CN110982114B - Aramid fiber/carbon nanotube hybrid aerogel film, and preparation method and application thereof - Google Patents
Aramid fiber/carbon nanotube hybrid aerogel film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an aramid fiber/carbon nanotube hybrid aerogel film, a preparation method and application thereof. The aramid fiber/carbon nanotube hybrid aerogel film comprises a communicated three-dimensional network-shaped porous structure and a hydrophobic layer covering the three-dimensional network-shaped porous structure, wherein the three-dimensional network-shaped porous structure is formed by mutually lapping aramid fiber nanofibers and carbon nanotubes. The preparation method comprises the following steps: mixing the carbon nano tube dispersion liquid and the aramid nano fiber dispersion liquid to form a mixed dispersion liquid; and applying the hybrid aerogel film on a substrate, transferring the hybrid aerogel film to a coagulating bath, forming a hybrid gel film through sol-gel displacement, drying the hybrid aerogel film to obtain a hybrid aerogel film, and finally soaking the hybrid aerogel film with a hydrophobic resin solution to obtain the aramid fiber/carbon nanotube hybrid aerogel film. The hybrid aerogel film disclosed by the invention has good mechanical, electrical and hydrophobic properties, and excellent Joule heat effect and electromagnetic shielding properties, and can be applied to the fields of intelligent films, personal heat management, wearable electromagnetic protection and the like.
Description
Technical Field
The invention relates to an aerogel film, in particular to an aramid fiber/carbon nanotube hybrid aerogel film and a preparation method and application thereof, and belongs to the technical field of novel nano materials.
Background
The aerogel originates from the beginning of the 30 th of the 20 th century, is a synthetic solid material, has extremely low density, ultrahigh specific surface area and ultralow heat conductivity coefficient due to a continuous porous network structure, and has important values in the fields of catalyst carriers, environment purification, temperature management, energy storage systems and the like. There has been an expansion from inorganic aerogels to organic aerogels and carbon aerogels, and development of aerogel fibers and aerogel films from aerogel blocks. The aerogel film not only has the porosity of aerogel, but also inherits the structural characteristics of the film, and has wide application prospect in emerging fields of batteries, water purification, supercapacitors, personal wearability and the like.
Self-supporting aerogel films are generally not produced due to the weak interaction between the inorganic nanoparticles that make up the inorganic aerogel. The organic aerogel thin film has good mechanical properties, such as polyimide aerogel thin film (sci.rep.2019,9,1370), cellulose aerogel thin film (adv.funct.mater.2015,25, 6618-. However, organic aerogel thin films lack functionality due to their low electrical/thermal conductivity, light color, and inability to be driven electrically or optically. The carbon aerogel thin film (such as graphene, carbon nano tubes and carbon nano fibers) has high electric/heat conduction performance and can be applied to the aspects of sensors, heat management, energy storage, electromagnetic shielding and the like. However, the carbon aerogel thin film reported previously needs to be prepared by chemical vapor deposition or carbonized by organic aerogel, for example, the aromatic heterocyclic fiber-based nano carbon fiber aerogel is a nano carbon fiber aerogel (CN108910861A) obtained by putting the aromatic heterocyclic fiber aerogel into a tube furnace for carbonization, and the production cost is high, and large-scale and continuous production cannot be performed.
It can be seen that the one-component aerogel films have excellent properties in some respects, but also have some unavoidable problems. Therefore, industry researchers have designed hybrid aerogel films that avoid the disadvantages while retaining the advantages of their components. Among them, organic-inorganic or organic-carbon hybridization is a common strategy for constructing hybrid aerogel thin films. For example, organic/silica hybrid aerogels (CN109133071A), polyimide/carbon nanotube aerogels (CN106317407A), nylon/carbon nanotube aerogels (CN109810499A), and the like. However, the hybrid aerogel prepared at present is a block and is difficult to meet the market demand.
Disclosure of Invention
The invention mainly aims to provide an aramid fiber/carbon nanotube hybrid aerogel film and a preparation method thereof, so as to overcome the defects in the prior art.
