阅读说明：本技术 石墨化炭管材料及其制备方法和应用 (Graphitized carbon tube material and preparation method and application thereof ) 是由 何海勇 王德宇 赵泽华 陈伟林 陈勤勤 潘林海 王珏 于 2018-07-20 设计创作，主要内容包括：本发明公开了一种石墨化炭管材料及其制备方法和应用,所述石墨化炭管材料包括石墨化炭管纤维,所述石墨化炭管纤维内部沿其纵向贯通所述石墨化炭管纤维设有空心通腔。所制得石墨化炭管材料内部导通,无竹节状结构,而且纯度高杂质少不含催化剂杂质。本发明同时还提供了该方法制备得到的石墨化炭管材料的制备方法及其应用。(The invention discloses graphitized carbon tube materials and a preparation method and application thereof, wherein the graphitized carbon tube materials comprise graphitized carbon tube fibers, the graphitized carbon tube fibers are longitudinally communicated with the graphitized carbon tube fibers along the inside of the graphitized carbon tube fibers and are provided with hollow through cavities.)

1, kind graphitization carbon tube material, its characterized in that, graphitization carbon tube material includes graphitization carbon tube fibre, graphitization carbon tube fibre is inside to link up along its vertically graphitization carbon fiber is equipped with hollow logical chamber.

2. The graphitized carbon tube material of claim 1, wherein the wall thickness of the graphitized carbon tube fibers is 5-30 nm;

preferably, the wall thickness of the graphitized carbon tube fiber is 10-20 nm;

preferably, the length of the graphitized carbon tube fiber is 10-1000 μm;

preferably, the diameter of the graphitized carbon tube fiber is 50-3000 nm;

preferably, the diameter of the graphitized carbon tube fiber is 200-3000 nm;

preferably, the graphitized carbon tube material is a graphitized carbon tube film material, the graphitized carbon tube film material comprises a body formed by interweaving fibers of the graphitized carbon tube, and the thickness of the body is 100nm-50 μm.

3, a method for preparing a graphitized carbon tube material as claimed in claim 1 or 2, which comprises the steps of:

preparing a template phase material;

growing a graphitized carbon film layer on the surface of the template phase material by adopting a chemical vapor deposition method to obtain a film layer material, and removing the template phase material in the film layer material by adopting a wet chemical method to obtain the graphitized carbon tube material.

4. The graphitized carbon tube material preparation method according to claim 3, wherein the graphitized carbon tube material preparation method adopts wet etching to remove the template phase material in the film layer material;

preferably, the template phase material comprises a nano-scale fiber material, wherein the nano-scale fiber material is at least of a silicon oxide nano-scale fiber material, an aluminum oxide nano-scale fiber material and a magnesium oxide nano-scale fiber material, and the fiber diameter of the nano-scale fiber material is 200-3000 nm;

preferably, the step of preparing the template phase material comprises a step of growing active particles inside the template phase material.

5. The preparation method of the graphitized carbon tube material according to claim 4, wherein the wet etching treatment time is 2-24 hours, and the etchant used in the wet etching is at least kinds of hydrofluoric acid, sodium hydroxide, hydrochloric acid and nitric acid solution.

6. The method for preparing the graphitized carbon tube material according to claim 4, wherein the template phase material is prepared by an electrostatic spinning method; adding the active particles into a raw material solution used in the electrostatic spinning method;

preferably, the active particles are inorganic nanoparticles, and the inorganic nanoparticles are inorganic elementary substance nanoparticles or inorganic compound nanoparticles.

7. The graphitized carbon tube material preparation method of claim 6, wherein the inorganic simple substance nanoparticles are metal nanoparticles;

preferably, the inorganic compound nanoparticles are oxide nanoparticles or metal compound nanoparticles;

preferably, the inorganic substance in the raw material solution is mixed with the raw material solution in a mass ratio of the inorganic substance to the raw material solution of 1: 100-1: 100000 adding;

preferably, the inorganic substance in the raw material solution is added according to the mass ratio of the inorganic substance to the raw material solution of 1: 1000.

8. The graphitized carbon tube material of claim 7, wherein the metal nanoparticles are noble metal nanoparticles.

9. The method for preparing the graphitized carbon tube material according to claim 3, wherein the carbon source used for growing the graphitized carbon film layer in the chemical vapor deposition method is at least carbon sources selected from methane, acetylene, ethylene hydrocarbon and ethanol;

preferably, the temperature for growing the graphitized carbon film layer in the chemical vapor deposition method is 1000-1500 ℃, and the heat preservation time is 5-30 minutes.

