CN114275747A - Preparation method of thin silk-like nitrogen-doped carbon - Google Patents
Preparation method of thin silk-like nitrogen-doped carbon Download PDFInfo
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- CN114275747A CN114275747A CN202111636354.1A CN202111636354A CN114275747A CN 114275747 A CN114275747 A CN 114275747A CN 202111636354 A CN202111636354 A CN 202111636354A CN 114275747 A CN114275747 A CN 114275747A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 239000007833 carbon precursor Substances 0.000 claims abstract description 29
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 28
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Abstract
The invention discloses a preparation method of thin silk-shaped nitrogen-doped carbon, which comprises the following steps: (1) directly and mechanically mixing the heavy oil residue of the high-temperature self-flowing carbon precursor powder with graphite-phase carbon nitride; (2) or directly stirring and mixing the liquid cheap carbon precursor and graphite-phase carbon nitride powder into a viscous state; (3) and (3) calcining the mixed substance at high temperature, wherein in the process, the carbon precursor is self-coated on the surface of the template by virtue of fluidity, cracked, carbonized and cooled to directly obtain the thin silk-like nitrogen-doped carbon. The method for preparing the thin silk-like nitrogen-doped porous carbon has the advantages of preparing the thin silk-like nitrogen-doped porous carbon in an environment-friendly manner with simple steps, reducing the cost, simplifying the process, solving the problem of graphene coalescence and the problem of efficient utilization of active carbon pores, having good conductivity and excellent wettability, and meeting the requirements of serving as a lithium battery cathode or other high-power energy storage components.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of thin silk-shaped nitrogen-doped carbon.
Background
With the increasing pressure on the development and application of new green energy in China, the demand and development of electrode materials are also endless. Carbonaceous materials have excellent physicochemical stability and good electrical conductivity, and therefore they always occupy a place in electrode materials. Activated carbonaceous materials have developed more and more, and have been widely used as capacitor electrode materials for a long time. With the discovery of graphene, researchers mostly condense the eyesight on the development and modification of graphene materials, and apply the graphene materials to electrochemical energy storage components. The graphene becomes a star electrode material in a super capacitor or a lithium ion capacitor.
For a long time, coal-based or biomass is mostly used as a carbon precursor of the activated carbon, and the activated carbon with different specific surface areas is obtained by physically or chemically activating and pore-forming. However, the obtained micropores are all micropores, and the inner pore channels cannot be effectively utilized during high-power charge and discharge.
At present, the preparation method of graphene or carbon nano-sheet mostly focuses on mechanical stripping, chemical stripping and vapor deposition methods, wherein the vapor deposition method has already been industrialized preliminarily. The mechanical stripping can not realize large-scale preparation, the chemical stripping needs strong acid and strong oxidizing substances, the requirement on equipment is high, the danger is high, and the reagent is easy to cause environmental pollution. Vapor deposition processes typically use small molecular gaseous carbon sources such as methane, ethylene, propylene, and the like, which are expensive to manufacture and are flammable and explosive. Secondly, a large amount of template needs to be used, and recycling of the template is a new challenge.
The doping can improve the conductivity and wettability of the carbonaceous material, and the carbon material is usually doped by mixing the carbon material and a heteroatom precursor and calcining at high temperature, so that the steps are complicated and purification is required again.
Therefore, it is necessary to find a preparation method of thin-layer nitrogen-doped carbon with simple process, low cost and environmental friendliness.
Disclosure of Invention
At present, the thin-layer graphene is high in manufacturing cost and easy to coalesce, and is not beneficial to the transmission and ion storage of electrolyte, so that the whole capacity of the electrolyte cannot be exerted. The activated carbon has a rich pore structure, but the conductivity is insufficient, and the abundant bulk phase pores cannot be effectively utilized under the condition of large current. The high-quality activated carbon has higher manufacturing cost. The method for preparing the thin silk-like nitrogen-doped porous carbon has the advantages of preparing the thin silk-like nitrogen-doped porous carbon in an environment-friendly manner with simple steps, reducing the cost, simplifying the process, solving the problem of graphene coalescence and the problem of efficient utilization of active carbon pores, having good conductivity and excellent wettability, and meeting the requirements of serving as a lithium battery cathode or other high-power energy storage components.