Still another object of the present invention is to provide the use of the aforementioned aramid/carbon nanotube hybrid aerogel thin film.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an aramid fiber/carbon nanotube hybrid aerogel film, which comprises a communicated three-dimensional network-shaped porous structure and a hydrophobic coating layer coated on the three-dimensional network-shaped porous structure, wherein the three-dimensional network-shaped porous structure is formed by mutually lapping aramid fiber nanofibers and carbon nanotubes, the thickness of the aramid fiber/carbon nanotube hybrid aerogel film is 10-1000 mu m, and the specific surface area of the aramid fiber/carbon nanotube hybrid aerogel film is 100m2/g～1000m2G, density 0.01g/cm3～0.10g/cm3The tensile strength is 0.1MPa to 10MPa, the hydrophobic angle is 100 degrees to 170 degrees, and the conductivity is 0.1S/m to 103S/m, electromagnetic shielding efficiency of 10 dB-80 dB, and specific electromagnetic shielding efficiency of 103dB·cm2·g-1～105dB·cm2·g-1。
The embodiment of the invention also provides a preparation method of the aramid fiber/carbon nanotube hybrid aerogel film, which comprises the following steps:
at least uniformly mixing the carbon nano tube dispersion liquid and the aramid nano fiber dispersion liquid to form an aramid nano fiber/carbon nano tube mixed dispersion liquid;
applying the aramid nano-fiber/carbon nanotube mixed dispersion liquid on a substrate, transferring the substrate to a coagulation bath, and forming a hybrid gel film through sol-gel displacement;
drying the hybrid gel film to obtain a hybrid aerogel film;
and (3) at least soaking the hybrid aerogel film with a hydrophobic resin solution, drying, and coating at least part of hydrophobic resin on the hybrid aerogel film to obtain the aramid/carbon nanotube hybrid aerogel film.
The embodiment of the invention also provides the aramid fiber/carbon nanotube hybrid aerogel film prepared by the method.
The embodiment of the invention also provides application of the aramid fiber/carbon nanotube hybrid aerogel film in the fields of preparing intelligent films, personal heat management or wearable electromagnetic protection and the like.
Compared with the prior art, the invention has the advantages that:
(1) the aramid fiber/carbon nanotube hybrid aerogel film provided by the invention has excellent mechanical, electrical and hydrophobic properties, as well as excellent joule heating effect and electromagnetic shielding property; meanwhile, the aramid fiber/carbon nanotube hybrid aerogel film can be cut, bent and twisted;
(2) the preparation process of the aramid fiber/carbon nanotube hybrid aerogel film is simple, and large-scale production is easy to carry out;
(3) the aramid fiber/carbon nanotube hybrid aerogel film provided by the invention has wide application prospect, and can be applied to the fields of intelligent films, personal heat management, wearable electromagnetic protection and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of the aramid/carbon nanotube hybrid aerogel film according to a typical embodiment of the present invention.
FIG. 2 is a scanning electron micrograph of the aramid/carbon nanotube hybrid aerogel thin film obtained in example 1 of the present invention.
Fig. 3 is a nitrogen isothermal adsorption and desorption curve diagram of the aramid fiber/carbon nanotube hybrid aerogel film obtained in example 2 of the present invention.
Fig. 4 is a stress-strain curve diagram of the aramid/carbon nanotube hybrid aerogel thin film obtained in example 3 of the present invention in a stretching mode.
Fig. 5 is a photograph of the hydrophobic angle of the aramid/carbon nanotube hybrid aerogel thin film obtained in example 4 of the present invention.
Fig. 6 is a bar graph of the electrical conductivity of the aramid/carbon nanotube hybrid aerogel thin films obtained in examples 2 to 5 of the present invention.
Fig. 7 is a schematic diagram of joule heating effect of the aramid/carbon nanotube hybrid aerogel thin film obtained in example 6 of the present invention under different voltages.
Fig. 8 is a schematic diagram of electromagnetic shielding effectiveness of the aramid/carbon nanotube hybrid aerogel thin films obtained in examples 7 to 10 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention.
Carbon nanotubes have the advantages of excellent electrical conductivity, thermal conductivity, strong mechanical properties, light weight, good stability and the like, and are widely noticed as shielding materials and joule heating elements. Aramid fiber has the characteristics of high strength, high modulus, high temperature resistance and the like, and the nanofiber of the aramid fiber becomes a new driving force of the high-strength composite aerogel film. Therefore, the aramid nano-fiber and the carbon nano-tube are compounded to prepare the aerogel film, and then the hydrophobic coating is applied, so that the aerogel film has high strength, high conductivity, good hydrophobicity, joule heating effect, electromagnetic shielding performance and the like. Therefore, the invention can be applied to intelligent films and personal thermal management, and more importantly provides a direction for developing electromagnetic shielding materials in complex environments.
The technical solution, its implementation and principles, etc. will be further explained as follows.
Referring to fig. 1, according to an aspect of an embodiment of the present invention, an aramid/carbon nanotube hybrid aerogel film is provided, which includes aramid nanofibers, carbon nanotubes, and a hydrophobic coating.