10, use of the graphitized carbon tube material described in claim 1 or 2 in an electrically conductive material or a catalyst support.

Technical Field

The invention relates to graphitized carbon tube materials and a preparation method and application thereof, belonging to the field of carbon materials.

Background

The electrostatic spinning technology is technology for preparing nano/micron fibers by using high-voltage electric field acting force, the diameter of the nano/micron fibers prepared by the method can be from nano to micron, and the fibers are stretched, solidified and deposited on a receiving plate to form a film or form fibers.

Chemical Vapor Deposition (CVD) is a technique that mainly uses kinds or several kinds of gas phase compounds or simple substances containing film elements to chemically react on the surface of a substrate to form a film, chemical vapor deposition is a new technique for preparing inorganic materials that has been developed in recent decades, and chemical vapor deposition has been used in for purifying materials, developing new crystals, and depositing various single crystal, polycrystalline or glassy inorganic thin film materials.

At present, the carbon nano tube needs to be added with catalysts such as iron, cobalt, nickel and the like in the synthesis process, and the catalysts are usually coated by a compact graphitized layer and are difficult to remove, so that the commonly used carbon nano tube contains a large amount of metal catalysts.

Disclosure of Invention

According to aspects of the application, graphitized carbon tube materials are provided, the interior of the graphitized carbon tube materials is communicated, a bamboo-shaped structure is avoided, and the graphitized carbon tube materials are high in purity and few in impurities and do not contain catalyst impurities.

Compared with the carbon nano tube prepared by a catalyst method, the invention provides methods for synthesizing the high-purity graphitized carbon tube, the diameter and the tube thickness of the graphitized carbon tube are adjustable, and the graphitized carbon tube has no bamboo joint structure inside, thereby being beneficial to loading and filling active substances.

Graphitized carbon tube material includes graphitized carbon tube fibre, graphitized carbon tube fibre is inside to link up along its vertically graphitized carbon tube fibre is equipped with hollow logical chamber.

Optionally, the graphitized carbon tube material has no bamboo-like structure inside the graphitized carbon tube fibers. The graphitized carbon tube fiber herein includes an inner wall of the graphitized carbon tube fiber and a hollow through cavity portion inside.

Preferably, the wall thickness of the graphitized carbon tube fiber is 5-30 nm; more preferably, the wall thickness of the graphitized carbon tube fiber is 10-20 nm. The graphitized carbon tube fiber with the size is prepared, and the prepared graphitized carbon tube material can improve the conductivity of the material and the loading efficiency of the catalyst.

More preferably, the length of the graphitized carbon tube fiber is 10 μ 0 to 1000 μm.

Preferably, the diameter of the graphitized carbon tube fiber is 50-3000 nm; more preferably, the diameter of the graphitized carbon tube fiber is 200-3000 nm. The diameter here refers to the vertical distance from the central axis to the outer wall of the graphitized carbon fiber, and includes the diameter of the hollow through cavity. The prepared graphitized carbon fiber with the size can improve the conductivity of the obtained graphitized carbon tube material and improve the filling efficiency of the catalyst.

Preferably, the graphitized carbon tube material is a graphitized carbon tube film material, the graphitized carbon tube film material comprises a body formed by interweaving graphitized carbon fibers, and the thickness of the body is 100nm-50 μm. The prepared graphitized carbon tube film material with the size can be applied to the field of sensors.

The invention also provides a preparation method of the graphitized carbon tube material in the aspect of , which comprises the following steps:

preparing a template phase material;

growing a graphitized carbon film layer on the surface of the template phase material by adopting a chemical vapor deposition method to obtain a film layer material, and removing the template phase material in the film layer material by adopting a wet chemical method to obtain the graphitized carbon tube material.

Optionally, the graphitized carbon tube material has no bamboo-like structure inside the graphitized carbon tube fiber.

By adopting the method, a catalyst containing metal is not needed, other impurities in the obtained graphitized carbon are avoided, and the purity of the obtained graphitized carbon tube material can be improved. The template phase material obtained in the method can be prepared by adopting the existing method, and only the surface of the obtained template phase material is required to be ensured to grow the graphitized carbon film layer by a chemical vapor deposition method. The template phase material can be fiber, film formed by fiber interweaving or member with macroscopic structure formed by fiber interweaving, and the specific structure is determined according to the structure of the required graphitized carbon tube material.

