WO2020224431A1

WO2020224431A1 - Aeolotropic layered carbon-fiber-based aerogel material and preparation method therefor

Info

Publication number: WO2020224431A1
Application number: PCT/CN2020/085989
Authority: WO
Inventors: 伍晖; 贾超
Original assignee: 清华大学
Priority date: 2019-05-07
Filing date: 2020-04-21
Publication date: 2020-11-12
Also published as: CN110184683A; CN110184683B

Abstract

Provided are an aeolotropic layered carbon-fiber-based aerogel material and a preparation method therefor. The method for preparing the aeolotropic layered carbon-fiber-based aerogel material comprises: mixing a polymer solution, an inorganic precursor and a chloride to obtain a spinning precursor mixed liquid; jet spinning the spinning precursor mixed liquid to obtain a composite fiber aerogel; and subjecting the composite fiber aerogel to pre-oxidation and carbonization treatments successively, to obtain the aeolotropic layered carbon-fiber-based aerogel material. Thus, the preparation method is simple, easy to operate, low in preparation cost, high in efficiency, and easy for industrial production. The carbon-fiber-based aerogel material prepared by the method is composed of multiple layers of stacked microfibers, has an aeolotropic layered structure, and can be cut into any desired shape and stacked into a desired thickness; moreover, the material has good flexibility, compressibility and electrical conductivity.

Description

Anisotropic layered carbon fiber-based aerogel material and preparation method thereof

Priority information

This application requests the priority and rights of the patent application with the patent application number 201910375720.9 filed with the State Intellectual Property Office of China on May 7, 2019, and the full text is incorporated herein by reference.

Technical field

The invention relates to the technical field of materials, in particular to an anisotropic layered carbon fiber-based aerogel material and a preparation method thereof.

Background technique

Aerogel material is an ultra-light material with a three-dimensional network structure. Due to its ultra-low density, high specific surface area and porosity, and low thermal conductivity, it is used in heat insulation, sound absorption and noise reduction. , Catalyst carrier, air filtration and other fields show broad application prospects. Among them, in addition to the advantages of general aerogel materials, carbon aerogel materials also have the advantages of wide sources of raw materials and high electrical conductivity, so they have broad market prospects in the fields of energy storage, sensors, and electromagnetic shielding. At present, the preparation of fiber materials mainly adopts the electrostatic spinning method. Due to the direct spinning and deposition, the fibrous materials obtained by electrospinning are usually randomly stacked in the form of non-woven fabrics. Although the fiber-based aerogel materials can be prepared by reasonable design of the receiving device, the real three-dimensional air with regular shapes is obtained. Gelation is still difficult. In addition, the aerogel obtained by direct electrospinning has a disordered structure and therefore has poor compression resistance.

Therefore, the preparation method of carbon fiber-based aerogel materials needs further research.

Summary of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent. To this end, an object of the present invention is to provide a method for preparing an anisotropic layered carbon fiber-based aerogel material, which is simple, easy to operate, low in cost, and high in efficiency. Good flexibility, high compressibility or good conductivity.

In one aspect of the present invention, the present invention provides a method for preparing an anisotropic layered carbon fiber-based aerogel material. According to an embodiment of the present invention, the method includes: mixing a polymer solution, an inorganic precursor, and a chloride to obtain a spinning precursor mixture; and performing jet spinning on the spinning precursor mixture to obtain a composite fiber Aerogel; the composite fiber aerogel is sequentially subjected to pre-oxidation treatment and carbonization treatment to obtain an anisotropic layered carbon fiber-based aerogel material. Therefore, the above-mentioned preparation method is simple, easy to operate, low-cost, high-efficiency, and easy for industrial production; the carbon fiber-based aerogel material prepared by the above-mentioned method is composed of multi-layer stacked microfibers and has an anisotropic layered shape. The structure can be cut into any desired shape and stacked to the required thickness; and the prepared carbon fiber-based aerogel material has good flexibility and compressibility; the layered structure of the carbon fiber-based aerogel material The carbon component makes aerogel materials have good electrical conductivity, and the electrical conductivity increases with the increase of compressive strain, which in turn makes it have broad application prospects in the fields of stress sensing, electromagnetic shielding, air filtration, energy storage and so on.