The aramid fiber/carbon nanotube hybrid aerogel thin film is provided with a communicated three-dimensional network-shaped porous structure and a hydrophobic coating which is arranged on the three-dimensional network-shaped porous structure in a covering mode and is nanometer in thickness, the aramid fiber nanofiber and the carbon nanotubes are mutually overlapped to form the aerogel thin film with the three-dimensional network-shaped porous structure, and the hydrophobic coating is uniformly applied to the surface of the aerogel thin film.
In some preferred embodiments, the aramid nanofibers have a diameter of 2nm to 50nm and a length of 200nm to 5 μm.
In some preferred embodiments, the carbon nanotubes have a diameter of 1nm to 50nm and a length of 500nm to 30 μm.
In some preferred embodiments, the aramid nanofibers include any one or a combination of two or more of para-aramid nanofibers, meta-aramid nanofibers, and ortho-aramid nanofibers, etc., but are not limited thereto.
Further, the carbon nanotube includes any one or a combination of two or more of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, and the like, but is not limited thereto.
Further, the mass ratio of the aramid nanofibers to the carbon nanotubes is 1: 1-10: 1.
in some embodiments, the aramid/carbon nanotube hybrid aerogel film has a thickness of 10 μm to 1000 μm and a specific surface area of 100m2/g～1000m2G, density 0.01g/cm3～0.10g/cm3The tensile strength is 0.1 MPa-10 MPa, the mechanical property is good, and the coating can be bent, twisted and coated on the surface of an object with an irregular shape.
In some embodiments, the hydrophobic angle of the aramid/carbon nanotube hybrid aerogel film is 100-170 degrees, and the aramid/carbon nanotube hybrid aerogel film has a good self-cleaning function.
In some embodiments, the electrical conductivity of the aramid/carbon nanotube hybrid aerogel thin film is 0.1S/m to 103S/m, and can be stably and durably heated by joule heat effect, and the heating temperature is adjustable from room temperature to 300 ℃.
In some embodiments, the aramid/carbon nanotube hybrid aerogel film has an electromagnetic shielding efficiency of 10dB to 80dB and a specific electromagnetic shielding efficiency of 103dBcm2·g-1～105dB·cm2·g-1。
Another aspect of the embodiments of the present invention also provides a preparation method of an aramid/carbon nanotube hybrid aerogel thin film, including:
at least uniformly mixing the carbon nano tube dispersion liquid and the aramid nano fiber dispersion liquid to form an aramid nano fiber/carbon nano tube mixed dispersion liquid;
applying the aramid nano-fiber/carbon nanotube mixed dispersion liquid on a substrate, transferring the substrate to a coagulation bath, and forming a hybrid gel film through sol-gel displacement;
drying the hybrid gel film to obtain a hybrid aerogel film;
and (3) at least soaking the hybrid aerogel film with a hydrophobic resin solution, drying, and coating at least part of hydrophobic resin on the hybrid aerogel film to obtain the aramid/carbon nanotube hybrid aerogel film.
In a more preferred embodiment, the preparation method of the aramid/carbon nanotube hybrid aerogel thin film comprises the following steps:
(1) dispersing the carbon nano tube to obtain a carbon nano tube dispersion liquid A;
(2) dispersing macroscopic aramid fiber to obtain aramid nanofiber dispersion liquid B,
(3) uniformly mixing the dispersion liquid A, B to obtain an aramid nano-fiber/carbon nanotube mixed dispersion liquid C;
(4) coating the aramid nano-fiber/carbon nano-tube mixed dispersion liquid C on a substrate, transferring the substrate to a coagulating bath, and forming a hybrid gel film through a sol-gel process;
(5) drying the gel film to obtain a hybrid aerogel film;
(6) and soaking and drying the hybrid aerogel film by using hydrophobic resin to finally obtain the multifunctional hybrid aerogel film.
In a more preferred embodiment, step (1) may specifically include: and uniformly dispersing the carbon nano tube in the solvent to form carbon nano tube dispersion liquid.
Further, the solvent includes any one or a combination of two or more of acetone, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, N-dimethylformamide and the like, but is not limited thereto.
Further, the carbon nanotube includes any one or a combination of two or more of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, and the like, but is not limited thereto.
Further, the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.1 wt% to 2 wt%.
In a preferred embodiment, step (2) may specifically include: macroscopic aramid fiber and alkaline substances are mixed according to the mass ratio of 1: 0.2-1: 1, adding the mixture into a polar solvent, and magnetically stirring the mixture at a certain temperature (20-70 ℃) until a viscous and uniform dispersion liquid is formed to obtain the aramid nano-fiber dispersion liquid.
Further, the basic substance includes any one or a combination of two or more of sodium hydroxide, potassium tert-butoxide, and the like, but is not limited thereto.