The method can adjust the thickness of the formed graphitized carbon film layer by adjusting various parameters in the chemical vapor deposition method, for example, the thickness of the graphitized carbon film layer is adjusted by adjusting the ventilation time. The diameter of the obtained graphitized carbon tube material is adjusted by adjusting the diameter of the template phase material used. Therefore, the method realizes the adjustability of various parameters of the prepared graphitized carbon tube material and widens the application range of the obtained graphitized carbon tube material.

The graphitized carbon tube material obtained by the method can be in a fiber shape, a tubular shape, a film shape or a device shape with a macroscopic structure according to requirements. If the graphitized carbon tube material is fibrous or tubular, the formed graphitized carbon tube material is the graphitized carbon fiber or the graphitized carbon tube with the hollow through cavity.

If the graphitized carbon tube material is in a film shape or other macroscopic structures, the film shape is taken as an example for explanation: is formed by interweaving (orderly/disorderly) a plurality of graphitized carbon tube fibers with hollow through cavities.

Preferably, the preparation method of the graphitized carbon tube material adopts wet etching to remove the template phase material in the film layer material.

By adopting wet etching, the formed film material structure can be well maintained, the damage to the graphitized carbon tube material structure is reduced, the tubular structure is maintained, and meanwhile, the bamboo-like structure can be prevented from being formed on the inner wall of the formed graphitized carbon tube material.

Preferably, the template phase material comprises a nano-scale fiber material, the nano-scale fiber material is at least of a silicon oxide nano-scale fiber material, an aluminum oxide nano-scale fiber material and a magnesium oxide nano-scale fiber material, and the fiber diameter of the nano-scale fiber material is 200-3000 nm.

Optionally, the template phase material comprises silica, alumina or magnesia nanowires.

Optionally, the template phase material further comprises inorganic particles.

The specific template phase material may be prepared by any of conventional methods such as electrospinning, templating, chemical vapor deposition, laser ablation, thermal evaporation, gas-liquid-solid or sol-gel methods, using procedures well established in the art for such methods.

The following examples of the electrostatic spinning method, the template method, and the gas-liquid-solid method for preparing the silica fiber are described:

the method I comprises the following steps of preparing a silicon oxide nanowire by an electrostatic spinning method:

the electrostatic spinning apparatus for electrostatic spinning generally comprises a high voltage power supply, a receiving substrate for receiving polymer fibers, a syringe for containing a spinnable polymer solution or a polymer mixed solution with additives, and a copper wire, the receiving substrate may be any conductive material such as copper foil and aluminum foil, the syringe may have a capacity of 1-10mL, a needle with a 0.1-0.5mm tip at end, the positive pole of the high voltage power supply is connected to the copper wire, the negative pole of the high voltage power supply is connected to the receiving substrate, as shown in FIG. 1, the method places the spinnable polymer mixed solution in the syringe, then connects the positive pole of the high voltage power supply to the needle, the negative pole to the substrate, opens the high voltage power supply and starts the electrostatic spinning apparatus, thus forming a high voltage electric field between the needle and the receiving substrate, the polymer solution in the syringe, through the needle, forming disordered and ordered micro/nano fibers under the action of the high voltage, finally depositing the nano fibers on the receiving apparatus, forming a polymer nano fiber film by depositing the nano fibers on the receiving apparatus, wherein the high voltage power supply is selected at 7-15KV, preferably 9-12KV, the receiving nozzle, the receiving substrate, the nozzle, the receiving distance is 12 KV., the high voltage, the nano fibers are preferably, the high temperature is increased from 1-600 min, the temperature of the receiving apparatus is preferably, and the calcining time is increased from 600-1 min, and the high temperature of.

The method II comprises the steps of preparing silicon oxide nanowires by a template method, wherein templates for preparing the silicon oxide nanowires mainly comprise three types, namely types of -dimensional templates which are based on other nanowires or nanotubes, such as carbon nanotubes and silicon nanowires, the second type of three-dimensional templates which are based on a nano array structure and comprise anodized aluminum templates, organic high polymer templates and the like, the third type of soft templates which are based on ionic surfactants, for example, the silicon oxide nanotubes are obtained by taking the carbon nanotubes as a base material and introducing tetraethyl silicate and heat treatment, the silicon oxide nanotubes are prepared by taking vertical silicon nanowires as templates and adopting a thermal oxidation etching method, and the silicon oxide nanowires are used as templates and are combined with a sol gel method to prepare a large number of controllable silicon oxide nanotubes.

