CN108313999A - A kind of preparation method of nitrogen, sulphur, phosphorus heteroatoms doping carbon material - Google Patents

Abstract

The invention discloses a method for preparing carbon materials doped with heteroatoms of nitrogen, sulfur and phosphorus, and belongs to the technical field of carbon material preparation. This method uses fluorinated carbon materials or fluorinated carbon nanotubes as the carbon substrate, and one or more of the liquid sources containing nitrogen, sulfur, and phosphorus heteroatoms are doped into carbon by pyrolysis deposition at 400‑1000 ° C. In the substrate, or grind and mix the solid source containing nitrogen, sulfur, and phosphorus heteroatoms with the carbon substrate, and calcinate at 400-800°C to achieve doping, and obtain nitrogen, sulfur, and phosphorus heteroatom-doped carbon materials. The liquid source includes pyridine, thiophene, triphenylphosphine solution, etc., and the solid source includes sublimated sulfur, dibenzyl disulfide, etc. The method is simple to operate and has strong universality. The high-concentration vacancies generated by high-temperature defluorination of fluorinated carbon nanotubes can be used to achieve high-efficiency doping of heteroatoms.

Description

A kind of preparation method of nitrogen, sulfur, phosphorus heteroatom doped carbon material

technical field

The invention belongs to the technical field of carbon material preparation, and in particular relates to a preparation method of nitrogen, sulfur and phosphorus heteroatom-doped carbon material.

technical background

Heteroatom doping of carbon materials refers to the introduction of heteroatoms such as O, N, B, P, and S into the carbon skeleton, which can strengthen the inherent excellent properties of carbon materials and even endow them with new functions, so that carbon materials have higher electron density. Transmission rate, richer pore structure, stronger wettability, larger specific surface area, obvious surface acidity and alkalinity, etc., thus broadening the application of carbon materials in fuel cells, secondary batteries, supercapacitors, heterogeneous catalysis and other fields Applications.

The preparation methods of heteroatom-doped carbon materials are generally divided into in-situ doping and post-treatment doping, including chemical vapor deposition, solvothermal method, arc method, laser evaporation and other methods. In recent years, carbon materials doped with one or several heteroatoms among O, N, B, P, and S have been studied more, among which nitrogen-doped carbon materials are the most common. Compared with N and B doping whose atomic diameter is similar to that of C atoms, it is much more difficult to incorporate S and P into the lattice of carbon materials, Dines et al. (ChemPhysChem, 2009, 10(4):715–722) Theoretical calculations show that the main reason is that S and P doping will not be able to maintain the planar structure of carbon materials, and there will be large stress and tension. In 2011, Schmidt et al. (Chemical Communications, 2011, 47(29):8283-8285) used a porous network polymer containing thienyl groups as a precursor to synthesize a porous sulfur-doped carbon material with a structure similar to the precursor. Patent CN106207109 reports a preparation method of a nitrogen-sulfur double-doped three-dimensional structure carbon material, using thiophene and pyridine as the sulfur source and nitrogen source respectively, and successfully preparing a double-doped three-dimensional structure on the foamed nickel substrate by chemical vapor deposition Carbon materials that can be used as battery electrodes. Patent CN105752961 uses a combination of silicon-based hard template and activation to prepare a nitrogen-phosphorus double-doped and connected multi-level porous carbon material, which improves the rapid diffusivity of the carbon material. But in general, the content of phosphorus and sulfur in doped carbon materials reported so far is mostly in the range of 1wt%-4wt%, and the adjustable range is small, which is not conducive to further exploration of the effects of different concentrations of sulfur, phosphorus and other heteroatoms on the structure of carbon materials, The influence of physical and chemical properties and performance.

At present, the efficient and controllable doping of heteroatoms, especially heteroatoms with large S and P atomic radii, is still a major challenge for researchers, and it is also the primary problem to be solved in further research. According to recent literature reports, generating a high concentration of effective vacancies in the carbon lattice is the key to achieving high-efficiency doping. Li et al. (J.Am.Chem.Soc.,2012,134(1):15–18) successfully prepared doped carbon with high nitrogen content by using the vacancies caused by the shedding of oxygen-rich functional group carbon materials during heat treatment. Material. Patent CN103553027 uses fluorinated graphene as a raw material to prepare graphene doped with high content of nitrogen. Liu (Nat.Commun.2016 _, 7, 10921) achieved _N , S, B doping. Compared with materials such as graphene, graphene carbon quantum dots, and single-walled carbon nanotubes, ordinary carbon nanotubes have lower specific surface area, lower price, simpler preparation process, and difficult to achieve high content of heteroatom doping, but they have wider and more important meanings. The invention uses fluorinated carbon nanotubes as the base, combines the high-temperature defluorination process of fluorinated carbon nanotubes with the heteroatom doping process, and provides a universal heteroatom doping process while realizing efficient doping of heteroatoms Preparation method of doped carbon material.