Further, the polar solvent includes any one or a combination of two or more of acetone, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, N-dimethylformamide, and the like, but is not limited thereto.
Further, the concentration of the aramid nano-fibers in the aramid nano-fiber dispersion liquid is 0.1 wt% -10.0 wt%.
In a more preferred embodiment, in the step (3), the carbon nanotube dispersion liquid and the aramid nanofiber dispersion liquid are mixed according to a mass ratio of 1: 0.2-0.2: 1, mixing and stirring uniformly.
In a more preferred embodiment, the preparation method of the present invention specifically includes: the aramid fiber nanofibers and the carbon nanotubes are uniformly dispersed in a dimethyl sulfoxide solution, an aerogel film with a three-dimensional porous network structure is obtained through coating film making, sol-gel and special drying processes, and finally, the hydrophobic coating is uniformly applied to the surface of the aerogel film.
In a more preferred embodiment, in the step (4), the aramid nanofiber/carbon nanotube mixed dispersion may be coated on the substrate by at least blade coating, spin coating, roll-to-roll coating, and the like, and the thickness of the porous film may be adjusted by controlling the distance (10 μm to 1000 μm) between the blade and the substrate, the rotation speed (200rpm to 5000rpm) of the spin coater, or the distance (10 μm to 1000 μm) between the scroll and the roll; other methods of coating may also be used.
Further, the coated sample is transferred to a coagulation bath, the components of which include but are not limited to one or a combination of two or more of water (preferably deionized water), ethanol, methanol, ethylene glycol, and hydrochloric acid solution, and the gel film is formed by standing.
In a more preferred embodiment, in step (5), the preparation method comprises drying the hybrid gel film, wherein the drying treatment comprises atmospheric pressure drying, supercritical drying, freeze drying, preferably freeze drying. Solvent replacement is carried out before the freeze drying, namely, the solvent replacement is carried out on the hybrid gel film by using a replacement solvent, and then the freeze drying is carried out. The used replacement solvent includes, but is not limited to, one or a combination of two or more of water, ethanol, acetone, tert-butanol, and the like. The cold trap temperature of the freeze dryer is set to be-40 ℃ to-80 ℃, and the vacuum degree is not more than 0.1 kPa.
In a more preferred embodiment, in step (6), the hybrid aerogel film is soaked in a hydrophobic resin, wherein the hydrophobic resin includes, but is not limited to, silicone resin, silicone modified resin, fluorocarbon modified resin, and the like, and preferably is fluorocarbon resin.
Further, the fluorocarbon resin includes, but is not limited to, any one or a combination of two or more of polytetrafluoroethylene, polyvinylidene fluoride, chlorotrifluoroethylene copolymer, polyvinyl chloride copolymer, and the like.
Further, the soaking time is 1-30 s.
The aramid fiber/carbon nanotube hybrid aerogel film provided by the invention is simple in preparation process and easy for large-scale production.
Another aspect of the embodiments of the present invention also provides an aramid/carbon nanotube hybrid aerogel thin film prepared by the foregoing method, which has excellent mechanical, electrical and hydrophobic properties, as well as excellent joule heating effect and electromagnetic shielding property, especially specific electromagnetic shielding property; meanwhile, the aramid fiber/carbon nanotube hybrid aerogel film can be cut, bent and twisted.
The aramid fiber/carbon nanotube hybrid aerogel film disclosed by the invention has good mechanical property, an excellent self-cleaning function, an excellent Joule heat effect and an excellent electromagnetic shielding function, integrates a plurality of functions, and has a wide application prospect.
In another aspect of the embodiment of the invention, the wide application prospect of the aramid/carbon nanotube hybrid aerogel film is provided, including but not limited to the fields of preparing an intelligent film, or personal thermal management, wearable electromagnetic protection, and the like.
By the technical scheme, the aramid fiber/carbon nanotube hybrid aerogel film provided by the invention is composed of aramid fiber nanofibers, carbon nanotubes and a hydrophobic coating, the aramid fiber nanofibers and the carbon nanotubes are mutually lapped to form the aerogel film with a continuous three-dimensional porous network structure, and the hydrophobic coating is applied to obtain the aramid fiber/carbon nanotube hybrid aerogel film. The aramid fiber/carbon nanotube hybrid aerogel film has adjustable density, porosity and conductivity; meanwhile, the device has the functions of self-cleaning, temperature regulation, electromagnetic shielding and the like, and has a very wide application prospect.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustration and are not to be construed as limiting the scope of the invention, which may be varied in practice by those skilled in the art.