According to an embodiment of the present invention, the polymer solution includes a polymer material and a solvent, wherein the mass ratio of the polymer material to the solvent is (2-30):100.

According to an embodiment of the present invention, the spinning precursor mixture further includes a catalyst.

According to an embodiment of the present invention, the spinning precursor mixture includes: 2-30 parts by weight of the polymer material; 100 parts by weight of the solvent; 0.5-100 parts by weight of the inorganic precursor; 0.001 -1 parts by weight of the catalyst; and 1-100 parts by weight of the chloride.

According to an embodiment of the present invention, the polymer material is selected from polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, polyvinylpyrrolidone, cellulose acetate, methylcellulose, carboxymethylcellulose, polyvinylidene fluoride At least one of ethylene, polymethyl methacrylate, polyacrylamide, polyethylene oxide, polylactic acid, polyamide, polycaprolactone, polyvinyl butyral, polyaniline, polyimide, and polycarbonate Species

Optionally, the solvent is selected from water, formic acid, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane, n-heptane, acetonitrile, N-methylpyrrolidone, 1,2-propanediol, chloroform, dichloromethane , 1,2-Dichloroethane, methanol, ethanol, isopropanol, tert-butanol, n-butanol, toluene, xylene, ethylenediamine, dimethyl sulfoxide, N,N-dimethylformamide , At least one of N,N-dimethylacetamide and carbon tetrachloride;

Optionally, the inorganic precursor is at least one of zirconium oxychloride, zirconium acetate, aluminum isopropoxide, zirconium n-propoxide, ethyl orthosilicate, and methyl orthosilicate;

Optionally, the catalyst is selected from at least one of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, citric acid, oxalic acid and maleic acid.

According to an embodiment of the present invention, the chloride is selected from lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride , Radium chloride, zinc chloride, copper chloride, nickel chloride, cobalt chloride, ferric chloride, ferrous chloride, manganese chloride, chromium chloride, vanadium chloride, titanium tetrachloride, scandium chloride , Aluminum chloride, gallium chloride, indium chloride, thallium chloride, tin chloride, lead chloride, cadmium chloride, palladium chloride, rhodium chloride, ruthenium chloride, zirconium chloride, hafnium chloride, three At least one of osmium chloride, platinum chloride, gold chloride, and mercury chloride.

According to an embodiment of the present invention, compressed air is used to eject the spinning precursor mixture from the nozzle of a jet spinning device. In the jet spinning, the spinning precursor mixture is extruded The speed is 0.1-15 ml/hour, the distance between the spinneret and the receiver is 20-100 cm, and the air flow velocity of the compressed air is 1-50 m/sec.

According to an embodiment of the present invention, the conditions of the pre-oxidation treatment and the carbonization treatment are respectively: in the air at a temperature increase rate of 0.5-10 ℃/min to 180 ℃ ~ 300 ℃, the pre-oxidation treatment 0.5 ~3 hours; in an inert gas atmosphere, the temperature is increased to 700°C to 1500°C at a temperature increase rate of 0.5 to 10°C/min, the carbonization treatment is performed for 0.5 to 3 hours, and then the temperature is lowered to room temperature.

In another aspect of the present invention, the present invention provides an anisotropic layered carbon fiber-based aerogel material. According to an embodiment of the present invention, the anisotropic layered carbon fiber-based aerogel material is prepared by the aforementioned method. Thus, the carbon fiber-based aerogel material is composed of multiple stacked microfibers and has an anisotropic layered structure, which can be cut into any desired shape and stacked to a desired thickness; moreover, the Carbon fiber-based aerogel materials have good flexibility and compressibility; the layered structure and carbon component of carbon fiber-based aerogel materials make carbon fiber-based aerogel materials have good electrical conductivity, and the conductivity varies with compression strain Increase and increase, and make it have broad application prospects in stress sensing, electromagnetic shielding, air filtration, energy storage and other fields.

According to an embodiment of the present invention, the bulk density of the carbon fiber-based aerogel material is 5 to 200 mg/cm ³ , and optionally, the average diameter of the fibers in the carbon fiber-based aerogel material is 0.2 to 10 microns.