Contents of the invention

In view of the deficiencies in the prior art, the present invention aims to provide a universal preparation method of heteroatom-doped carbon materials, which can realize efficient and controllable preparation of heteroatom-doped carbon materials. The preparation method is simple in process, Fast and efficient.

The above object of the present invention is achieved through the following technical solutions.

A preparation method of nitrogen, sulfur, phosphorus heteroatom doped carbon material, comprising the following steps:

Using fluorinated carbon materials or fluorinated carbon nanotubes as the carbon substrate, the liquid source containing one or several heteroatoms in nitrogen, sulfur and phosphorus is incorporated into the carbon substrate by pyrolysis deposition at 400-1000°C , or grind and mix the solid source containing one or more heteroatoms of nitrogen, sulfur, and phosphorus with the carbon substrate, and calcinate at 400-800°C to achieve doping to obtain nitrogen, sulfur, and phosphorus heteroatom-doped carbon materials .

Preferably, fluorinated carbon material is used as the carbon substrate, wherein the fluorine content is 1wt%-58wt%.

Preferably, the carbon substrate is fluorinated carbon nanotubes.

Preferably, the liquid source is one or more of pyridine, thiophene, triphenylphosphine toluene solution and dibenzyl disulfide solution; the solid source is one of sublimated sulfur and dibenzyl disulfide, etc. or several.

Preferably, when thiophene is used to achieve sulfur doping, the pyrolysis deposition temperature is 500-1000°C, the injection rate of thiophene is 1-10mL/h, the deposition time is 2-6h, and the amount of fluorinated carbon nanotubes is 50-500mg .

Preferably, when sublimed sulfur is used to realize sulfur doping, the temperature of calcination is 400-800° C., and the time is 0.5-4 h.

Preferably, when the phosphorus-doped carbon material is prepared using the triphenylphosphine toluene solution, the concentration of the triphenylphosphine toluene solution is 0.1-1 g/mL.

Preferably, when pyridine and thiophene are used to achieve nitrogen-sulfur co-doping, the volume ratio of pyridine to thiophene is 1:1-1:20.

Preferably, when pyridine and dibenzyl disulfide are used to achieve nitrogen-sulfur co-doping, the concentration of dibenzyl disulfide in pyridine is 0.1-0.8 g/mL.

Preferably, when pyridine and triphenylphosphine are used to realize nitrogen and phosphorus co-doping, the concentration of the pyridine solution of triphenylphosphine is 0.01-0.4 g/mL.

Preferably, a kind of preparation method of nitrogen, sulfur, phosphorus heteroatom doped carbon material, comprises the following steps:

Weigh a certain amount of fluorinated carbon materials or carbon nanotubes and evenly spread them in the porcelain boat, then put them into the center of the tube furnace, and mix one or more of the liquid sources into carbon by pyrolysis deposition at 500-1000°C In the material, the injection speed is 1-10mL/h, and the injection time is 2-6h; or the solid source is ground and mixed with fluorinated carbon nanotubes, and calcined at 400-800°C to achieve doping; the heating method of the pyrolysis deposition In order to: first raise the tube furnace to 500-1000 °C at a rate of 10 °C/min in an argon atmosphere, and then push the porcelain boat with carbon fluoride nanotubes directly into the high temperature zone of the tube furnace from the air outlet , start cracking the deposition.

Compared with the prior art, the present invention has the following advantages:

(1) The present invention uses fluorinated carbon nanotubes as the carbon substrate, and adopts a rapid heating method. With the removal of CF _n , high-concentration vacancies are generated in the carbon lattice, which is conducive to heteroatom doping, especially atomic Atoms such as S and P with larger radii.

(2) The process of the present invention is simple, easy to operate, can realize efficient and controllable doping of heteroatoms, has strong universal applicability to different heteroatom sources, and is a synthesis method of carbon materials with great popularization value.