A method III for preparing silicon oxide nanowires by a gas-liquid-solid method is a method which is used most for preparing dimensional nano silicon oxide, and the method is mainly characterized in that silicon oxide nanowires are prepared by different evaporation sources and raw materials, the gas-liquid-solid method for growing the nanowires has two processes of depositing gaseous atoms in a gas-liquid system in a liquid solution, and separating out solids from a supersaturated liquid solution state at a liquid-solid interface of the liquid-solid system, and a protective gas is introduced by the gas-liquid-solid method for growing, wherein the protective gas is argon, and mixed powder of silicon and aluminum oxide is heated at 1150-1200 ℃ to obtain a large amount of silicon oxide nanowires, the diameter range of the silicon oxide nanowires is 20-200nm, and the length of the silicon oxide nanowires is several millimeters.

The following examples of the preparation of alumina nanofibers by electrospinning and the preparation of magnesium oxide fibers by sol-gel method are given:

and IV, preparing the alumina nano fiber by an electrostatic spinning method. Mixing AlCl₃·6H₂O and A1 (NO)₃)₃Adding into nitric acid, stirring and dissolving. The above solution was transferred to a round bottom flask and then aluminum isopropoxide was slowly added to the above solution. And adding the pot powder after the aluminum isopropoxide is completely dissolved. The above solution was stirred at 80 ℃. Then adding a void former and a spinning inhibitor to obtain the sol spinning solution. And (3) carrying out electrostatic spinning on the sol spinning solution. The spinning conditions are that an external electric field is 20kV, the distance between a spinning needle head and a receiving plate is 20cm, the inner diameter of the spinning needle head is 0.9mm, and the feeding speed is 2.0 mL/h. The environmental humidity is less than 10% and the temperature is less than 10 ℃ in the spinning process. The xerogel fiber obtained was dried in an oven at 80 ℃ for 2 hours. The specific forging process is that the sintering is carried out for 12h at 450 ℃, or respectively carried out for 0.5h at 700 ℃, 800 ℃ and 900 ℃, and the heating rate is 10 ℃/min.

The method V is characterized in that the magnesium oxide fiber is prepared by a sol-gel method, magnesium oxide and propionic acid are used as basic raw materials, a magnesium oxysulfate (PPM) precursor fiber is prepared by the sol-gel method, and then the pure magnesium oxide fiber is obtained after heat treatment.

Preferably, the carbon source used for growing the graphitized carbon film layer in the chemical vapor deposition method is at least of methane, acetylene, ethylene hydrocarbon and ethanol, the temperature for growing the graphitized carbon film layer in the chemical vapor deposition method is 1000-1500 ℃, and the heat preservation time is 5-30 minutes.

Preferably, the wet etching treatment time is 2-24 hours, and the etchant used in the wet etching is at least of hydrofluoric acid, sodium hydroxide, hydrochloric acid and nitric acid solution.

Preferably, the step of preparing the template phase material comprises a step of growing active particles inside the template phase material.

The specific step of growing the active particles can be adjusted according to different preparation methods of the template phase material, for example, when the template phase material is prepared by a sol-gel method, the active particles can be added into the base raw material.

Preferably, the template phase material is prepared by an electrostatic spinning method. The method for preparing the template phase material can conveniently control the fiber size in the obtained graphitized carbon tube material.

The electrospinning process can be carried out according to the procedures and parameters of the prior art. Preferably, a thin film formed by interweaving silica fibers is prepared by an electrostatic spinning method and is used as a template phase material. The electrostatic spinning conditions include: the voltage of the high-voltage power supply is 7-15 KV; more preferably 9-12 KV. The distance between the nozzle and the receiving substrate is 10-25mm, more preferably 15-20 mm. The receiving time is 1 minute to 600 minutes. The receiving area is 1-150 square centimeters.

