plays an important role in electrochemical performance. If the pore size of the carbon material is smaller than the solvated ions, the carbon material is less wettable by the electrolyte, which limits the capacitance. Ordered mesoporous carbon is considered to be a very promising metamaterial due to its uniform and appropriate pore size (2-50 nm) and ordered channels that can shorten the electron transport path, thus leading to excellent electrochemical properties. However, due to the disadvantages of high chemical reaction inertness, poor surface wettability and the like of the pure ordered mesoporous carbon, when the pure ordered mesoporous carbon is used as an electrode material of a super capacitor, only few active sites can be used for charge storage, so that the electrochemical capacitance performance is not ideal, and the practical application of the pure ordered mesoporous carbon is severely restricted. Therefore, the physicochemical modification of the ordered mesoporous carbon material becomes a hot content in the ordered mesoporous carbon research field.
Recently, non-metal heteroatom doped mesoporous carbon materials have attracted great attention in energy storage. For example, it has been found that incorporation of nitrogen into the carbon skeleton can significantly improve specific capacitance. This is because the incorporation of nitrogen enables: the total pseudo capacitance is improved by the Faraday oxidation-reduction reaction. Secondly, the conductivity of the carbon electrode material is increased, and the capacity retention rate of the double-layer capacity and the pseudo capacity is further improved. And improving the surface wettability of the carbon electrode material to the electrolyte. Thus, nitrogen doping can ensure full utilization of the exposed surface for storing charge. Carbon materials in various forms have been treated with nitrogen doping and exhibit excellent electrochemical capacitance properties. Non-metallic heteroatoms currently used for doping include nitrogen (N), phosphorus (P), sulfur (S), boron (B), and the like. The heteroatoms are connected with carbon atoms through covalent bonds to introduce functional groups into the carbon material, and the physicochemical properties of the carbon material are changed through electron-donating or electron-withdrawing effects. Since these functional groups can generate faradaic reaction with the electrolyte, they can enhance the total specific capacitance by pseudocapacitance effect. Among these, nitrogen doping is the most effective method to enhance specific capacitance while maintaining good rate capability of carbon materials. The nitrogen atoms have an electron donating effect with respect to the carbon atoms, and thus can improve physicochemical properties of the carbon material such as surface polarity, conductivity, and wettability. Therefore, nitrogen-doped ordered mesoporous carbon materials have received much attention.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material. Thereby solving the problem that the capacitance performance of the mesoporous carbon material is improved to a limited extent by doping single heteroatom.
The preparation method of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material is realized according to the following steps:
firstly, synthesizing an ordered mesoporous silica template (KIT-6) by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on the dried KIT-6 in deionized water to obtain a uniform dispersion liquid; while adding sucrose, phosphoric acid and thiosemicarbazide to deionized water, stirring to obtain a uniform solution. (2) The latter is transferred into the former and is continuously stirred for 10 to 14 hours in a fume hood at the temperature of between 40 and 60 ℃. (3) The resulting paste-like compound is dried in an oven at 70-90 ℃ for 10-14 h, and the remaining solid is then ground to a powder. (4) The composite material powder is put into a tubular furnace to be pyrolyzed for 1-3 h at 700-900 ℃ under high-purity nitrogen, and the heating rate is 2 ℃/min. (5) The carbonized composite was immersed in HF solution and stirred to remove the silica template. (6) And (4) carrying out suction filtration, washing with ultrapure water and ethanol respectively, and drying to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).
The method comprises the steps of mixing nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material powder with Polytetrafluoroethylene (PTFE) solution, stirring to form slurry, uniformly coating the slurry on foamed nickel, and pressing to form a sheet to obtain the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material supercapacitor electrode.
According to the invention, the ordered mesoporous silicon dioxide membrane plate (KIT-6) is formed by adopting a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and tetraethoxysilane in a hydrothermal mode, and nitrogen, phosphorus and sulfur ternary codoped ordered mesoporous carbon with good ordering is synthesized by a nano perfusion method. The functions of the silicon dioxide membrane plate and the cane sugar, the phosphoric acid and the thiosemicarbazide mainly comprise:
1. the silicon dioxide template mainly provides a pore channel structure for synthesizing the ordered mesoporous carbon material, so that the carbon material poured by the template can keep the ordered mesoporous structure; 2. the sucrose as a carbon source for synthesizing nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon can form good compatibility with a hard template KIT-6, so that the perfusion degree is more complete; 3. phosphoric acid as a phosphorus source for synthesizing the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon can provide a Faraday pseudo-capacitance for the material, so that the capacitance performance of the material is improved; 4. the thiosemicarbazide is used as a nitrogen source and a sulfur source for synthesizing the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon, so that the wetting of the material can be improved, and the Faraday pseudocapacitance of the material can be improved.