Description of the drawings

Fig. 1 is a flow chart of a preparation method of an anisotropic layered carbon fiber-based aerogel material in an embodiment of the present invention.

Fig. 2 is a scanning electron micrograph of an anisotropic layered carbon fiber-based aerogel material in another embodiment of the present invention.

Detailed description of the invention

The embodiments of the present invention are described in detail below. The embodiments described below are exemplary, and are only used to explain the present invention, but should not be construed as limiting the present invention. Where specific techniques or conditions are not indicated in the examples, the procedures shall be carried out in accordance with the techniques or conditions described in the literature in the field or in accordance with the product specification. The reagents or instruments used without the manufacturer's indication are all conventional products that are commercially available.

In one aspect of the present invention, the present invention provides a method for preparing an anisotropic layered carbon fiber-based aerogel material (referred to as carbon fiber-based aerogel material herein). According to an embodiment of the present invention, referring to FIG. 1, the preparation method of the anisotropic layered carbon fiber-based aerogel material includes:

S100: Mixing the polymer solution, the inorganic precursor and the chloride to obtain a spinning precursor mixture. In this process, the inorganic precursors are hydrolyzed to obtain inorganic oxides so as to subsequently obtain carbon fiber-based aerogel materials.

According to an embodiment of the present invention, the polymer solution includes a polymer material and a solvent, wherein the mass ratio of the polymer material to the solvent is (2-30): 100, such as 2: 100, 5: 100, 8: 100, 10 : 100, 15: 100, 20: 100, 25: 100, 30: 100. As a result, a uniformly dissolved polymer solution can be obtained, and the polymer solution with the above concentration is conducive to subsequent jet spinning, and a carbon fiber-based aerogel material with excellent compressibility and flexibility can be obtained; if the polymer material is compatible with If the mass ratio of the solvent is less than 2:100, the concentration of the polymer solution is too low and fibers cannot be formed; if the mass ratio of the polymer material to the solvent is higher than 30:100, the polymer material is not easy to dissolve completely, and the second is high The viscosity of the molecular solution is too high to be ejected from the spinneret of the jet spinning equipment to form fibers.

According to an embodiment of the present invention, in order to obtain a fully dissolved polymer solution, the step of preparing the polymer solution includes: adding a certain amount of polymer material to a certain amount of solvent, and then at room temperature (25°C) to 100°C Under the conditions of stirring and dissolving at a speed of 50-1000 rpm for 0.1-10 hours, a polymer solution with a suitable concentration can be obtained. Among them, the specific amount of polymer materials and solvents and specific process conditions can be determined by those skilled in the art according to specific The polymer material and the selected solvent are set. There are no restrictions here, as long as the polymer material is fully and quickly dissolved. Among them, the stirring can be accomplished by mechanical stirring or magnetic stirring.

According to an embodiment of the present invention, the polymer material is selected from polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, polyvinylpyrrolidone, cellulose acetate, methylcellulose, carboxymethylcellulose, polyvinylidene fluoride, At least one of polymethyl methacrylate, polyacrylamide, polyethylene oxide, polylactic acid, polyamide, polycaprolactone, polyvinyl butyral, polyaniline, polyimide, and polycarbonate. Therefore, the material source is wide, easy to spin, and it is convenient to carbonize the polymer material in the subsequent process.

According to an embodiment of the present invention, the solvent is selected from water, formic acid, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane, n-heptane, acetonitrile, N-methylpyrrolidone, 1,2-propanediol, chloroform, dichloro Methane, 1,2-dichloroethane, methanol, ethanol, isopropanol, tert-butanol, n-butanol, toluene, xylene, ethylenediamine, dimethyl sulfoxide, N,N-dimethylformaldehyde At least one of amide, N,N-dimethylacetamide and carbon tetrachloride. Therefore, those skilled in the art can choose suitable solvents according to different polymer materials to ensure that the polymer materials can be quickly and effectively dissolved.

According to an embodiment of the present invention, the inorganic precursor is at least one of zirconium oxychloride, zirconium acetate, aluminum isopropoxide, zirconium n-propoxide, ethyl orthosilicate, and methyl orthosilicate. Thus, the above-mentioned inorganic precursors are hydrolyzed to obtain oxides (such as zirconia, alumina, and silica), and composite fiber aerogel materials are obtained by jet spinning.