Description of drawings

FIG. 1 is a TEM image of the sulfur-doped carbon material in Example 27.

2a, 2b, 2c, and 2d are STEM mapping images of the sulfur-doped carbon material in Example 27.

3 is the X-ray photoelectron spectrum of the sulfur-doped carbon material in Example 27.

Detailed ways

The specific implementation of the present invention will be further described below in conjunction with the accompanying drawings and examples, but the present invention is not limited to the following examples. In the following examples, the mass fractions of N and S were measured by an elemental analyzer, and the mass fraction of P was measured by an electron probe microanalyzer.

Fluorinated carbon nanotubes (with fluorine content of 40wt%-48wt%, 56wt%-58wt%, respectively marked as FCNTs-40, FCNTs-56) are prepared by putting carbon nanotubes and xenon difluoride into polytetrafluoroethylene In an ethylene kettle, treated at 200 °C in an Ar atmosphere for 30 h, the fluorinated carbon nanotubes with different fluorination degrees were prepared by adjusting the mass ratio of carbon nanotubes to xenon difluoride (FCNTs-40, FCNTs-56 during the preparation process The mass ratios of carbon nanotubes to xenon difluoride are 1:15 and 1:20, respectively).

The preparation method of fluorinated carbon materials (the fluorine content is 1wt%, 2.5wt%, marked as FC-1, FC-2.5 respectively) is as follows: 1.5g (the final product obtained is FC-1) or 3g (the final product obtained is FC-2.5) Polyvinylidene fluoride was dispersed in 100mL of absolute ethanol, ultrasonicated for 2h, and dried at 110°C. The resulting solid product was calcined at 700°C for 2h in an Ar atmosphere to obtain FC-1 and FC-2.5.

In the following examples, unless otherwise specified, the fluorinated carbon nanotubes used are all FCNTs-56.

Examples 1-6

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat, and place the porcelain boat in the center of the tube furnace until the temperature of the tube furnace rises to the target shown in Table 1 at a rate of 10°C/min under an argon atmosphere. Temperature: Inject thiophene into the high temperature area with a micro-injection pump at a rate of 1.5mL/h, and continue the injection for 2 hours. After the tube furnace is cooled to room temperature, take out the sample, wash it with ethanol and acetone three times, and measure it with an elemental analyzer. The sulfur content of doped carbon materials is shown in Table 1.

Table 1

Example 1 2 3 4 5 6 temperature/℃ 500 600 700 800 900 1000 Sulfur content/wt% 4.601 4.542 4.547 5.217 4.645 4.428

It can be seen from Table 1 that the sulfur doping content of fluorinated carbon nanotubes in the selected temperature range is above 4wt%, and the doping effect is the best at 800°C, and the sulfur content is 5.217wt%, which realizes the efficient doping of sulfur.

Example 7-9

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat, and place the porcelain boat in the center of the tube furnace. The syringe pump injected thiophene into the high temperature area at the injection speed shown in Table 2, and continued to inject for 2 hours. After the tube furnace was cooled to room temperature, the samples were taken out and washed 4 times with ethanol and acetone respectively. The sulfur content is shown in Table 2.

Table 2

Example 7 4 8 9 Injection speed/mL/h 1 1.5 5 10 Sulfur content/wt% 3.115 5.217 4.865 4.744

It can be seen from Table 2 that when the injection speed of fluorinated carbon nanotubes is 1.5mL/h, a relatively ideal sulfur doping effect can be achieved.

Examples 10-11

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat, and place the porcelain boat in the center of the tube furnace. The syringe pump injects thiophene into the high-temperature area at a rate of 1.5mL/h, and continues the injection for the time shown in Table 3. After the tube furnace is cooled to room temperature, the sample is taken out, washed with ethanol and acetone for 5 times, and measured by an elemental analyzer. The sulfur content of the doped carbon materials is shown in Table 3.

table 3

Example 4 10 11 Injection time/h 2 4 6 Sulfur content/wt% 5.217 4.364 3.925

It can be seen from Table 3 that the ideal sulfur content can be achieved after thermal deposition of fluorinated carbon nanotubes for 2 hours, and the sulfur species on the surface decrease with the increase of the holding time.