Meanwhile, the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon has a higher specific surface area, can provide more reactive sites for capacitance reaction, further improves the capacitance of the material, and the ordered mesoporous structure of the carbon can shorten the transportation path of conductive particles, thereby improving the electrochemical performance of the material.
Under the condition of a KOH solution with the electrolyte concentration of 6 mol/L, the specific capacitance of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon can reach 343F/g.
Drawings
FIG. 1 is an XRD pattern of ordered mesoporous silica KIT-6 obtained in step one of the examples;
FIG. 2 is a TEM image of ordered mesoporous silica KIT-6 obtained in step one of the examples;
FIG. 3 is an XRD (X-ray diffraction) diagram of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first example;
FIG. 4 is a physical adsorption-desorption and pore size distribution diagram of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first embodiment;
FIG. 5 is a TEM image of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first example;
FIG. 6 is an SEM image of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first example;
FIG. 7 is an EDS diagram of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first example;
FIG. 8 is an XPS diagram of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material obtained in the first example;
FIG. 9 is a cyclic voltammetry graph of nitrogen, phosphorus and sulfur ternary codoped ordered mesoporous carbon materials in examples I, II and III;
FIG. 10 is a constant current charge-discharge curve diagram of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material in examples I, II and III.
Detailed Description
The first embodiment is as follows: the preparation method of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material is implemented according to the following steps:
firstly, synthesizing an ordered mesoporous silica template (KIT-6) by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on the dried KIT-6 in deionized water to obtain a uniform dispersion liquid; meanwhile, adding sucrose, phosphoric acid and thiosemicarbazide into deionized water, and stirring to obtain a uniform solution, wherein the mass ratio of m (KIT-6): m (sucrose): m (phosphoric acid): m (thiosemicarbazide) = 8: 8 (2-1): 2-1. (2) The latter was transferred to the former and stirring was continued in a fume hood at 40 ℃ for 12 h. (3) The resulting paste-like compound was dried in an oven at 80 ℃ for 12h, and the dried solid was then ground to a powder. (4) The composite powder was pyrolyzed in a high purity nitrogen (50 ml/s) at 800 ℃ for 2h in a tube furnace at a heating rate of 2 ℃/min. (5) And immersing the carbonized composite material in 100 mL of HF solution with the mass fraction of 5% and stirring for 24 h to remove the silicon dioxide template. (6) And (4) performing suction filtration, washing with ultrapure water and ethanol respectively until the pH is =7, and drying to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).
In the embodiment, a carbon source, a nitrogen source, a phosphorus source and a sulfur source are respectively poured into the ordered mesoporous silica template (KIT-6) by a nano pouring method, and the silicon template is removed after carbonization, so that the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon nano material is obtained.
The second embodiment is as follows: this embodiment differs from one of the first to fourth embodiments in that the pyrolysis temperature in the second step is 700 ℃, and other steps and parameters are the same as those in the first to fourth embodiments.
The third concrete implementation mode: this embodiment differs from one of the first to fifth embodiments in that the pyrolysis temperature in the second step is 900 ℃, and other steps and parameters are the same as those in the first to fifth embodiments.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is that the second step is stirred in a fume hood at 60 ℃ for 12h, and the other steps and parameters are the same as those of the first to sixth embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to seventh embodiments is that the second step is stirred in a fume hood at 70 ℃ for 12h, and the other steps and parameters are the same as those of the first to seventh embodiments.
The sixth specific implementation mode: the present embodiment is different from the first to eighth embodiments in that the second step is performed by baking at 800 ℃ for 3 hours. Other steps and parameters are the same as those in one to eight of the embodiments.