According to an embodiment of the present invention, in order to obtain a layered structure of carbon fiber-based aerogel material, the chloride is selected from lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, Calcium chloride, strontium chloride, barium chloride, radium chloride, zinc chloride, copper chloride, nickel chloride, cobalt chloride, ferric chloride, ferrous chloride, manganese chloride, chromium chloride, chlorine Vanadium chloride, titanium tetrachloride, scandium chloride, aluminum chloride, gallium chloride, indium chloride, thallium chloride, tin chloride, lead chloride, cadmium chloride, palladium chloride, rhodium chloride, chloride At least one of ruthenium, zirconium chloride, hafnium chloride, osmium chloride, platinum chloride, gold chloride, and mercury chloride. Therefore, in the process of jet spinning, under the action of chloride, a composite fiber aerogel material with a layered structure can be obtained, thereby greatly improving the compressibility of the carbon fiber-based aerogel material.

According to an embodiment of the present invention, in order to promote the hydrolysis of the inorganic precursor, a catalyst is further included in the spinning precursor mixture. In an embodiment of the present invention, the catalyst is selected from at least one of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, citric acid, oxalic acid and maleic acid . Therefore, under the action of the above-mentioned catalyst, the inorganic precursor can be hydrolyzed into inorganic oxides quickly, effectively and more fully to obtain composite fiber aerogel materials, which is beneficial for subsequent production of carbon fiber-based aerogel materials with excellent performance. .

According to the embodiments of the present invention, there is no restriction on the specific process of mixing the above-mentioned reagents and components, and those skilled in the art can flexibly set according to actual needs. In some embodiments of the present invention, the inorganic precursor, catalyst and chloride are added to the polymer solution separately, and a spinning precursor mixture with a certain viscosity is obtained by stirring; in other embodiments of the present invention, The inorganic precursor, catalyst and chloride are mixed first, and then added to the polymer solution, and a spinning precursor mixture with a certain viscosity is obtained by stirring. Among them, the specific method of stirring is also not limited. It can be mechanical stirring or magnetic stirring, which is not limited here.

According to an embodiment of the present invention, in order to obtain a carbon fiber-based aerogel material with better performance, the spinning precursor mixture includes: 2-30 parts by weight of polymer material; 100 parts by weight of solvent; 0.5-100 parts by weight Inorganic precursor; 0.001 to 1 parts by weight of catalyst; and 1 to 100 parts by weight of chloride. Therefore, the carbon fiber-based aerogel material prepared by the above ratio has good compressibility, flexibility, and an anisotropic layered structure, wherein the amount of chloride can effectively ensure the layered shape of the carbon fiber-based aerogel structure. If the amount of chloride is too low, the layered structure of the carbon fiber-based aerogel material is not obvious, resulting in relatively poor compressibility; if the amount of chloride is too high, it will also cause the compressibility of the aerogel material Getting worse.

S200: Jet spinning the spinning precursor mixture to obtain composite fiber aerogel. In this process, under the action of chloride, the obtained composite fiber aerogel has a multi-layer stacked layered structure, which makes it anisotropic, so that the final carbon fiber-based aerogel material can be cut to the desired The shape is stacked to get the desired thickness. Among them, "anisotropy" means that the carbon fiber-based aerogel material is compressed from different directions relative to the carbon fiber layer in the carbon fiber-based aerogel material, and its compressibility is different, and the recovery performance is different, such as compression from a direction perpendicular to the carbon fiber layer Carbon fiber-based aerogel materials, carbon fiber-based aerogel materials can be completely restored to their original state, while compressing carbon fiber-based aerogel materials from a direction parallel to the carbon fiber layer, carbon fiber-based aerogel materials cannot be restored to their original state.