In order to solve the technical problems, the invention adopts a technical scheme that: a preparation method of thin silk-shaped nitrogen-doped carbon comprises the following steps:
(1) directly and mechanically mixing the heavy oil residue of the high-temperature self-flowing carbon precursor powder with graphite-phase carbon nitride;
(2) or directly stirring and mixing the liquid cheap carbon precursor and graphite-phase carbon nitride powder into a viscous state;
(3) and (3) calcining the mixed substance at high temperature, wherein in the process, the carbon precursor is self-coated on the surface of the template by virtue of fluidity, cracked, carbonized and cooled to directly obtain the thin silk-like nitrogen-doped carbon.
Further, the preparation method of the graphite phase carbon nitride powder comprises the following steps: and (3) placing the urea or the melamine in a muffle furnace, slowly heating to 550 ℃, and calcining for 2-4 h to obtain the faint yellow graphite-phase carbon nitride.
Further, in the step (3), the atmosphere of the high-temperature calcination is under the protection of nitrogen.
In the step (1), the carbon precursor powder heavy oil residue is pitch.
Further, in the step (2), the liquid cheap carbon precursor is coal tar or residual oil.
Further, in the step (1), mechanical mixing of the carbon precursor powder heavy oil residue and the graphite phase carbon nitride is achieved by a mixing device.
Further, the mixing device comprises:
the top end of the vertical mixing tank is arranged in an open manner;
and the stirring mechanism is arranged at the bottom end of the vertical mixing tank.
Further, the stirring mechanism includes:
the stirring seat is fixedly arranged at the bottom end of the vertical mixing tank;
the rotating chamber is arranged in the stirring seat;
the two air bag mounting chambers are symmetrically arranged in the stirring seat by taking the rotating chamber as a center;
the stirring shaft is positioned in the vertical mixing tank, and the bottom end of the stirring shaft penetrates through the bottom end of the vertical mixing tank and extends into the rotating chamber;
the stirring rods are positioned in the vertical mixing tank, and the stirring rods are uniformly connected to the stirring shaft;
the stirring motor is arranged at the bottom in the rotating chamber;
the permanent magnet rod is positioned in the rotating chamber, one end of the permanent magnet rod is connected with the bottom end of the stirring shaft, and the other end of the permanent magnet rod is connected with the output end of the stirring motor;
the two air inlets with valves are oppositely arranged at the side end of the stirring seat, the air inlets with valves are communicated with the air bag installation chamber, and one-way valves are arranged on the air inlets with valves;
the air outlets with the valves are distributed at the top end of the stirring seat, the air outlets with the valves are communicated between the air bag installation chamber and the bottom end of the vertical mixing tank, and one-way valves are installed on the air outlets with the valves;
the outer elastic bag body is arranged in the air bag installation chamber and is filled with heat conduction oil;
the inner elastic bag body is fixedly arranged between the top and the bottom of the outer elastic bag body;
the two air storage bag bodies are oppositely arranged on the inner wall of the rotating chamber, and the permanent magnet rod is positioned between the two air storage bag bodies;
the permanent magnet plate is embedded in the end, close to the permanent magnet rod, of the air storage bag body, and the permanent magnet plate is matched with the permanent magnet rod;
one end of the air pipe extends into the rotating chamber and is communicated with the air storage bag body, and the other end of the air pipe extends into the air bag installation chamber, penetrates through the outer elastic bag body and is communicated with the inner elastic bag body;
the friction disc is positioned in the rotating chamber and fixedly connected to the output end of the stirring motor;
the two friction blocks are oppositely arranged on the inner wall of the rotating chamber, the friction blocks are positioned below the air storage bag body, the friction disc is positioned between the two friction blocks, the friction disc is arranged by being attached to the friction blocks, a cavity is formed in each friction block, and heat conduction oil is stored in the cavity;
one end of the oil inlet pipe with the valve extends into the air bag installation chamber and is communicated with the outer elastic bag body, the other end of the oil inlet pipe with the valve extends into the rotating chamber and is communicated with the cavity of the friction block, and the oil inlet pipe with the valve is provided with a one-way valve;
take the valve to go out oil pipe, it stretches into to take valve play oil pipe one end in the gasbag installation room, and with outer elasticity utricule is kept away from and is taken valve oil feed pipe end intercommunication, it stretches into to take the valve to go out the oil pipe other end rotate indoorly, and communicate in the cavity of clutch blocks, it locates to take the valve to go out oil pipe subsides the indoor top of gasbag installation, and establish ties respectively take the valve gas outlet to set up, take the valve to go out to install the check valve on the oil pipe.