Example 1
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion liquid with the mass fraction of 0.1 wt%, adding the para-aramid and sodium hydroxide into the dimethyl sulfoxide according to the mass ratio of 1:0.2, stirring at 20 ℃, and preparing a para-aramid nanofiber dispersion liquid with the mass fraction of 0.1 wt%; uniformly mixing the multi-walled carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid according to the mass ratio of 0.2:1, carrying out spin coating at the rotation speed of 5000rpm, transferring the mixture into an ethanol coagulation bath, carrying out sol-gel replacement with water to form a hybrid gel film, and carrying out supercritical drying to obtain the hybrid aerogel film; and (3) immersing the hybrid aerogel film into an organic silicon resin solution for 1s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 10 microns. Fig. 2 shows SEM photographs of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example, and please refer to table 1 for other parameters.
Example 2
Adding a single-walled carbon nanotube into N-methylpyrrolidone to prepare a single-walled carbon nanotube dispersion liquid with the mass fraction of 0.5 wt%, adding para-aramid and potassium tert-butoxide into the N-methylpyrrolidone according to the mass ratio of 1:1, stirring at 30 ℃, and preparing a para-aramid nanofiber dispersion liquid with the mass fraction of 10 wt%; uniformly mixing the single-walled carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid according to the mass ratio of 1:0.2, carrying out spin coating at the rotating speed of 500rpm, transferring the mixture into a methanol coagulation bath, carrying out sol-gel replacement by using ethanol to form a hybrid gel film, and carrying out freeze drying at the temperature of-80 ℃ and under the condition of less than 0.1kPa to obtain the hybrid aerogel film; and (3) immersing the hybrid aerogel film into an organic silicon modified resin solution for 30s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 500 microns. Fig. 3 shows a nitrogen isothermal adsorption and desorption curve diagram of the aramid/carbon nanotube hybrid aerogel film obtained in this embodiment, fig. 6 shows a conductivity histogram of the aramid/carbon nanotube hybrid aerogel film obtained in this embodiment, and please refer to table 1 for other parameters.
Example 3
Adding the single-walled carbon nanotube into N, N-dimethylformamide to prepare a single-walled carbon nanotube dispersion liquid with the mass fraction of 0.74 wt%, adding para-aramid and potassium tert-butoxide into the N, N-dimethylformamide according to the mass ratio of 1:1, stirring at 40 ℃, and preparing a para-aramid nanofiber dispersion liquid with the mass fraction of 4 wt%; uniformly mixing the single-walled carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid according to the mass ratio of 1:0.5, carrying out spin coating at the rotation speed of 200rpm, transferring the mixture into an ethylene glycol coagulation bath, carrying out sol-gel replacement with acetone to form a hybrid gel film, and drying the hybrid gel film at normal pressure to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon modified resin solution for 2s, then taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 1000 microns. Fig. 4 shows a stress-strain curve diagram of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example in a stretching mode, fig. 6 shows a conductivity histogram of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example, and other parameters are shown in table 1.
Example 4
Adding the single-walled carbon nanotube into dimethyl sulfoxide to prepare a single-walled carbon nanotube dispersion liquid with the mass fraction of 1.03 wt%, adding para-aramid and potassium tert-butoxide into the dimethyl sulfoxide according to the mass ratio of 1:1, stirring at 50 ℃, and preparing a para-aramid nanofiber dispersion liquid with the mass fraction of 4 wt%; uniformly mixing the single-walled carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid according to the mass ratio of 1:0.5, carrying out spin coating at the rotating speed of 500rpm, transferring the mixture into a hydrochloric acid solution coagulation bath, carrying out sol-gel replacement by using tert-butyl alcohol to form a hybrid gel film, and carrying out freeze drying at the temperature of 50 ℃ below zero and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon resin solution with polyvinylidene fluoride as a main component for 5s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 500 mu m. Fig. 5 shows a photograph of the hydrophobic angle of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example, fig. 6 shows a histogram of the conductivity of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example, and please refer to table 1 for other parameters.
Example 5
Adding the single-walled carbon nanotube into dimethyl sulfoxide to prepare a single-walled carbon nanotube dispersion liquid with the mass fraction of 1.33 wt%, adding para-aramid and potassium tert-butoxide into the dimethyl sulfoxide according to the mass ratio of 1:1, stirring at 60 ℃, and preparing a para-aramid nanofiber dispersion liquid with the mass fraction of 4 wt%; uniformly mixing the single-walled carbon nanotube and the para-aramid nano-fiber dispersion liquid according to the mass ratio of 1:0.5, coating by using a scraper, wherein the distance between the scraper and the substrate is 500 mu m, transferring the mixture into a water coagulation bath, performing sol-gel replacement by using water and ethanol to form a hybrid gel film, and performing freeze drying at the temperature of-60 ℃ and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon resin solution with polytetrafluoroethylene as a main component for 10s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 500 mu m. Fig. 6 shows a conductivity bar chart of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example, and please refer to table 1 for other parameters.