Examples 12-14

Weigh the carbon fluoride nanotubes with the mass shown in Table 4 and lay them flat on the porcelain boat, and place the porcelain boat in the center of the tube furnace, and wait for the temperature of the tube furnace to rise at a rate of 10 °C/min to 800°C, inject thiophene into the high-temperature area with a micro-injection pump at a rate of 1.5mL/h, and continue the injection for 2 hours. After the tube furnace is cooled to room temperature, take out the sample, wash it with ethanol and acetone four times, and use an elemental analyzer to The measured sulfur content of doped carbon materials is shown in Table 4.

Table 4

Example 12 4 13 14 Mass/mg 50 100 300 500 Sulfur content/wt% 5.049 5.217 4.158 3.685

It can be seen from Table 4 that when the mass of fluorinated carbon nanotubes is 100 mg, high-efficiency sulfur doping can be achieved. When too much carbon substrate is invested, uneven doping will occur, resulting in a decrease in the average sulfur content.

Example 15-20

Weigh 100 mg of carbon nanotubes and lay them flat on a porcelain boat, place the porcelain boat in the center of the tube furnace, and wait until the temperature of the tube furnace rises to the target temperature shown in Table 5 at a rate of 10°C/min under an argon atmosphere. Use a micro-injection pump to inject thiophene into the high-temperature area at a rate of 1.5 mL/h, and continue to inject for 2 hours. After the tube furnace is cooled to room temperature, take out the sample, wash it with ethanol and acetone three times, and measure the doping concentration with an elemental analyzer. The sulfur content of carbon materials is shown in Table 5.

table 5

Example 15 16 17 18 19 20 temperature/℃ 500 600 700 800 900 1000 Sulfur content/wt% 0.355 0.432 0.735 1.926 1.525 1.127

It can be seen from the table that the sulfur doping content of carbon nanotubes in the selected temperature range is below 2wt%, and the doping effect is the best at 800°C, and the sulfur content is 1.926wt%, which is far lower than the fluorine shown in Examples 1-6. The effect of sulfur doping on carbon nanotubes under the same conditions.

Examples 21-26

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to the target temperature shown in Table 6 at a rate of 10°C/min under an argon atmosphere, place the porcelain boat from the gas outlet end at 10 Quickly push it into the center of the tube furnace within seconds (need to ensure the argon atmosphere), inject thiophene into the high temperature area at a rate of 1.5mL/h with a micro-injection pump, and continue to inject for 2 hours. After the tube furnace cools down to room temperature, take out the sample, and Wash with ethanol and acetone for 5 times respectively, and the sulfur content of the doped carbon material was measured with an elemental analyzer, as shown in Table 6.

Table 6

Example twenty one twenty two twenty three twenty four 25 26 temperature/℃ 500 600 700 800 900 1000 Sulfur content/wt% 5.236 6.528 6.039 5.725 5.017 4.823

It can be seen from Table 6 that the rapid heating method in the selected temperature range can more effectively match the high-temperature defluorination process of fluorinated carbon nanotubes with the heteroatom doping process, thereby increasing the sulfur-doped content of fluorinated carbon nanotubes.

Examples 27-29

Weigh 100 mg of carbon substrates with different fluorine contents shown in Table 7 and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to 800°C at a rate of 10°C/min under an argon atmosphere, place the porcelain boat from the gas outlet end on Quickly push into the center of the tube furnace within 10 seconds (need to ensure the argon atmosphere), inject thiophene into the high temperature area at a rate of 1.5mL/h with a micro-injection pump, and continue to inject for 2 hours. After the tube furnace cools down to room temperature, take out the sample. And washed with ethanol and acetone for 5 times respectively, and the sulfur content of the doped carbon material was measured with an elemental analyzer, as shown in Table 7.

Table 7

Example 27 28 29 twenty four carbon base FC-1 FC-2.5 FCNTs-40 FCNTs-56 Sulfur content/wt% 2.034 2.213 3.554 5.725

It can be seen from Table 7 that by changing the degree of fluorination of the carbon substrate, the doping level of heteroatoms can be effectively regulated. When the degree of fluorination is the largest and the fluorine content reaches 56%-58%, the sulfur content is the highest.

Examples 25-29

Grind and mix 100mg carbon fluoride nanotubes and 1000mg sublimated sulfur evenly and spread them on a porcelain boat. After the temperature of the tube furnace rises to the target temperature shown in Table 8 at a rate of 10°C/min under an argon atmosphere, place the porcelain Quickly push the boat into the center of the tube furnace within 10 seconds from the gas outlet (need to ensure the argon atmosphere), keep it warm for 2 hours, wait for the tube furnace to cool down to room temperature, take out the sample, wash it with ethanol and acetone for 5 times, and wash it with element The sulfur content of the sulfur-doped carbon material measured by the analyzer is shown in Table 8.