The first embodiment is as follows:
firstly, synthesizing an ordered mesoporous silica template (KIT-6) by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on dried KIT-6 (1.0 g) in 15 mL of DI water for 1 h to obtain a uniform dispersion liquid; while this was done, 1.0 g sucrose, 0.25 g phosphoric acid and 0.25 g thiosemicarbazide were added to 15 mL DI water and stirred for 1 h to give a homogeneous solution. (2) The latter was transferred to the former and stirring was continued in a fume hood at 50 ℃ for 12 h. (3) The resulting paste-like compound was placed in an oven to dry at 80 ℃ for 12h, and then the remaining solid was ground to a powder. (4) The composite powder was pyrolyzed in a high purity nitrogen (50 mL/s) at 800 ℃ for 2h in a tube furnace at a heating rate of 2 ℃/min. (5) The carbonized composite material was immersed in 100 mL of a 5% by mass HF solution and stirred for 24 hours to remove the silica template. (6) And (3) carrying out suction filtration, washing with ultrapure water and ethanol respectively for 3 times, and drying at 100 ℃ for 12h to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).
Example two:
firstly, synthesizing an ordered mesoporous silica template (KIT-6) by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on dried KIT-6 (1.0 g) in 15 mL of DI water for 1 h to obtain a uniform dispersion liquid; while this was done, 1.0 g sucrose, 0.33 g phosphoric acid and 0.33 g thiosemicarbazide were added to 15 mL DI water and stirred for 1 h to give a homogeneous solution. (2) The latter was transferred to the former and stirring was continued in a fume hood at 50 ℃ for 12 h. (3) The resulting paste-like compound was placed in an oven to dry at 80 ℃ for 12h, and then the remaining solid was ground to a powder. (4) The composite powder was pyrolyzed in a high purity nitrogen (50 mL/s) at 800 ℃ for 2h in a tube furnace at a heating rate of 2 ℃/min. (5) The carbonized composite material was immersed in 100 mL of a 5% by mass HF solution and stirred for 24 hours to remove the silica template. (6) And (3) carrying out suction filtration, washing with ultrapure water and ethanol respectively for 3 times, and drying at 100 ℃ for 12h to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).
Example three:
firstly, synthesizing an ordered mesoporous silica template (KIT-6) by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on dried KIT-6 (1.0 g) in 15 mL of DI water for 1 h to obtain a uniform dispersion liquid; while adding 1.0 g of sucrose, 0.17 g of phosphoric acid and 0.17 g of thiosemicarbazide to 15 mL of DI water, stirring for 1 h gave a homogeneous solution. (2) The latter was transferred to the former and stirring was continued in a fume hood at 50 ℃ for 12 h. (3) The resulting paste-like compound was placed in an oven to dry at 80 ℃ for 12h, and then the remaining solid was ground to a powder. (4) The composite powder was pyrolyzed in a high purity nitrogen (nitrogen flow rate 50 mL/s) at 800 ℃ for 2h in a tube furnace at a heating rate of 2 ℃/min. (5) The carbonized composite material was immersed in 100 mL of a 5% by mass HF solution and stirred for 24 hours to remove the silica template. (6) And (3) carrying out suction filtration, washing with ultrapure water and ethanol respectively for 3 times, and drying at 100 ℃ for 12h to obtain the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).
In this embodiment, a process of preparing an ordered mesoporous silica template (KIT-6) by a hydrothermal method includes:
6.0 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was dissolved in 217.0 g of deionized water and 11.8 g of hydrochloric acid (HCl), and 6.0 g of n-butanol (BuOH) and ethyl orthosilicate (TEOS) were slowly added with stirring at 35 ℃ with TEOS: P-123: HCl: H2O BuOH = 1: 0.017: 1.83: 195: 1.31. The mixed solution is stirred for 24 hours at 35 ℃, then transferred into a reaction kettle and reacted for 24 hours at 100 DEG C. After the sample is filtered, white powder is obtained, dried at 80 ℃ for 12h and then transferred to a muffle furnace, and roasted at 550 ℃ for 6 h. Obtaining the ordered mesoporous silica template (KIT-6).