Example 6
Adding single-walled carbon nanotubes into acetone to prepare a single-walled carbon nanotube dispersion liquid with the mass fraction of 2 wt%, adding ortho-aramid and potassium hydroxide into dimethyl sulfoxide according to the mass ratio of 1:0.5, stirring at 70 ℃, and preparing an ortho-aramid nanofiber dispersion liquid with the mass fraction of 1 wt%; uniformly mixing the single-walled carbon nanotube dispersion liquid and the ortho-position aramid nanofiber dispersion liquid according to the mass ratio of 0.5:1, coating by using a scraper, wherein the distance between the scraper and the substrate is 1000 microns, transferring the mixture into a mixed coagulation bath of ethanol and methanol, performing sol-gel replacement by using the ethanol to form a hybrid gel film, and performing freeze drying at the temperature of-70 ℃ and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon resin solution with the main component of chlorotrifluoroethylene copolymer for 12s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nano tube hybrid aerogel film with the thickness of 1000 microns. Fig. 7 shows joule heating effect of the aramid/carbon nanotube hybrid aerogel film obtained in this example, please refer to table 1 for other parameters.
Example 7
Adding the double-walled carbon nano tube into acetonitrile to prepare a double-walled carbon nano tube dispersion liquid with the mass fraction of 0.5 wt%, adding the meta-aramid and the potassium hydroxide into dimethyl sulfoxide according to the mass ratio of 1:0.5, stirring at 30 ℃, and preparing a meta-aramid nano fiber dispersion liquid with the mass fraction of 0.5 wt%; uniformly mixing the double-wall carbon nanotube dispersion liquid and the meta-aramid nanofiber dispersion liquid according to the mass ratio of 0.25:1, coating by using a scraper, wherein the distance between the scraper and a substrate is 10 mu m, transferring the mixture into a mixed coagulation bath of ethanol and glycol to perform sol-gel displacement by using acetone to form a hybrid gel film, and freeze-drying the hybrid gel film at the temperature of 50 ℃ below zero and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon resin solution with polytetrafluoroethylene as a main component for 20s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 10 microns. Fig. 8 shows the electromagnetic shielding effectiveness of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example at 8.2GHz-12.4GHz, please refer to table 1 for other parameters.
Example 8
Adding the double-wall carbon nano tube into dimethyl sulfoxide to prepare a double-wall carbon nano tube dispersion liquid with the mass fraction of 0.74 wt%, adding meta-aramid and potassium hydroxide into the dimethyl sulfoxide according to the mass ratio of 1:0.5, stirring at 45 ℃, and preparing a meta-aramid nano fiber dispersion liquid with the mass fraction of 2 wt%; uniformly mixing the double-wall carbon nanotube dispersion liquid and the meta-aramid nano-fiber dispersion liquid in equal mass, coating in a reel-to-reel manner, transferring the mixture to an ethanol coagulation bath, performing sol-gel replacement by using ethanol and tert-butyl alcohol to form a hybrid gel film, and freeze-drying at-50 ℃ and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) soaking the aerogel film into a fluorocarbon resin solution with polytetrafluoroethylene as a main component for 25s, then taking out, and drying at room temperature to obtain the aramid fiber/carbon nano tube hybrid aerogel film with the thickness of 500 mu m. Fig. 8 shows the electromagnetic shielding effectiveness of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example at 8.2GHz-12.4GHz, please refer to table 1 for other parameters.
Example 9
Adding the double-wall carbon nano tube into dimethyl sulfoxide to prepare double-wall carbon nano tube dispersion liquid with the mass fraction of 1.03 wt%, adding para-aramid and potassium hydroxide into acetone according to the mass ratio of 1:0.5, stirring at 50 ℃, and preparing para-aramid nano fiber dispersion liquid with the mass fraction of 2 wt%; uniformly mixing the double-wall carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid in equal mass, coating in a roll-to-roll manner, wherein the distance between a reel and the reel is 1000 mu m, transferring the mixture into a methanol coagulation bath, performing sol-gel replacement by using water to form a hybrid gel film, and freeze-drying the hybrid gel film at the temperature of-45 ℃ and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) soaking the aerogel film into a fluorocarbon resin solution with polytetrafluoroethylene as a main component for 15s, then taking out, and drying at room temperature to obtain the aramid fiber/carbon nano tube hybrid aerogel film with the thickness of 1000 microns. Fig. 8 shows the electromagnetic shielding effectiveness of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example at 8.2GHz-12.4GHz, please refer to table 1 for other parameters.