Further, a sealing cover is installed at the top end of the vertical mixing tank, and a traveling wheel is installed at the bottom end of the stirring seat.
The invention has the following beneficial effects:
1. the invention takes the cheap carbon precursor with self-fluidity at high temperature as the carbon source, takes the graphite phase carbon nitride as the template and the nitrogen source at the same time, has simple mixing mode, direct physical mixing, and direct mixing without other media, avoids the use of other organic solvents such as toluene, acetone and even aqueous media, saves the cost, greatly reduces the environmental pollution, and saves the energy consumption required by the drying process.
2. Although the thin-layer carbon is prepared by the template method, the post-treatment of the carbon material is not needed, and the steps are very simple;
3. the thin silk-like nitrogen-doped carbon prepared by the method has great application potential in the fields of electrochemical energy storage and electrocatalysis.
4. The self-flowable carbon precursor in the present invention is not limited to pitch and coal tar used in the present invention. All precursors with fluidity at normal temperature or high temperature belong to the category of the scheme;
5. the conventional high-temperature calcination method and other similar heating methods used in the invention can also obtain similar effects to the present application, and belong to the protection scope of the present application, such as plasma-assisted calcination, graphite furnace calcination, infrared furnace calcination, microwave heating and the like.
6. In the invention, carbon precursor powder heavy oil residue and graphite phase carbon nitride are fed into a vertical mixing tank from the top end of the vertical mixing tank, a stirring motor works to drive a friction disc and a permanent magnet rod which are arranged at the output end of the stirring motor to rotate in a rotating chamber, a stirring shaft connected with the output end of the stirring motor rotates in the vertical mixing tank, the stirring shaft drives a stirring rod to rotate in the vertical mixing tank, so that the carbon precursor powder heavy oil residue and the graphite phase carbon nitride are stirred and mixed, the permanent magnet rod rotates between two air storage bags, so that two poles of the permanent magnet rod are alternately contacted with permanent magnet plates in the two air storage bags, for example, when the N pole of the permanent magnet rod is oppositely attracted with the permanent magnet plate in the air storage bag at the left side, the S pole of the permanent magnet rod is like to the permanent magnet plate in the air storage bag at the right side, and the air storage bag at the left side is pulled to be large under the magnetic action, the volume of the inner elastic bag body in the left air bag installation chamber is reduced, the volume of the outer elastic bag body in the left air bag installation chamber is dragged to be reduced, heat conducting oil in the outer elastic bag body is pressed into the oil outlet pipe with the valve in the left air bag installation chamber, the volume of the outer elastic bag body in the left air bag installation chamber is reduced, air flow is sucked into the left air bag installation chamber from the air inlet with the valve, conversely, the volume of the right air bag body is reduced under the magnetic action, the volume of the inner elastic bag body in the right air bag installation chamber is increased, the volume of the outer elastic bag body in the left air bag installation chamber is increased, heat conducting oil in the inner cavity of the friction block is sucked into the right outer elastic bag body from the oil inlet pipe with the valve, the volume of the outer elastic bag body in the right air bag installation chamber is increased, air flow in the right air bag installation chamber is sent into the vertical mixing tank from the air outlet with the valve, and when the friction disc is attached to the friction block to rotate, the heat conducting oil in the cavity of the friction block has heat, the heat conducting oil with the heat flows back into the cavity of the friction block through the outer elastic bag body and the oil inlet pipe with the valve in sequence, and flows back into the cavity of the friction block through the oil outlet pipe with the valve, and the heat conducting oil with the heat flows into the vertical mixing tank from the air outlet of the valve to exchange heat, so that the bottom end of the self-standing mixing tank with the heat flows into the vertical mixing tank, the flowability of the carbon precursor powder heavy oil residue and the graphite phase carbon nitride in the vertical mixing tank is increased, certain drying is carried out on the carbon precursor powder heavy oil residue and the graphite phase carbon nitride, and the phenomenon that the carbon precursor powder heavy oil residue and the graphite phase carbon nitride are bonded together to influence the stirring effect is avoided.