According to the embodiment of the present invention, the spinning precursor mixture is spun using the jet spinning technology, and the spinning precursor mixture is ejected from the spinneret of the jet spinning equipment by compressed air, specifically: Jet spinning adopts a pair of coaxial nozzles, using compressed air to extrude the spinning precursor mixture through the inner nozzle, and the high-speed airflow is ejected through the outer nozzle. The spinning precursor mixture is polymerized under the shearing action of the high-speed airflow. When the material jet reaches the receiving device, the jet further splits, stretches, and refines. At the same time, the solvent continuously volatilizes, and the fibers are formed and solidified and collected on the receiving device (also called "receiver"). Compared with electrospinning, the jet spinning equipment is simple, uses high-speed airflow as the driving force, does not require high-voltage electrostatic field, has higher spinning efficiency, and the composite fiber aerogel can be deposited on any substrate. Therefore, it is of great significance to use jet spinning technology to prepare large-scale carbon fiber-based aerogel materials with good flexibility and conductivity.

According to the embodiment of the present invention, there is no restriction on the specific type of the receiving device, and those skilled in the art can flexibly choose according to actual needs. In some embodiments of the present invention, the receiving device includes but is not limited to metal mesh, plastic mesh, and non-woven fabric.

According to the embodiment of the present invention, in order to obtain a carbon fiber-based aerogel material with excellent flexibility and conductivity, in jet spinning, the extrusion speed of the spinning precursor mixture is 0.1-15 ml/h (E.g. 0.1mL/h, 0.5mL/h, 1mL/h, 2mL/h, 3mL/h, 4mL/h, 5mL/h, 6mL/h, 7mL/h, 8mL/h, 9mL/h, 10mL/ h, 11mL/h, 12mL/h, 13mL/h, 14mL/h, 15mL/h), the distance between the spinneret and the receiver is 20-100 cm (such as 20cm, 30cm, 40cm, 50cm, 60cm, 70cm, 80cm, 90cm, 100cm), the compressed air flow velocity is 1-50m/s (such as 1m/s, 5m/s, 10m/s, 15m/s, 20m/s, 25m/s, 30m/s , 35m/s, 40m/s, 45m/s, 50m/s). Thus, a carbon fiber-based aerogel material with excellent performance can be prepared.

S300: Perform pre-oxidation treatment and carbonization treatment on the composite fiber aerogel in sequence to obtain an anisotropic layered carbon fiber-based aerogel material. In this process, through the pre-oxidation treatment and carbonization treatment, the polymer material is pyrolyzed, and the elements such as hydrogen and oxygen are removed to form carbon fibers. The carbon fiber-based aerogel material is obtained, making the layered structure of the carbon fiber-based aerogel material excellent The conductivity.

According to the embodiment of the present invention, in order to fully pyrolyze the polymer material to form carbon fiber, the conditions of the pre-oxidation treatment and the carbonization treatment are respectively: 0.5-10℃/min (such as 0.5℃/min, 1℃/min) in the air , 2℃/min, 3℃/min, 4℃/min, 5℃/min, 6℃/min, 7℃/min, 8℃/min, 9℃/min, 10℃/min) To 180℃～300℃ (such as 180℃, 200℃, 230℃, 250℃, 280℃ or 300℃), carry out pre-oxidation treatment for 0.5～3 hours (such as 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 Hours or 3 hours); In an inert gas atmosphere, 0.5～10℃/min (such as 0.5℃/min, 1℃/min, 2℃/min, 3℃/min, 4℃/min, 5℃/min , 6°C/min, 7°C/min, 8°C/min, 9°C/min, 10°C/min) rise to 700°C～1500°C (such as 700°C, 800°C, 900°C, 1000°C, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ or 1500 ℃), carry out carbonization treatment for 0.5 to 3 hours (such as 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours), then cool to room temperature, where Those skilled in the art can flexibly set the specific parameters according to the actual situation. It should be noted that the temperature of the carbonization treatment can be raised on the basis of the pre-oxidation temperature, thereby shortening the process time and saving energy.

According to the embodiment of the present invention, the preparation method of the above-mentioned carbon fiber-based aerogel material is simple, easy to operate, low-cost, high-efficiency, and easy for industrial production; the carbon-fiber-based aerogel material prepared by the above method is stacked by multiple layers It is composed of microfibers and has an anisotropic layered structure, which can be cut into any desired shape and stacked to a desired thickness; and the prepared carbon fiber-based aerogel material has good flexibility and compressibility; The layered structure and carbon component of carbon fiber-based aerogel materials make the aerogel materials have good electrical conductivity, and the electrical conductivity increases with the increase of compressive strain, which in turn makes it useful for stress sensing, electromagnetic shielding, and air filtration. , Energy storage and other fields have broad application prospects.