The crystal form of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material obtained in the embodiment is characterized by an X-ray diffractometer (XRD, RigakuD/max-II); the morphology and microstructure are characterized by scanning electron microscopy analysis (SEM, S-3400) and transmission electron microscope (TEM, H-7650); the material element distribution is characterized by an energy spectrometer (EDS, S-3400); the valence state information of the material surface is characterized by X-ray photoelectron spectroscopy (XPS, 250 Xi); the pore channel information such as the specific surface area of the material is characterized by a physical adsorption analyzer (BET, AUTONORB-1).
Fig. 1 is an XRD pattern of the ordered mesoporous silica template (KIT-6) obtained by the above example, and it is clearly seen that characteristic diffraction peaks appear at two positions of 2 θ ═ 0.8 ° and 1.2 °, corresponding to the (211) and (220) crystal planes, respectively. This indicates that KIT-6 obtained after the surfactant P123 is removed by pyrolysis has a highly ordered pore structure. FIG. 2 is a TEM image of the ordered mesoporous silica template (KIT-6) in the first example. It is evident from the figure that the KIT-6 silicon template has a highly ordered 3D pore channel structure, which is consistent with the characterization results of XRD in fig. 1.
Fig. 3 is an XRD chart of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in example i, and it can be clearly seen from the XRD chart that distinct characteristic diffraction peaks appear at two positions of 2 θ ═ 0.8 ° and 1.2 °, which correspond to the (211) and (220) crystal planes, respectively. However, compared with the characteristic peak of the (220) crystal face of the KIT-6 silicon template in fig. 1, the characteristic diffraction peak of the (220) crystal face of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon tends to be smooth, which indicates that the high-temperature heat treatment can cause the skeleton of the material to shrink to some extent.
Fig. 4 is a nitrogen adsorption-desorption isothermal curve diagram of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material and a BJH pore size distribution curve embedded by adsorption branches in example one. The nitrogen adsorption-desorption isotherm of the material is a type IV adsorption curve and is in a medium pressure zone (P/P)0=0.4-0.8) occurrence of H1 type caused by capillary condensation phenomenonThe hysteresis ring corresponds to the mesoporous structure of the synthetic carbon material. The specific surface area of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material is 637 m2In terms of/g, the mean pore diameter is 1.9 nm. The larger specific surface area of the material can provide more active sites for electrochemical reaction, and the specific capacitance of the material is improved.
FIG. 5 is a TEM image of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in the first example. Fig. 5 clearly shows that the stripes showing order illustrate that the material has a higher degree of order, which is a typical 3D mesoporous structure. It is also clearly observed from the images that there are a large number of open uniform channels in the carbon material, which are the inverse replica of the KIT-6 template 3D mesostructure. Consistent with the results characterized by nitrogen adsorption-desorption in figure 4 and TEM in figure 2 KIT-6.
FIG. 6 is an SEM image of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in the first example. The nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon particles are relatively independent and uniformly distributed.
FIG. 7 is an EDS diagram of carbon, nitrogen, phosphorus and sulfur elements in the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in example I. It can be clearly observed from the figure that the elements of carbon, nitrogen, phosphorus and sulfur are uniformly distributed. This shows that nitrogen, phosphorus and sulfur are uniformly doped into the ordered mesoporous carbon material.
Fig. 8 is an XPS full spectrum of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in the first embodiment, and from the XPS full spectrum, the existence of peak patterns of carbon, nitrogen, phosphorus, sulfur, and oxygen can be observed, which indicates that the nitrogen, phosphorus, and sulfur elements are indeed doped into the ordered mesoporous carbon material. This is consistent with the results for the EDS of fig. 7.
The application example is as follows: mixing 5mg of nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material powder with 5 wt% of Polytetrafluoroethylene (PTFE) solution, stirring to form slurry, uniformly coating the slurry on 1 x 10 cm of foamed nickel, and pressing to form a sheet to obtain the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material supercapacitor electrode.
In the application example, a mercury oxide electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode, and a CHI660E electrochemical workstation (Shanghai Chenghua) is used for carrying out performance tests such as cyclic voltammetry characteristic curve, constant current charge and discharge, alternating current impedance and the like on the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material electrode.