Table 8

Example 25 26 27 28 29 temperature/℃ 400 500 600 700 800 Sulfur content/wt% 2.858 3.259 5.011 4.321 4.015

It can be seen from Table 8 that when sublimed sulfur is used as the sulfur source, the effect of sulfur doping at 600°C is the best within the selected temperature range.

The TEM images, STEM mapping images and X-ray photoelectron spectra of the sulfur-doped carbon material in Example 27 are shown in Figure 1, Figure 2a, Figure 2b, Figure 2c, Figure 2d, and Figure 3. The typical morphology of carbon nanotubes can be seen from Figure 1. Due to the incorporation of sulfur atoms, an amorphous carbon layer appears on the tube wall. The uniform distribution of S on the surface of carbon tubes can be clearly seen from STEM mapping. XPS characterization further confirmed the successful incorporation of sulfur, and the incorporated sulfur mainly exists in the form of -C-S-C-.

Examples 30-32

Grind and mix 100mg carbon fluoride nanotubes and 1000mg sublimated sulfur evenly and spread them on a porcelain boat. After the temperature of the tube furnace rises to 600°C at a rate of 10°C/min under an argon atmosphere, put the porcelain boat out of the gas outlet Quickly push the tip into the center of the tube furnace within 10 seconds (need to ensure the argon atmosphere). The sulfur content of the doped carbon material measured by the elemental analyzer is shown in Table 9.

Table 9

Example 30 31 27 32 Holding time/h 0.5 1 2 4 Sulfur content/wt% 2.712 3.457 5.011 4.965

It can be seen from Table 9 that when sublimed sulfur is used as the sulfur source, the doping effect achieved at 600°C and 2h is the best.

Examples 33-37

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to 800°C at a rate of 10°C/min in an argon atmosphere, quickly push the porcelain boat from the gas outlet within 10 seconds. into the center of the tube furnace (need to ensure the argon atmosphere), inject the dibenzyl dithiopyridine solution with the concentration shown in Table 10 into the high temperature zone at a speed of 1.5mL/h with a micro-injection pump, and continue to inject for 2h. After cooling to room temperature, the sample was taken out and washed five times with ethanol and acetone respectively. The nitrogen and sulfur contents of the doped carbon material were measured with an elemental analyzer, as shown in Table 10.

Table 10

It can be seen from Table 10 that the nitrogen-sulfur co-doping of carbon materials can be successfully achieved by using the pyridine solution of dibenzyl disulfide as the heteroatom source.

Examples 38-42

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to 800°C at a rate of 10°C/min in an argon atmosphere, quickly push the porcelain boat from the gas outlet within 10 seconds. Into the center of the tube furnace (need to ensure the argon atmosphere), inject the liquid mixed with different volume ratios of thiophene and pyridine shown in Table 11 into the high temperature zone with a micro injection pump at a speed of 1.5mL/h, continue to inject for 2h, and wait for the tube type The furnace was cooled to room temperature, the samples were taken out, and washed five times with ethanol and acetone respectively. The nitrogen and sulfur contents of the doped carbon materials were measured by an elemental analyzer, as shown in Table 11.

Table 11

Example 38 39 40 41 42 Pyridine to Thiophene Volume Ratio 1:1 1:3 1:5 1:8 1:20 Nitrogen content/wt% 4.75 2.66 2.04 1.84 1.26 Sulfur content/wt% 2.158 3.399 3.912 3.362 3.25

It can be seen from Table 11 that nitrogen and sulfur co-doped carbon materials can be successfully prepared by using fluorinated carbon nanotubes as the carbon substrate and the mixture of pyridine and thiophene as the heteroatom source.

Examples 43-47

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to 800°C at a rate of 10°C/min in an argon atmosphere, quickly push the porcelain boat from the gas outlet within 10 seconds. Inject the toluene solution of triphenylphosphine with the concentration shown in Table 12 into the high-temperature zone with a micro-injection pump at a rate of 1.5mL/h (the argon atmosphere needs to be ensured) in the center of the tube furnace, and keep injecting for 2 hours. After cooling to room temperature, the sample was taken out and washed five times with ethanol and acetone respectively. The phosphorus content of the doped carbon material was measured with an electron probe microanalyzer, as shown in Table 12.