The spinnable polymer solution used in the electrostatic spinning method can be any polymer capable of finally forming a micro/nano-scale polymer film by a spinning technology, preferably, the spinnable polymer solution used in the electrostatic spinning method is or more of polyvinyl alcohol, polyvinyl pyrrolidone and polyethylene glycol, preferably polyvinyl alcohol, and preferably, the concentration of the spinnable polymer solution is 5-30 wt%.

Preferably, the solvent for the spinnable polymer used in the electrospinning method may be at least kinds selected from deionized water, tetrahydrofuran and N, N-dimethylformamide.

According to the invention, the molar weight ratio of the tetraethyl orthosilicate and the water for preparing the silicon oxide nanowires by the electrostatic spinning method is or more of 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1.5:5, 1.5:6, 1.5:7, 1.5:8, 1.5:9, 1.5:10, 2:6, 2:7, 2:8, 2:9, 2:10, 2:11 and 2:12, and the types of the acid are nitric acid, phosphoric acid and hydrochloric acid, and the addition amount of the acid is 8 muL to 32 muL.

When the silicon oxide template phase is prepared by adopting an electrostatic spinning method, the raw material solution and the spinnable polymer solution are mixed according to the mass ratio of 1:1, 2:1, 3:2 and 4: 3. More preferably 3: 2.

Preferably, the template phase material is prepared by an electrostatic spinning method; the active particles are added to the raw material solution used in the electrospinning method. The active particles added here may be inorganic nanoparticles dispersed in the raw material solution or inorganic compounds soluble in the raw material solution. Inorganic nanoparticles refer to nanoscale particles formed of inorganic substances or inorganic compounds. When the inorganic nanoparticles may be soluble in the raw material solution, the size of the inorganic nanoparticles may not be limited.

The graphitized carbon tube material obtained by the electrostatic spinning method comprises a structure of inorganic nano particles coated by a graphitized carbon film.

More preferably, the active particles are inorganic nanoparticles, and the inorganic nanoparticles are inorganic elementary substance nanoparticles or inorganic compound nanoparticles. More preferably, the inorganic elementary substance nanoparticles are metal nanoparticles, and more preferably, the metal nanoparticles are noble metal nanoparticles. More preferably, the inorganic compound nanoparticles are oxide nanoparticles or metal compound nanoparticles.

By dispersing inorganic nano particles in the raw material solution, a template with active particles on the surface can be prepared, and a plurality of active sites can be formed on the inner wall of the fiber of the prepared graphitized carbon tube material through subsequent steps, so that active reaction sites are provided for catalysis, conduction and other purposes, and the conductivity and catalytic performance of the prepared graphitized carbon tube material are improved.

Preferably, the inorganic substance in the raw material solution is mixed with the raw material solution in a mass ratio of the inorganic substance to the raw material solution of 1: 100-1: 100000 are added. More preferably, the inorganic substance is added according to the mass ratio of the inorganic nano-particles to the raw material solution of 1: 1000.

When the template phase material is prepared by an electrostatic spinning method, a spinnable polymer solution is mixed with a raw material solution to obtain a mixed solution, the mixed solution is subjected to electrostatic spinning to form a film, and the obtained film is sintered to obtain a fiber film material as a template.

The solute in the spinnable polymer solution can be any organic matter capable of finally forming the micro/nano-scale fiber material by an electrostatic spinning technology, for example, at least of polyvinyl alcohol solution, polyvinyl pyrrolidone solution and polyethylene glycol solution can be adopted, and the solute in the spinnable polymer solution is more preferably polyvinyl alcohol, the mass percent of the solute in the spinnable polymer solution is 5-30 wt.%, and the mass percent of the solute in the spinnable polymer solution is more preferably 6-20 wt.%.

The solvent of the spinnable polymer solution can be at least of deionized water, tetrahydrofuran and N, N-dimethylformamide.

The raw material solution comprises tetraethyl orthosilicate, water and acid, wherein the molar weight ratio of the tetraethyl orthosilicate to the water in the raw material solution is of 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1.5:5, 1.5:6, 1.5:7, 1.5:8, 1.5:9, 1.5:10, 2:6, 2:7, 2:8, 2:9, 2:10, 2:11 and 2:12, the types of the acid are at least of nitric acid, phosphoric acid and hydrochloric acid, and the addition amount of the acid is added according to the molar ratio of the acid to the tetraethyl orthosilicate of 1: 0.01.

Specifically, the electrostatic spinning method provided by the invention comprises the following steps:

(1) the spinnable polymer is dissolved in a solvent to prepare a spinnable polymer solution with the concentration of 6-30 wt%.