FIG. 9 is a cyclic voltammetry curve of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material electrode in the first, second and third examples at a scan rate of 1 mV/s and in an electrolytic solution of 6 mol/LKOH. It is obvious from the figure that the CV curve of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material electrode is closest to the rectangular shape of an ideal capacitor, which shows that the prepared nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material has very small resistance and good symmetry and reversibility when being used as a supercapacitor electrode, and therefore can be used as an ideal electrode material of a supercapacitor; in the second example, the doping amounts of nitrogen, phosphorus and sulfur were increased, and the specific capacitance was rather decreased, so that it was not found that the more the doping amounts of nitrogen, phosphorus and sulfur were, the better; in the third example, the doping amount of nitrogen, phosphorus and sulfur is reduced, so that the specific capacitance is reduced, and therefore, the lower doping amount of nitrogen, phosphorus and sulfur cannot remarkably increase the Faraday pseudo-capacitance of the material.
FIG. 10 is a constant current charge-discharge curve of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon in examples I, II and III. It can be seen from the figure that the charging time period and the discharging time period of the constant current charging and discharging curve are basically close, which indicates that the compounded electrode material has good recycling performance. And the constant current charge-discharge curve has certain symmetry, which shows that the reversibility of the electrode material is better. Consistent with the electrochemical performance exhibited by the cyclic voltammogram of fig. 9: too much or too little nitrogen, phosphorus and sulfur doping amount can affect the Faraday pseudo-capacitance of the material. It is obvious from the figure that when the concentration of the electrolyte (KOH electrolyte) is 6 mol/L, the specific capacitance of the nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material in the first embodiment reaches 343F/g.
Claims (1)
1. The preparation method of the nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon material is characterized by comprising the following steps of:
firstly, synthesizing an ordered mesoporous silica template by adopting a hydrothermal synthesis method;
secondly, (1) carrying out ultrasonic treatment on the dried KIT-6 in deionized water to obtain a uniform dispersion liquid; meanwhile, adding sucrose, phosphoric acid and thiosemicarbazide into deionized water and stirring to obtain a uniform solution; (2) adding a mixed solution of sucrose, phosphoric acid and thiosemicarbazide into the KIT-6 dispersion liquid, and stirring and aging for 10-14 h in a fume hood at 40-60 ℃; (3) drying the obtained pasty compound in an oven at 70-90 ℃ for 10-14 h, and grinding into powder; (4) putting the powder into a tubular furnace, and pyrolyzing the powder for 1 to 3 hours at 700 to 900 ℃ under high-purity nitrogen at a heating rate of 2 ℃/min; (5) immersing the carbonized composite material in an HF solution with the mass concentration of 5% and stirring to remove the silicon dioxide template; (6) performing suction filtration, washing with ultrapure water and ethanol respectively, and drying to obtain nitrogen-phosphorus-sulfur ternary codoped ordered mesoporous carbon;
wherein the process of preparing the ordered mesoporous silica template by the hydrothermal synthesis method comprises the following steps:
6.0 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P-123 is dissolved in 217.0 g of deionized water and 11.8 g of hydrochloric acid, and ethyl orthosilicate and 6.0 g of n-butanol are slowly added under stirring at 35 ℃; stirring the mixed solution at 35 ℃ for 24 hours, then transferring the mixed solution into a reaction kettle, reacting at 100 ℃ for 24 hours, carrying out suction filtration on a sample to obtain white powder, drying at 80 ℃ for 12 hours, transferring the white powder into a muffle furnace, and roasting at 550 ℃ for 6 hours to obtain an ordered mesoporous silica template;
in the second step, the mass ratio of KIT-6 to sucrose to phosphoric acid to thiosemicarbazide is 8: 8 (2-1) to (2-1).
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| CN109455701A (en) * | 2018-09-10 | 2019-03-12 | 北京理工大学 | A kind of preparation method of the highly doped nitrogen phosphorus carbon nanosheet of highly effective hydrogen yield |
| CN109133276B (en) * | 2018-10-08 | 2021-09-07 | 天津科技大学 | Functionalized mesoporous carbon electrode material and preparation method thereof |
| CN114497598A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Sulfur-nitrogen-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
| CN112624084B (en) * | 2020-12-10 | 2023-06-30 | 浙江师范大学 | Nitrogen-sulfur-phosphorus doped ordered mesoporous carbon material, and preparation method and application thereof |
| CN113233461B (en) * | 2021-07-07 | 2023-02-21 | 河北省科学院能源研究所 | Preparation of non-metal biomass-based porous carbon material and hydrogen production application thereof |
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