In another aspect of the present invention, the present invention provides an anisotropic layered carbon fiber-based aerogel material. According to an embodiment of the present invention, the anisotropic layered carbon fiber-based aerogel material is prepared by the aforementioned method. Thus, the carbon fiber-based aerogel material is composed of multiple stacked microfibers and has an anisotropic layered structure, which can be cut into any desired shape and stacked to a desired thickness; moreover, the Carbon fiber-based aerogel materials have good flexibility and compressibility; the layered structure and carbon component of carbon fiber-based aerogel materials make the aerogel materials have good electrical conductivity, and the electrical conductivity increases with the increase in compression strain. Increase, and make it have broad application prospects in stress sensing, electromagnetic shielding, air filtration, energy storage and other fields.

According to an embodiment of the present invention, the bulk density of the carbon fiber-based aerogel material is 5 to 200 mg/cm ³ (such as 5 mg/cm ³ , 25 mg/cm ³ , 50 mg/cm ³ , 75 mg/cm ³ , 100 mg/cm ³ , 125mg/cm ³ , 150mg/cm ³ , 175mg/cm ³ , 200mg/cm ³ , ), the average diameter of the fibers in the carbon fiber-based aerogel material is 0.2-10 microns (such as 0.2 microns, 0.5 microns, 1 microns, 2 Microns, 4 microns, 6 microns, 8 microns or 10 microns). As a result, the bulk density and fiber diameter of carbon fiber-based aerogel materials have a wide range. Those skilled in the art can prepare carbon fiber-based aerogel materials with different bulk densities and fiber diameters according to different needs and applications to meet different requirements. Market demand.

Example

Example 1

A preparation method of anisotropic layered carbon fiber-based aerogel material adopts the following process steps:

(1) Preparation of polymer solution: 15g of polyvinyl butyral was added to 100g of deionized water, stirred and dissolved at 800rpm at 90℃ for 1h to obtain a polymer with a polymer material and solvent mass ratio of 15:100. Vinyl butyral solution;

(2) Preparation of spinning precursor mixture: 35g of zirconium oxychloride, 0.2g of nitric acid, and 40g of ferric chloride were added to the above polyvinyl butyral solution, and a spinning precursor with a certain viscosity was obtained by stirring. liquid;

(3) Jet spinning: using jet spinning technology to use compressed air with a flow rate of 5m/s to eject the spinning precursor mixture from the spinneret at a speed of 5mL/h, and the resulting fiber is deposited at a distance from the spinneret Obtain composite fiber aerogel on a 60cm metal mesh receiver;

(4) Pre-oxidation and carbonization: The obtained composite fiber aerogel is heated at 2°C/min to 300°C for 2h in an air atmosphere, and then heated at 5°C/min to 800°C in a nitrogen atmosphere. After carbonization treatment for 1 h, and after cooling to room temperature, an anisotropic layered carbon fiber-based aerogel material was obtained.

The obtained anisotropic layered carbon fiber-based aerogel material has a bulk density of 20 mg/cm ³ and an average fiber diameter of 3.3 μm. Refer to FIG. 2 for the scanning electron microscope image.

Example 2

(1) Preparation of polymer solution: Add 5g of polyethylene oxide to 100g of deionized water, stir and dissolve at 800 rpm at 90°C for 1 hour to obtain a polyethylene oxide solution with a polymer material to solvent mass ratio of 5:100 ；

(2) Preparation of spinning precursor mixture: adding 50 g of zirconium acetate, 0.1 g of phosphoric acid, and 40 g of magnesium chloride to the above polyethylene oxide solution, and stirring to obtain a spinning precursor mixture with a certain viscosity;

(4) Pre-oxidation and carbonization: The obtained composite fiber aerogel is heated at 1℃/min to 300℃ for 2h in air atmosphere, and then heated at 5℃/min to 850℃ in nitrogen atmosphere. After carbonization treatment for 1 h, and after cooling to room temperature, an anisotropic layered carbon fiber-based aerogel material was obtained.