Table 12

It can be seen from Table 12 that by using fluorinated carbon nanotubes as the carbon substrate and triphenylphosphine as the phosphorus source, carbon materials can be efficiently doped with phosphorus, and the highest phosphorus content can reach 6.37wt%.

Examples 48-55

Weigh 100 mg of carbon fluoride nanotubes and lay them flat on a porcelain boat. After the temperature of the tube furnace rises to 800°C at a rate of 10°C/min in an argon atmosphere, quickly push the porcelain boat from the gas outlet within 10 seconds. into the center of the tube furnace (need to ensure the argon atmosphere), inject the pyridine solution of triphenylphosphine with the concentration shown in Table 13 into the high temperature area with a micro-injection pump at a rate of 1.5mL/h, and continue to inject for 2 hours. After cooling to room temperature, the samples were taken out and washed five times with ethanol and acetone respectively. The nitrogen and phosphorus contents of the doped carbon materials were measured with an electron probe microanalyzer, as shown in Table 13.

Table 13

It can be seen from Table 13 that nitrogen and phosphorus co-doping can be realized on the carbon fluoride nanotube substrate by using the pyridine solution of triphenylphosphine as the heteroatom source, and the amount of heteroatom doping can be easily adjusted by changing the solution concentration. The highest phosphorus content can reach 6.24wt%.

The above-mentioned embodiments are only examples for clearly illustrating the present invention, rather than fully limiting the implementation. Those of ordinary skill in the art can also make other changes in different forms on the basis of the above description. It is impossible and unnecessary to give examples for all implementation modes here, but the obvious changes derived from this are still within the scope of the present invention. within the scope of protection.

Claims (8)

1. a preparation method of nitrogen, sulfur, phosphorus heteroatom-doped carbon material, is characterized in that, comprises the following steps: Using fluorinated carbon materials or fluorinated carbon nanotubes as the carbon substrate, the liquid source containing one or several heteroatoms in nitrogen, sulfur and phosphorus is incorporated into the carbon substrate by pyrolysis deposition at 400-1000°C , or grind and mix the solid source containing one or more heteroatoms of nitrogen, sulfur, and phosphorus with the carbon substrate, and calcinate at 400-800°C to achieve doping to obtain nitrogen, sulfur, and phosphorus heteroatom-doped carbon materials . 2. The method for preparing a carbon material doped with nitrogen, sulfur, and phosphorus heteroatoms according to claim 1, wherein a fluorinated carbon material is used as the carbon substrate, wherein the fluorine content is 1wt%-58wt%. 3. the preparation method of a kind of nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, is characterized in that, described liquid source is pyridine, thiophene, triphenylphosphine toluene solution and dibenzyl di One or more of the sulfur solution; the solid source is one or more of the sublimated sulfur and dibenzyl disulfide. 4. The preparation method of a nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, characterized in that, when thiophene is used to realize sulfur doping, the temperature of cracking and deposition is 500-1000°C, and the injection The rate of thiophene is 1-10mL/h, the deposition time is 2-6 h, and the amount of fluorinated carbon nanotubes is 50-500 mg. 5. the preparation method of a kind of nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, is characterized in that, when adopting sublimation sulfur to realize sulfur doping, the temperature of calcination is 400-800 ℃, time 0.5-4 h. 6. a kind of preparation method of nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, is characterized in that, when using triphenylphosphine toluene solution to prepare phosphorus-doped carbon material, triphenylphosphine The concentration of the toluene solution is 0.1-1 g/mL. 7. the preparation method of a kind of nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, is characterized in that, when adopting pyridine and thiophene to realize nitrogen-sulfur co-doping, the volume ratio of pyridine and thiophene is 1:1-1:20. 8. the preparation method of a kind of nitrogen, sulfur, phosphorus heteroatom-doped carbon material according to claim 1, is characterized in that, when adopting pyridine and dibenzyl disulfide to realize nitrogen-sulfur co-doping, dibenzyl disulfide The concentration of disulfide in pyridine is 0.1-0.8 g/mL; when pyridine and triphenylphosphine are used to achieve nitrogen and phosphorus co-doping, the concentration of triphenylphosphine in pyridine is 0.01-0.4 g/mL.