Drawings
FIG. 1 is a transmission electron microscope image of a thin silk-like nitrogen-doped porous carbon prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nitrogen-doped porous carbon in the form of a thin silk prepared in example 1;
FIG. 3 is a graph of rate capability of the tissue-like nitrogen-doped porous carbon prepared in example 1 at 100mA/g to 8A/g;
FIG. 4 is a cycle chart of the tissue-like nitrogen-doped porous carbon prepared in example 1 at 2A/g;
FIG. 5 is a scanning electron microscope image of the nitrogen-doped porous carbon in the form of a thin silk prepared in example 2;
FIG. 6 is a scanning electron and transmission electron micrograph of nitrogen-rich porous graphene prepared according to comparative example 1;
FIG. 7 is a schematic view of the mixing device of the present invention;
fig. 8 is an enlarged view of the rolling chamber of the present invention.
In the figure: 11. a vertical mixing tank; 12. a stirring mechanism; 13. a stirring seat; 14. a rotating chamber; 15. an airbag installation chamber; 16. a stirring shaft; 17. a stirring rod; 18. a stirring motor; 19. a permanent magnet bar; 10. a valved gas inlet; 21. an air outlet with a valve; 22. an outer elastomeric bladder; 23. an inner elastic bladder body; 24. a gas storage bag body; 25. a permanent magnet plate; 26. an air tube; 27. a friction disk; 28. a friction block; 29. an oil inlet pipe with a valve; 20. an oil outlet pipe with a valve.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Example 1:
5g of asphalt powder crushed to 200 meshes and graphite-phase carbon nitride prepared from 5g of urea are directly and rapidly crushed and mixed in a crusher;
and placing the mixture in a porcelain boat, calcining for 1h at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out to obtain the thin silk-like nitrogen-doped porous carbon.
The specific surface area of the prepared thin silk-shaped nitrogen-doped porous carbon is 692m2In terms of a/g, the nitrogen content was 8.6% by weight. The transmission electron microscope photograph showsFIG. 1 shows a scanning electron micrograph of FIG. 2.
The rate performance of the lithium ion battery negative electrode is shown in figure 3 under the conditions of 100mA/g to 8A/g. Preliminary tests show that the cell is in a slow activation state all the time when the cell is cycled for 600 cycles without attenuation under the current density of 2A/g, and the cycle curve is shown in figure 4.
Example 2:
5g of asphalt powder crushed to 200 meshes and graphite-phase carbon nitride prepared from 10g of urea are directly and rapidly crushed and mixed in a crusher;
and placing the mixture in a porcelain boat, calcining for 1h at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out to obtain the thin silk-like nitrogen-doped porous carbon.
The specific surface area of the prepared thin silk-shaped nitrogen-doped porous carbon nitrogen is 885m2In terms of a/g, the nitrogen content was 10.8 wt.%. The morphology is similar to example 1. The transmission electron micrograph is shown in FIG. 5.