(2) Preparing a raw material solution, wherein the raw material solution comprises tetraethyl orthosilicate, acid and water, the molar weight ratio of tetraethyl orthosilicate to water is (1-2): (5-12), the molar weight ratio is more preferably 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1.5:5, 1.5:6, 1.5:7, 1.5:8, 1.5:9, 1.5:10, 2:6, 2:7, 2:8, 2:9, 2:10, 2:11 or 2:12, the added acid is at least of nitric acid, phosphoric acid and hydrochloric acid, the addition amount of the acid is at least of the acid and the tetraethyl orthosilicate is 1:0.01, and then the inorganic nanoparticles are dispersed in the raw material solution in the step (2), the inorganic nanoparticles are inorganic oxide nanoparticles or noble metal nanoparticles, and the addition of the inorganic nanoparticles in the step (2) can be omitted as required.

(3) And (3) mixing and stirring the spinnable polymer solution obtained in the step (1) and the raw material solution obtained in the step (2) for 2-4h according to the mass ratio of (1-3) to (1-4) to obtain a spinnable polymer mixed solution, wherein the mixing mass ratio is more preferably 1:1, 3:4, 2:3 and 1:2, and further is more preferably 2: 3.

(4) And (4) filling the spinnable polymer mixed solution in the step (3) into a glass tube injector with an -end nozzle, wherein the diameter of the outlet end of the nozzle is 0.5-3 cm, and the total volume of the injector is 1-10 ml.

(5) And (4) fixing the injector filled with the spinnable polymer mixed solution in the step (3), wherein the central axis of the nozzle is 0-45 degrees to the horizontal plane.

(6) And connecting the nozzle with the positive pole of a high-voltage power supply, wherein the voltage of the high-voltage power supply is 8-15 KV. The receiving bottom is connected with the negative pole of the power supply, and the voltage range of the negative pole is 0-minus 3 KV. The vertical distance between the end of the injector close to the receiving base and the receiving base is 8-25 cm.

(7) Laying 1-150 square centimeter of tin foil paper, copper foil or aluminum foil on a receiving substrate, wherein the fiber receiving time is 1-600 minutes, and forming a film on the receiving substrate through electrostatic spinning, wherein the film is formed by disordered/ordered interweaving of micron-sized or nano-sized fibers.

(8) And (3) heating the film obtained in the step (7) to 600-800 ℃ in a muffle furnace at the heating rate of 0.5-5 ℃/min, and calcining for 30-240 minutes to obtain the nano-scale or micron-scale fiber film, wherein the film does not contain high molecular substances and contains inorganic nano-particles coated by silicon oxide, and the inorganic nano-particles are metal nano-particles or inorganic oxide nano-particles.

(9) And (3) placing the fiber membrane obtained in the step (8) in a CVD (chemical vapor deposition) tube furnace, heating to 1100-1300 ℃ at the heating rate of 1-5 ℃/min, then introducing a gaseous organic substance at the rate of 4-10 sccm for 5-30 minutes, and forming an layer of graphitized carbon with the thickness of 10-30 nm on the surface of the silicon oxide fiber in the fiber membrane to obtain a membrane material, wherein the gaseous organic substance can be at least of methane, acetylene, ethylene hydrocarbon and ethanol.

(10) And (3) putting the membrane material obtained in the step (9) into hydrofluoric acid with the concentration of 5-15 wt% for wet etching for 10-720 minutes, removing the silicon oxide template phase to obtain a graphitized carbon tube material with the wall thickness of 10-30 nm, wherein inorganic nano particles are uniformly distributed on the inner wall of the tube of the graphitized carbon tube structure of the graphitized carbon tube material.

As another specific embodiment of , the method of electrospinning described above is the same as the above (1), (3) to (10) except that no inorganic particles are added in step (2).

As a specific embodiment of , the preparation method of the graphitized carbon tube material comprises the following steps:

(i) the preparation of the fiber material capable of growing the graphitized carbon layer on the surface thereof by a Chemical Vapor Deposition (CVD) method comprises the following steps: silicon oxide, aluminum oxide, magnesium oxide, or any combination of the three;

(ii) generating a graphitized carbon layer with the thickness of 10-20nm on the surface of the fiber by a CVD method;

(iii) silicon oxide, aluminum oxide and magnesium oxide fibers are removed by an etching method to prepare the graphitized carbon tube with the diameter of 50-3000 nm.

