CN115246746A - Soft layered carbon film and preparation method and application thereof - Google Patents
Soft layered carbon film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a soft layered carbon film and a preparation method and application thereof. The soft layered carbon film has a layered network porous structure, and the layered network porous structure is formed by laminating and densifying a nanofiber network and mutually overlapping. The soft layered carbon film is prepared by performing sol-gel, freeze drying, compression densification and high-temperature carbonization on an aramid nano fiber/carbon nano tube mixed solution. The density of the soft layered carbon film prepared by the invention is 0.06-0.5 g/cm 3 The thickness is 15-101 μm, the tensile strength is 5-26 MPa, the conductivity is 14-289.6S/cm, the electromagnetic shielding efficiency is 25-42 dB, and the specific electromagnetic shielding efficiency is 53697.3-200647.9 dB cm 2 A/g, at the same time hasThe adjusted hydrophilic and hydrophobic characteristics have wide application prospect in the field of electromagnetic protection.
Description
Technical Field
The invention relates to a soft layered carbon film, in particular to a soft layered carbon film for electromagnetic protection and a preparation method and application thereof, belonging to the technical field of novel nano materials and electromagnetic protection materials.
Background
With the wide use of electronic devices, the attention of people is paid to electromagnetic pollution caused by the electronic devices, and electromagnetic protection materials are also widely researched. Meanwhile, electronic equipment tends to be miniaturized, and the electromagnetic protection material is required to have low density when having efficient electromagnetic protection, so that the application of the traditional metal electromagnetic shielding material is greatly limited, and the carbon nano tube has low density and good conductivity, and is an ideal electromagnetic shielding material.
The electromagnetic protection capability of a material is not only related to the material itself, but also to the microstructure of the material. The layered structure similar to graphene and MXene has good microwave absorption capacity, on one hand, due to the high conductivity of the layered structure, and on the other hand, due to the fact that the layered microstructure of the layered structure can effectively improve multiple reflection and scattering of electromagnetic waves, the layered structure has wide application value when being introduced into the carbon nanotube film.
At present, a plurality of methods for preparing the carbon nanotube film, such as a suspension coating method, an electrophoresis method, a vacuum filtration method, a spraying method, a chemical vapor deposition method and the like, are not beneficial to the large-scale and continuous production of the carbon nanotube film. Meanwhile, the carbon nanotube films obtained by the methods have higher density. The aerogel is a continuous porous network structure material and has extremely low density, so that the carbon nanotubes are mixed with organic polymers, and the aerogel is used as an intermediate, so that the light weight of the carbon film can be realized. Meanwhile, the organic polymer dispersion liquid has a very mature process for continuous and large-scale production through a blade coating method, so that the preparation method of the soft layered carbon film has great feasibility for realizing large-scale and continuous production of the high-efficiency electromagnetic shielding carbon film.
Disclosure of Invention
The invention mainly aims to provide a soft layered carbon film and a preparation method thereof, so as to realize high-efficiency electromagnetic protection performance and overcome the defects in the prior art.
It is still another object of the present invention to provide use of the aforementioned soft layered carbon film.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a soft layered carbon film, which has a porous structure of a layered network, wherein the porous structure of the layered network is formed by laminating and densifying nanofiber networks and mutually lapping, the thickness of the soft layered carbon film is 15-101 mu m, and the density of the soft layered carbon film is 0.06-0.5 g/cm 3 The tensile strength is 5-26 MPa, the hydrophobic angle is 54.8-115.9 degrees, the conductivity is 14-289S/cm, the electromagnetic shielding efficiency is 25-42 dB, and the specific electromagnetic shielding efficiency is 53697.3-200647.9 dB cm 2 The pore diameter distribution of pores contained in the porous structure is 10-100 nm.
The embodiment of the invention also provides a preparation method of the soft layered carbon film, which comprises the following steps:
uniformly dispersing aramid nano-fibers in a carbon nano-tube 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, performing film forming treatment, transferring 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;
carrying out compression densification treatment on the hybrid aerogel film to obtain a layered hybrid film;
and under the protection of inert gas, carrying out high-temperature carbonization treatment on the layered hybrid film to obtain the soft layered carbon film.
In some embodiments, the compression densification process employs a pressure of 5 to 10Mpa, a compression temperature of 20 to 50 ℃, and a time of 10 to 30min.
In some embodiments, the temperature of the high temperature carbonization treatment is 550 to 950 ℃, and the time of the high temperature carbonization treatment is 0.5 to 7 hours.
The embodiment of the invention also provides the soft layered carbon film prepared by the method.
The embodiment of the invention also provides application of any one of the soft layered carbon films in the field of electromagnetic protection.