Comparative example 1:
the patent of Yangwang et al (publication No. CN 107416806A) is cited, and porous graphene is prepared by using a plasma enhanced chemical vapor deposition method and performing low-temperature cracking on a graphite-phase carbon nitride template by using a gaseous carbon source methane. Firstly, Ar/H is introduced into a tube furnace at low pressure2Heating the mixed gas to 550 ℃, introducing certain methane, starting a radio frequency power supply (Plasma power is 300W), and carrying out low-temperature pyrolysis for 2h by virtue of Plasma. After the reaction is finished, closing the carbon source and the plasma, and continuously introducing Ar and H2And heating to 750 ℃ and calcining for 1h to remove the template. And naturally cooling to obtain the low-density nitrogen-rich porous graphene. Specific surface area of 959m2Per g, nitrogen content 11.7 wt%. The appearance observed by a scanning electron microscope and a transmission electron microscope is shown in figure 6.
Example 3:
5g of asphalt powder crushed to 500 meshes and graphite-phase carbon nitride prepared from 10g of urea are directly and rapidly crushed and mixed in a crusher;
placing the mixture in a porcelain boat, and calcining for 1h at 850 ℃ in a high-temperature furnace under the protection of nitrogen; cooling to room temperature and taking out; obtaining the thin silk-shaped nitrogen-doped porous carbon.
Prepared thin silk-like nitrogen-doped porous carbon-nitrogen ratio meterArea of 801m2In terms of a/g, the nitrogen content was 10.2% by weight. The morphology is similar to example 2.
Example 4:
stirring 20g of coal tar and 10g of urea in a porcelain boat into paste, calcining for 1h at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out to obtain the thin silk-shaped nitrogen-doped porous carbon.
The specific surface area of the prepared thin silk-shaped nitrogen-doped porous carbon nitrogen is 759m2Per g, nitrogen content 9.86 wt%. The morphology is similar to example 1.
Example 5:
stirring 50g of vacuum residue and 10g of urea in a porcelain boat to form paste, calcining at 850 ℃ for 1h in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out to obtain the thin silk-shaped nitrogen-doped porous carbon.
The specific surface area of the prepared thin silk-shaped nitrogen-doped porous carbon nitrogen is 637m2In terms of a/g, the nitrogen content is 10.5 wt.%. The morphology is similar to example 1.
Example 6:
as an alternative embodiment of the present invention, as shown in fig. 7 and 8, in the step (1), mechanical mixing of the carbon precursor powder heavy oil residue and the graphite phase carbon nitride is achieved by a mixing device.
In this embodiment, the mixing device includes:
the top end of the vertical mixing tank 11 is arranged in an open manner;
and the stirring mechanism 12 is arranged at the bottom end of the vertical mixing tank 11.