The preparation method of the graphitized carbon tube mainly utilizes chemical vapor deposition, a gel sol method, an electrostatic spinning method and a template method to prepare kinds of silicon oxide, aluminum oxide and magnesium oxide nanowires, then carbon with the thickness of 10-20nm is deposited on the surfaces of the silicon oxide, the aluminum oxide and the magnesium oxide nanowires, and finally silicon, copper, silicon oxide, aluminum oxide and magnesium oxide in the silicon oxide, the aluminum oxide and the magnesium oxide are etched by etching liquid, so that the graphitized carbon tube is prepared.

In yet another aspect of the present invention, graphitized carbon tube materials prepared by the above method are provided for use in conductive materials or catalyst carriers.

The beneficial effects of the invention include but are not limited to:

(1) the preparation method of the graphitized carbon tube material provided by the invention combines a chemical vapor deposition technology, wet etching and a template method, forms a carbon layer on the surface of the nanofiber through chemical vapor deposition, and obtains the graphitized carbon tube after removing the template through etching. The prepared graphitized carbon tube material is internally conducted, has no bamboo joint structure, does not contain a catalyst, has high purity and less impurities, has an adjustable diameter range, is simple in preparation process, and has good application prospect, and used equipment is industrialized experimental equipment. The preparation method of the graphitized carbon tube material has the advantages of simple process, low cost and easy operation, and can prepare the graphitized carbon tube material with low impurity content and no bamboo joint structure inside.

(2) The graphitized carbon tube material provided by the invention has high purity, the diameter, the length and the wall thickness of the graphitized carbon tube can be adjusted according to requirements, and the graphitized carbon tube has no bamboo-like structure, so that the graphitized carbon tube material is beneficial to loading and filling active substances. The diameter of the graphitized carbon tube has a larger adjustable range, can meet different application requirements, is beneficial to filling and loading oxides, noble metal particles and inorganic matters, and expands the application range of the graphitized carbon tube.

(3) The graphitized carbon tube material provided by the invention can be prepared into a tubular carbon film material with a hollow structure, the film material has good conductivity and mechanical properties, and can be widely applied to the field of photoelectric devices such as catalysis, energy sources and sensors.

Drawings

FIG. 1 is a schematic process flow diagram of the preparation method of graphitized carbon tube material provided by the present invention;

fig. 2 is an SEM image of graphitized carbon tube-coated silver particles prepared in preferred example 2 of the present invention;

FIG. 3 is a TEM image of graphitized carbon tube-coated silver particles prepared in preferred embodiment 2 of the present invention;

FIG. 4 is a graph showing the charge and discharge electrochemical performance of the graphitized carbon tube-coated silver prepared in preferred embodiment 2 of the present invention;

fig. 5 is a schematic diagram of the cycle performance of the graphitized carbon tube coated silver prepared in the preferred embodiment 2 of the present invention.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.

Referring to fig. 1, the preparation method of the graphitized carbon tube material provided by the invention comprises the following steps:

step S100: preparing a template phase material;

step S200: growing a graphitized carbon film on the surface of the template phase material by adopting a chemical vapor deposition method to obtain a film material;

step S300: and removing the template phase material in the film layer material by adopting a wet chemical method to obtain the graphitized carbon tube material.

In another embodiment of the present invention, the method includes the step of electrostatically preparing the template material in step S100.

In another embodiment of the present invention, the method includes the step of dispersing inorganic nanoparticles in a solution of the template material used in the step S100 when the template material is electrostatically prepared.

In another embodiment of the present invention, the method includes the step of removing the template phase material from the film material by wet etching in step S300.

In the following examples, the electrospinning operation used included the following steps:

(1) after the electrostatic spinning device is assembled, the spinnable polymer mixed solution is filled into an injector.

(2) And (2) turning on a high-voltage power supply and starting the electrostatic spinning device, forming a high-voltage electric field between the needle head and the receiving substrate, forming disordered and ordered micro/nano fibers by the polymer solution in the injector under the action of the high-voltage electrostatic field through the needle head, depositing the formed nano fibers on the receiving device, and interweaving to form a polymer nano fiber film.

(3) And (4) stripping the polymer film from the receiving substrate to obtain the nano fiber.