The resulting product has an anisotropic layered carbon fiber-based aerogel material with a bulk density of 19 mg/cm ³ and an average fiber diameter of 3.6 μm.

Example 3

(1) Preparation of polymer solution: Add 10g of polyvinyl alcohol to 100g of deionized water, stir and dissolve at 800rpm at 90°C for 1h to obtain a polyvinyl alcohol solution with a polymer material to solvent mass ratio of 10:100 ；

(2) Preparation of the spinning precursor mixture: adding 40 g of ethyl orthosilicate, 0.2 g of phosphoric acid, and 40 g of aluminum chloride to the above polyvinyl alcohol solution, and stirring to obtain a spinning precursor mixture with a certain viscosity;

(4) Pre-oxidation and carbonization: The obtained composite fiber aerogel is heated at 1.5°C/min to 300°C for 1h in an air atmosphere, and then heated at 5°C/min to 900°C in a nitrogen atmosphere. The carbonization treatment was carried out for 2 hours, and the anisotropic layered carbon fiber-based aerogel material was obtained after being cooled to room temperature.

The resulting product has an anisotropic layered carbon fiber-based aerogel material with a bulk density of 17 mg/cm ³ and an average fiber diameter of 3.9 μm.

Example 4

(1) Preparation of polymer solution: add 5 g of carboxymethyl cellulose to 100 g of deionized water, stir and dissolve at 800 rpm at 60°C for 1 hour to obtain a polymer material and solvent mass ratio of 5:100 carboxymethyl Base cellulose solution;

(2) Preparation of spinning precursor mixture: 40g of zirconium acetate, 0.2g of hydrochloric acid, and 35g of magnesium chloride are added to the above carboxymethyl cellulose solution, and a spinning precursor mixture with a certain viscosity is obtained by stirring;

(4) Pre-oxidation and carbonization: The obtained composite fiber aerogel is heated at 1°C/min to 280°C for 1h in an air atmosphere, and then heated at 5°C/min to 850°C in a nitrogen atmosphere. After carbonization treatment for 1 h, and after cooling to room temperature, an anisotropic layered carbon fiber-based aerogel material was obtained.

The resulting product has an anisotropic layered carbon fiber-based aerogel material with a bulk density of 22 mg/cm ³ and an average fiber diameter of 3.6 μm.

Example 5

(1) Preparation of polymer solution: Add 15g of polyvinylpyrrolidone to 100g of deionized water, stir and dissolve at 800rpm at 60℃ for 1h to obtain a solution of polyvinylpyrrolidone with a mass ratio of polymer material to solvent of 15:100 ；

(2) Preparation of spinning precursor mixture: 40g of zirconium oxychloride, 0.1g of phosphoric acid, and 40g of magnesium chloride are added to the above polyvinylpyrrolidone solution, and a spinning precursor mixture with a certain viscosity is obtained by stirring;

(3) Jet spinning: using solution jet spinning technology to use compressed air with a flow rate of 5m/s to eject the spinning precursor mixture from the spinneret at a speed of 5mL/h, and the resulting fibers are deposited in the distance spinning The composite fiber aerogel is obtained on the metal mesh receiver with an opening of 60 cm;

(4) Pre-oxidation and carbonization: The obtained composite fiber aerogel is heated at 1°C/min to 300°C for 2h in an air atmosphere, and then heated at 5°C/min to 900°C in a nitrogen atmosphere. The carbonization treatment was carried out for 2 hours, and the anisotropic layered carbon fiber-based aerogel material was obtained after being cooled to room temperature.

The resulting product has an anisotropic layered carbon fiber-based aerogel material with a bulk density of 21 mg/cm ³ and an average fiber diameter of 4.3 μm.

In the description of this specification, descriptions with reference to the terms "one embodiment", "some embodiments", "examples", "specific examples" or "some examples" etc. mean the specific features described in conjunction with the embodiment or example, The structure, material or feature is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine the different embodiments or examples and the characteristics of the different embodiments or examples described in this specification without contradicting each other.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above-mentioned embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can comment on the foregoing within the scope of the present invention. The embodiment undergoes changes, modifications, substitutions and modifications.