Example 10
Adding the double-wall carbon nano tube into dimethyl sulfoxide to prepare double-wall carbon nano tube dispersion liquid with the mass fraction of 1.33 wt%, adding para-aramid and potassium hydroxide into acetonitrile according to the mass ratio of 1:0.5, stirring at 70 ℃, and preparing para-aramid nano fiber dispersion liquid with the mass fraction of 2 wt%; uniformly mixing the double-wall carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid in equal mass, coating in a reel-to-reel manner, wherein the distance between a reel and a reel is 10 mu m, transferring the mixture into an ethanol coagulation bath, performing sol-gel replacement by using water and acetone to form a hybrid gel film, and freeze-drying the hybrid gel film at the temperature of-40 ℃ and under the condition of less than 0.1kPa to obtain an aerogel film; and (3) immersing the aerogel film into a fluorocarbon resin solution with main components of chlorotrifluoroethylene copolymer and polyvinyl chloride copolymer for 2s, taking out, and drying at room temperature to obtain the aramid fiber/carbon nanotube hybrid aerogel film with the thickness of 10 microns. Fig. 8 shows the electromagnetic shielding effectiveness of the aramid/carbon nanotube hybrid aerogel thin film obtained in this example at 8.2GHz-12.4GHz, please refer to table 1 for other parameters.
Comparative example 1
Adding the double-wall carbon nano tube into dimethyl sulfoxide to prepare double-wall carbon nano tube dispersion liquid with the mass fraction of 1.33 wt%, and adding para-aramid and potassium hydroxide into the dimethyl sulfoxide according to the mass ratio of 1:0.5 to prepare para-aramid nano fiber dispersion liquid with the mass fraction of 2 wt%; and uniformly mixing the double-wall carbon nanotube dispersion liquid and the para-aramid nano-fiber dispersion liquid in equal mass, and performing scraper coating, and performing freeze drying at-50 ℃ and 0.1kPa to obtain an aramid/carbon nanotube hybrid aerogel film with the thickness of 568 mu m, wherein the parameters are shown in Table 1.
Comparative example 2
Adding para-aramid and potassium hydroxide into dimethyl sulfoxide according to the mass ratio of 1:0.5 to prepare a para-aramid nanofiber dispersion liquid with the mass fraction of 2 wt%, adopting a scraper coating method, carrying out freeze drying at the temperature of-50 ℃ and under the condition of 0.1kPa, then soaking the para-aramid nanofiber dispersion liquid into a fluorocarbon resin solution with the main component of polytetrafluoroethylene for 2s, taking out the para-aramid nanofiber dispersion liquid, and drying the para-aramid nanofiber dispersion liquid at room temperature to obtain an aramid aerogel film with the thickness of 500 mu m, wherein the parameters are shown in Table 1.
Comparative example 3
Adding 0.1g of double-wall carbon nano tube into 50g of dimethyl sulfoxide, adding 0.15g of aramid chopped fiber after uniform dispersion, stirring for several hours, coating with a scraper, and finally obtaining the aerogel film, wherein the parameters are shown in table 1.
TABLE 1 structural and performance parameters of the aerogel films obtained in examples 1 to 10 and comparative examples 1 to 3,
through the embodiments 1 to 10, it can be found that the hybrid aerogel thin film obtained by the technical scheme of the invention has good mechanical properties, excellent self-cleaning function, excellent joule heating effect and electromagnetic shielding function, and simple preparation process, and is easy for large-scale production.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (16)
1. The preparation method of the aramid fiber/carbon nanotube hybrid aerogel film is characterized by comprising the following steps of:
uniformly dispersing carbon nanotubes in a solvent to form a carbon nanotube dispersion liquid, wherein the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.1-2 wt%;
adding macroscopic aramid fiber and alkaline substances into a polar solvent, stirring at 20-70 ℃ until a uniform dispersion liquid is formed, and obtaining an aramid nanofiber dispersion liquid, wherein the mass ratio of the aramid fiber to the alkaline substances is 1: 0.2-1: 1, the concentration of aramid nano-fibers in the aramid nano-fiber dispersion liquid is 0.1-10.0 wt%;
uniformly mixing a carbon nano tube dispersion liquid and an aramid nano fiber dispersion liquid to form an aramid nano fiber/carbon nano tube mixed dispersion liquid, wherein the mass ratio of the carbon nano tube dispersion liquid to the aramid nano fiber dispersion liquid is 1: 0.2-0.2: 1;
applying the aramid nano-fiber/carbon nanotube mixed dispersion liquid on a substrate, transferring the substrate to a coagulating bath, and forming a hybrid gel film through sol-gel displacement, wherein the coagulating bath is any one or the combination of more than two of water, ethanol, methanol, ethylene glycol and hydrochloric acid solution;