In the present embodiment, the stirring mechanism 12 includes:
the stirring seat 13 is fixedly arranged at the bottom end of the vertical mixing tank 11;
the rotating chamber 14, the said rotating chamber 14 locates in the said mixing base 13;
the two airbag installation chambers 15 are symmetrically arranged in the stirring seat 13 by taking the rotating chamber 14 as a center;
the stirring shaft 16 is positioned in the vertical mixing tank 11, and the bottom end of the stirring shaft 16 penetrates through the bottom end of the vertical mixing tank 11 and extends into the rotating chamber 14;
the stirring rods 17 are positioned in the vertical mixing tank 11, and the stirring rods 17 are uniformly connected to the stirring shaft 16;
a stirring motor 18, wherein the stirring motor 18 is arranged at the bottom in the rotating chamber 14;
the permanent magnet rod 19 is positioned in the rotating chamber 14, one end of the permanent magnet rod 19 is connected with the bottom end of the stirring shaft 16, and the other end of the permanent magnet rod 19 is connected with the output end of the stirring motor 18;
the two valved air inlets 10 are oppositely arranged at the side end of the stirring seat 13, the valved air inlets 10 are communicated with the air bag installation chamber 15, and one-way valves are arranged on the valved air inlets 10;
the air outlets 21 with the valves are distributed at the top end of the stirring seat 13, the air outlets 21 with the valves are communicated between the air bag installation chamber 15 and the bottom end of the vertical mixing tank 11, and the air outlets 21 with the valves are provided with one-way valves;
the outer elastic bag body 22, the outer elastic bag body 22 is installed in the air bag installation chamber 15, and the heat conduction oil is filled in the outer elastic bag body 22;
an inner elastic bag body 23, wherein the inner elastic bag body 23 is fixedly arranged between the inner top and the inner bottom of the outer elastic bag body 22;
the two air storage bags 24 are oppositely arranged on the inner wall of the rotating chamber 14, and the permanent magnet rod 19 is positioned between the two air storage bags 24;
the permanent magnet plate 25 is embedded in the air storage bag body 24 close to the end of the permanent magnet rod 19, and the permanent magnet plate 25 is matched with the permanent magnet rod 19;
one end of the air pipe 26 extends into the rotating chamber 14 and is communicated with the air storage bag body 24, and the other end of the air pipe 26 extends into the air bag installation chamber 15, penetrates through the outer elastic bag body 22 and is communicated with the inner elastic bag body 23;
a friction disc 27, wherein the friction disc 27 is positioned in the rotating chamber 14, and the friction disc 27 is fixedly connected to the output end of the stirring motor 18;
the two friction blocks 28 are oppositely arranged on the inner wall of the rotating chamber 14, the friction block 28 is positioned below the air storage bag body 24, the friction disc 27 is positioned between the two friction blocks 28, the friction disc 27 is arranged by being attached to the friction block 28, a cavity is arranged in the friction block 28, and heat conduction oil is stored in the cavity;
one end of the oil inlet pipe 29 with the valve extends into the air bag installation chamber 15 and is communicated with the outer elastic bag body 22, the other end of the oil inlet pipe 29 with the valve extends into the rotating chamber 14 and is communicated with the cavity of the friction block 28, and the oil inlet pipe 29 with the valve is provided with a one-way valve;
take valve to go out oil pipe 20, take valve to go out oil pipe 20 one end and stretch into in the gasbag installation room 15, and with outer elasticity utricule 22 keeps away from taking the valve to advance oil pipe 29 end intercommunication, take valve to go out oil pipe 20 other end and stretch into rotate the indoor 14, and communicate in the cavity of clutch blocks 28, take valve to go out oil pipe 20 subsides to locate top in the gasbag installation room 15, and establish ties respectively take valve gas outlet 21 to set up, take the valve to go out oil pipe 20 and go up to install the check valve.