Claims

A method for preparing an anisotropic layered carbon fiber-based aerogel material, which is characterized in that it comprises:

Mixing the polymer solution, the inorganic precursor and the chloride to obtain a spinning precursor mixture;

Jet spinning the spinning precursor mixture to obtain a composite fiber aerogel;

The composite fiber aerogel is sequentially subjected to pre-oxidation treatment and carbonization treatment to obtain an anisotropic layered carbon fiber-based aerogel material.
The method according to claim 1, wherein the polymer solution comprises a polymer material and a solvent, wherein the mass ratio of the polymer material to the solvent is (2-30):100.
The method of claim 1 or 2, wherein the spinning precursor mixture further includes a catalyst.
The method of claim 3, wherein the spinning precursor mixture comprises:

2-30 parts by weight of the polymer material;

100 parts by weight of the solvent;

0.5-100 parts by weight of the inorganic precursor;

0.001 to 1 part by weight of the catalyst; and

1-100 parts by weight of the chloride.
The method according to claim 4, wherein the polymer material is selected from polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, polyvinylpyrrolidone, cellulose acetate, methyl cellulose, carboxymethyl Cellulose, polyvinylidene fluoride, polymethyl methacrylate, polyacrylamide, polyethylene oxide, polylactic acid, polyamide, polycaprolactone, polyvinyl butyral, polyaniline, polyimide and poly At least one of carbonates;

Optionally, the solvent is selected from water, formic acid, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane, n-heptane, acetonitrile, N-methylpyrrolidone, 1,2-propanediol, chloroform, dichloromethane , 1,2-Dichloroethane, methanol, ethanol, isopropanol, tert-butanol, n-butanol, toluene, xylene, ethylenediamine, dimethyl sulfoxide, N,N-dimethylformamide , At least one of N,N-dimethylacetamide and carbon tetrachloride;

Optionally, the inorganic precursor is at least one of zirconium oxychloride, zirconium acetate, aluminum isopropoxide, zirconium n-propoxide, ethyl orthosilicate, and methyl orthosilicate;

Optionally, the catalyst is selected from at least one of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, citric acid, oxalic acid and maleic acid.
The method according to any one of claims 1 to 5, wherein the chloride is selected from lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride , Calcium chloride, strontium chloride, barium chloride, radium chloride, zinc chloride, copper chloride, nickel chloride, cobalt chloride, ferric chloride, ferrous chloride, manganese chloride, chromium chloride, Vanadium chloride, titanium tetrachloride, scandium chloride, aluminum chloride, gallium chloride, indium chloride, thallium chloride, tin chloride, lead chloride, cadmium chloride, palladium chloride, rhodium chloride, chlorine At least one of ruthenium chloride, zirconium chloride, hafnium chloride, osmium chloride, platinum chloride, gold chloride, and mercury chloride.
The method according to any one of claims 1 to 6, characterized in that compressed air is used to eject the spinning precursor mixture from the spinneret of a jet spinning device, and in the jet spinning , The extrusion speed of the spinning precursor mixture is 0.1-15 ml/h, the distance between the spinneret and the receiver is 20-100 cm, and the air flow rate of the compressed air is 1-50 Meters per second.
The method according to any one of claims 1 to 7, characterized in that the conditions of the pre-oxidation treatment and the carbonization treatment are respectively: in the air at a temperature rise rate of 0.5-10 °C/min to 180 ℃～300℃, carry out the pre-oxidation treatment for 0.5～3 hours; in an inert gas atmosphere, increase to 700℃～1500℃ at a heating rate of 0.5～10℃/min, carry out the carbonization treatment for 0.5～3 hours, Then cool to room temperature.
An anisotropic layered carbon fiber-based aerogel material, characterized in that it is prepared by the method according to any one of claims 1 to 8.
The carbon fiber-based aerogel material according to claim 9, wherein the bulk density of the carbon fiber-based aerogel material is 5 to 200 mg/cm 3 ,

Optionally, the average diameter of the fibers in the carbon fiber-based aerogel material is 0.2-10 microns.