firstly, performing solvent replacement on the hybrid gel film by using a replacement solvent, and then performing freeze drying to obtain a hybrid aerogel film;
soaking the hybrid aerogel film with a hydrophobic resin solution, drying, and coating at least part of hydrophobic resin on the hybrid aerogel film to obtain an aramid/carbon nanotube hybrid aerogel film, wherein the hydrophobic resin is selected from any one or a combination of more than two of organic silicon resin, organic silicon modified resin, fluorocarbon resin and fluorocarbon modified resin, and the soaking time is 1-30 s;
the aramid fiber/carbon nano tube hybrid aerogel thin film comprises a communicated three-dimensional network-shaped porous structure and a hydrophobic coating layer coated on the three-dimensional network-shaped porous structure, wherein the three-dimensional network-shaped porous structure is formed by mutually lapping aramid fiber nano fibers and carbon nano tubes, and the aramid fiber/carbon nano tube hybrid aerogel thin filmThe thickness of the membrane is 10 mu m-1000 mu m, and the specific surface area is 100m2/g~1000 m2G, density 0.01g/cm3~0.10 g/cm3The tensile strength is 0.1MPa to 10MPa, the hydrophobic angle is 100 degrees to 170 degrees, and the conductivity is 0.1S/m to 10 degrees3S/m, electromagnetic shielding efficiency of 10 dB-80 dB, and specific electromagnetic shielding efficiency of 103 dB∙cm2∙g-1~105 dB∙cm2∙g-1The thickness of the hydrophobic coating is nanoscale, the diameter of the aramid nanofiber is 2 nm-50 nm, and the length of the aramid nanofiber is 200 nm-5 mu m; the diameter of the carbon nano tube is 1 nm-50 nm, the length of the carbon nano tube is 500 nm-30 mu m, and the mass ratio of the aramid nano fiber to the carbon nano tube is 1: 1-10: 1.
2. the method of claim 1, wherein: the solvent is selected from any one or the combination of more than two of acetone, acetonitrile, dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide.
3. The method of claim 1, wherein: the carbon nano tube is selected from any one or the combination of more than two of a single-wall carbon nano tube, a double-wall carbon nano tube and a multi-wall carbon nano tube.
4. The method of claim 1, wherein: the aramid nano-fiber is selected from any one or the combination of more than two of para-aramid nano-fiber, meta-aramid nano-fiber and ortho-aramid nano-fiber.
5. The method of claim 1, wherein: the alkaline substance is selected from any one or combination of more than two of sodium hydroxide, potassium hydroxide and potassium tert-butoxide.
6. The method of claim 1, wherein: the polar solvent is selected from any one or the combination of more than two of acetone, acetonitrile, dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide.
7. The production method according to claim 1, characterized by comprising: and coating the aramid nano-fiber/carbon nano-tube mixed dispersion liquid on a substrate by adopting any one of a scraper coating method, a rotary coating method and a roll-to-roll coating method.
8. The method for producing according to claim 7, characterized in that: the distance between the scraper and the substrate in the scraper coating method is 10-1000 mu m.
9. The method of claim 7, wherein: the rotating speed adopted by the spin coating method is 200-5000 rpm.
10. The method of claim 7, wherein: the distance between the scroll and the reel adopted by the roll-to-roll coating method is 10-1000 mu m.
11. The method of claim 1, wherein: the drying treatment is any one or combination of more than two of a normal pressure drying method, a supercritical drying method and a freeze drying method.
12. The method of claim 11, wherein: the drying treatment is a freeze drying method.
13. The method of claim 1, wherein: the replacement solvent is selected from any one or the combination of more than two of water, ethanol, acetone and tertiary butanol.
14. The method of manufacturing according to claim 12, wherein: the temperature of a cold trap of the freeze drying method is-80 to-40 ℃, and the vacuum degree is less than 0.1 kPa.
15. The production method according to claim 1, characterized in that: the hydrophobic resin is fluorocarbon resin, and the fluorocarbon resin is selected from one or the combination of more than two of polytetrafluoroethylene, polyvinylidene fluoride, chlorotrifluoroethylene copolymer and polyvinyl chloride copolymer.
16. Use of the aramid/carbon nanotube hybrid aerogel thin film prepared by the preparation method of any one of claims 1 to 15 for the preparation of smart films, personal thermal management or wearable electromagnetic protection fields.
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