The working principle and the beneficial effects of the technical scheme are as follows:
carbon precursor powder heavy oil residues and graphite phase carbon nitride are fed into the vertical mixing tank 11 from the top end of the vertical mixing tank 11, the stirring motor 18 works to further drive the friction disc 27 arranged at the output end of the stirring motor 18 and the permanent magnet rod 19 to rotate in the rotating chamber 14, the stirring shaft 16 connected with the output end of the stirring motor 18 rotates in the vertical mixing tank 11, the stirring shaft 16 drives the stirring rod 17 to rotate in the vertical mixing tank 11, so that the carbon precursor powder heavy oil residues and the graphite phase carbon nitride are stirred and mixed, the permanent magnet rod 19 rotates between the two air storage bags 24, so that two poles of the permanent magnet rod 19 are alternately contacted with the permanent magnet plates 25 in the two air storage bags 24, for example, when the N pole of the permanent magnet rod 19 is attracted oppositely to the permanent magnet plate 25 in the air storage bag 24 on the left side, the S pole of the permanent magnet rod 19 is repelled with the permanent magnet plate 25 in the permanent magnet air storage bag 24 on the right side, at this time, the volume of the left air bag 24 is increased by the magnetic action, the volume of the inner elastic bag body 23 in the left air bag installation chamber 15 is decreased, the volume of the outer elastic bag body 22 in the left air bag installation chamber 15 is decreased by the magnetic action, the heat transfer oil in the outer elastic bag body 22 is pressed into the valved oil outlet pipe 20 in the left air bag installation chamber 15, the volume of the outer elastic bag body 22 in the left air bag installation chamber 15 is decreased, the air flow is sucked into the left air bag installation chamber 15 from the valved air inlet 10, conversely, the volume of the right air bag body 24 is decreased by the magnetic action, the volume of the inner elastic bag body 23 in the right air bag installation chamber 15 is increased, the volume of the outer elastic bag body 22 in the left air bag installation chamber 15 is increased, the heat transfer oil in the cavity of the friction block 28 is sucked into the right outer elastic bag body 22 from the valved oil inlet pipe 29, and the volume of the outer elastic bag body 22 in the right air bag installation chamber 15 is increased, air flow in the right air bag installation chamber 15 is sent into the vertical mixing tank 11 from the air outlet 21 with the valve, when the friction disc 27 rotates by being attached to the friction block 28, heat conducting oil in a cavity of the friction block 28 is enabled to carry heat, the heat conducting oil flows back into the cavity of the friction block 28 from the oil inlet pipe 29 with the valve sequentially through the outer elastic bag body 22 and the oil outlet pipe 20 with the valve, and the heat conducting oil and the air outlet 21 with the valve are sent into the vertical mixing tank 11 for heat exchange, so that the bottom end of the self-supporting mixing tank 11 with the heat air flow is sent into the vertical mixing tank 11, certain drying is carried out on carbon precursor powder heavy oil residues and graphite phase carbon nitride while the mobility of the carbon precursor powder heavy oil residues and the graphite phase carbon nitride in the vertical mixing tank 11 is increased, and the carbon precursor powder heavy oil residues and the graphite phase carbon nitride are prevented from being bonded together to influence the stirring effect.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A preparation method of thin silk-shaped nitrogen-doped carbon is characterized by comprising the following steps: the method comprises the following steps:
(1) directly and mechanically mixing the heavy oil residue of the high-temperature self-flowing carbon precursor powder with graphite-phase carbon nitride;
(2) or directly stirring and mixing the liquid cheap carbon precursor and graphite-phase carbon nitride powder into a viscous state;
(3) and (3) calcining the mixed substance at high temperature, wherein in the process, the carbon precursor is self-coated on the surface of the template by virtue of fluidity, cracked, carbonized and cooled to directly obtain the thin silk-like nitrogen-doped carbon.
2. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 1, which is characterized in that: the preparation method of the graphite phase carbon nitride powder comprises the following steps: and (3) placing the urea or the melamine in a muffle furnace, slowly heating to 550 ℃, and calcining for 2-4 h to obtain the faint yellow graphite-phase carbon nitride.
3. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 1, which is characterized in that: in the step (3), the high-temperature calcination environment is under the protection of nitrogen.
4. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 1, which is characterized in that: in the step (1), the carbon precursor powder heavy oil residue is asphalt.
5. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 1, which is characterized in that: in the step (2), the liquid cheap carbon precursor is coal tar or residual oil.
6. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 1, which is characterized in that: in the step (1), the mechanical mixing of the carbon precursor powder heavy oil residue and the graphite phase carbon nitride is realized by a mixing device.
7. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 6, which is characterized in that: the mixing device comprises:
the top end of the vertical mixing tank (11) is arranged in an open manner;
and the stirring mechanism (12) is arranged at the bottom end of the vertical mixing tank (11).
8. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 7, which is characterized in that: the stirring mechanism (12) includes:
the stirring seat (13), the stirring seat (13) is fixedly arranged at the bottom end of the vertical mixing tank (11);
the rotating chamber (14), the rotating chamber (14) is arranged in the stirring seat (13);
the two airbag mounting chambers (15) are symmetrically arranged in the stirring seat (13) by taking the rotating chamber (14) as a center;
the stirring shaft (16) is positioned in the vertical mixing tank (11), and the bottom end of the stirring shaft (16) penetrates through the bottom end of the vertical mixing tank (11) and extends into the rotating chamber (14);
the stirring rods (17) are positioned in the vertical mixing tank (11), and the stirring rods (17) are uniformly connected to the stirring shaft (16);
the stirring motor (18), the stirring motor (18) is installed at the bottom in the rotating chamber (14);
the permanent magnet rod (19) is positioned in the rotating chamber (14), one end of the permanent magnet rod (19) is connected with the bottom end of the stirring shaft (16), and the other end of the permanent magnet rod (19) is connected with the output end of the stirring motor (18);
the two air inlets (10) with valves are oppositely arranged at the side end of the stirring seat (13), the air inlets (10) with valves are communicated with the air bag installation chamber (15), and one-way valves are arranged on the air inlets (10) with valves;
the air outlets (21) with valves are distributed at the top end of the stirring seat (13), the air outlets (21) with valves are communicated between the air bag installation chamber (15) and the bottom end of the vertical mixing tank (11), and one-way valves are installed on the air outlets (21) with valves;
the outer elastic bag body (22), the outer elastic bag body (22) is installed in the air bag installation chamber (15), and heat conduction oil is filled in the outer elastic bag body (22);
an inner elastic bag body (23), wherein the inner elastic bag body (23) is fixedly arranged between the inner top and the inner bottom of the outer elastic bag body (22);
the two air storage bags (24) are oppositely arranged on the inner wall of the rotating chamber (14), and the permanent magnet rod (19) is positioned between the two air storage bags (24);
the permanent magnet plate (25), the said permanent magnet plate (25) inlays and locates the said air storage bag body (24) and nears the end of the permanent magnet stick (19), the said permanent magnet plate (25) adapts to the said permanent magnet stick (19) to set up;
one end of the air pipe (26) extends into the rotating chamber (14) and is communicated with the air storage bag body (24), and the other end of the air pipe (26) extends into the air bag installation chamber (15), penetrates through the outer elastic bag body (22) and is communicated with the inner elastic bag body (23);
a friction disc (27), wherein the friction disc (27) is positioned in the rotating chamber (14), and the friction disc (27) is fixedly connected to the output end of the stirring motor (18);
the two friction blocks (28) are oppositely arranged on the inner wall of the rotating chamber (14), the friction blocks (28) are positioned below the air storage bag body (24), the friction disc (27) is positioned between the two friction blocks (28), the friction disc (27) is arranged by being attached to the friction blocks (28), a cavity is formed in each friction block (28), and heat conduction oil is stored in the cavity;
one end of the oil inlet pipe (29) with the valve extends into the air bag installation chamber (15) and is communicated with the outer elastic bag body (22), the other end of the oil inlet pipe (29) with the valve extends into the rotating chamber (14) and is communicated with the cavity of the friction block (28), and the oil inlet pipe (29) with the valve is provided with a one-way valve;
take valve to go out oil pipe (20), take valve to go out oil pipe (20) one end and stretch into in gasbag installation room (15), and with outer elasticity utricule (22) are kept away from and are taken valve oil inlet pipe (29) end intercommunication, take valve to go out oil pipe (20) other end and stretch into rotate in the room (14), and communicate in the cavity of clutch blocks (28), take valve to go out oil pipe (20) subside and locate top in gasbag installation room (15), and establish ties respectively take valve gas outlet (21) to set up, take the valve to go out to install the check valve on oil pipe (20).
9. The method for preparing the thin silk-like nitrogen-doped carbon according to claim 8, which is characterized in that: a sealing cover is installed at the top end of the vertical mixing tank (11), and a traveling wheel is installed at the bottom end of the stirring seat (13).
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