Compared with the prior art, the invention has the beneficial effects that:
(1) The soft layered carbon film provided by the invention is composed of a compact carbon nanotube layer and an interlayer porous structure, the compact layer provides good conductivity, the interlayer porous structure effectively reduces the density of the film, and the light and efficient electromagnetic shielding performance is realized;
(2) The soft layered carbon film provided by the invention has excellent mechanical, electrical and hydrophobic properties; meanwhile, the soft layered carbon film can be cut, bent and twisted;
(3) The preparation process of the soft layered carbon film provided by the invention is simple, large-scale production is easy to carry out, and pressure densification is favorable for building a conductive network of the carbon nano tube;
(4) The soft layered carbon film provided by the invention has high-efficiency electromagnetic shielding performance and can be applied to the field of electromagnetic protection.
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 a soft layered carbon film according to an exemplary embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a soft layered carbon film obtained in example 1 of the present invention;
FIG. 3 is a stress-strain curve of the soft layered carbon film obtained in example 2 of the present invention in a tensile mode;
FIG. 4 is a histogram of the density of the soft layered carbon films obtained in examples 1 to 5 of the present invention;
FIG. 5 is a bar graph of the conductivity of the soft layered carbon films obtained in examples 1 to 5 of the present invention;
FIG. 6 is a photograph of the hydrophobic angle of the soft layered carbon film obtained in example 5 of the present invention;
FIG. 7 is a graph showing the electromagnetic shielding properties of the soft layered carbon films obtained in examples 1 to 5 of the present invention;
FIG. 8 is a graph showing the specific electromagnetic shielding effectiveness of the soft layered carbon films obtained in examples 1 to 5 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution 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. The aramid aerogel has the characteristics of low density, high specific surface area, high strength, high modulus and the like. Therefore, the aramid nano-fiber and the carbon nano-tube are compounded, the aerogel is used as an intermediate, and the flexible layered carbon film with lower density is obtained through pressure densification and carbonization. The invention can provide a new direction for the development of the ultra-light and high-efficiency electromagnetic shielding material.
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, a soft layered carbon film is provided, which has a porous structure of a layered network, and the porous structure of the layered network is formed by stacking nanofiber networks and overlapping the nanofiber networks.
Further, the soft layered carbon film of the present invention is composed of carbon nanofibers, and has a layered and porous structure. The layered structure is formed by compressing and densifying the aramid fiber nanofiber and the carbon nanotube network through external force, and the porous structure is formed by mutually lapping carbonized aramid fiber nanofibers and carbon nanotubes.
In some embodiments, the soft layered carbon film has a thickness of 15 to 101 μm and a density of 0.06 to 0.5g/cm 3 The tensile strength is 5-26 MPa.
In some embodiments, the soft layered carbon film has adjustable hydrophilic and hydrophobic properties, a hydrophobic angle of 54.8-115.9 degrees, and a good self-cleaning function.
Furthermore, the conductivity of the soft layered carbon film is 14-289S/cm, which is beneficial to electromagnetic protection.
Furthermore, the electromagnetic shielding efficiency of the soft layered carbon film is 25-42 dB, and the specific electromagnetic shielding efficiency is 53697.3-200647.9 dB cm 2 And/g, has high-efficiency electromagnetic shielding performance.
Further, the pore size distribution of the porous structure is 10-100 nm.
In some embodiments, the nanofibers comprise aramid nanofibers and carbon nanotubes.
Wherein the aramid nanofibers preferably comprise para-aramid nanofibers.
In some embodiments, the aramid nanofibers have a diameter of 2nm to 50nm and a length of 200nm to 5 μm.
In some embodiments, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and the like, but are not limited thereto.
In some embodiments, the carbon nanotubes have a diameter of 1nm to 50nm and a length of 500nm to 30 μm.
In some embodiments, the mass ratio of the aramid nanofibers to the carbon nanotubes is 2:1 to 10:1.
in conclusion, the soft layered carbon film provided by the invention has excellent mechanical, electrical and hydrophobic properties and excellent electromagnetic shielding performance; meanwhile, the soft layered carbon film can be cut, bent and twisted.
The embodiment of the invention also provides a preparation method of the soft layered carbon film, the soft layered carbon film is mainly prepared by performing sol-gel, freeze drying, compression densification and high-temperature carbonization treatment on an aramid nano fiber/carbon nano tube mixed solution, and the pressure densification is favorable for building a conductive network of the carbon nano tube.
In some embodiments, a method of preparing the soft layered carbon film includes:
uniformly dispersing aramid nano-fibers in a carbon nano-tube 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, carrying out blade coating film forming treatment, transferring to a coagulation bath, and forming a hybrid gel film through sol-gel replacement;
drying the hybrid gel film to obtain a hybrid aerogel film;
carrying out compression densification treatment on the hybrid aerogel film to obtain a layered hybrid film;
and under the protection of inert gas, carrying out high-temperature carbonization treatment on the layered hybrid film to obtain the soft layered carbon film.
In a more preferred embodiment, the method for preparing the soft layered carbon film comprises the following steps:
(1) Dispersing the carbon nano tube to obtain a carbon nano tube dispersion liquid A;
(2) Adding aramid nano-fiber and alkaline substances into the carbon nano-tube dispersion liquid A to obtain aramid nano-fiber/carbon nano-tube mixed dispersion liquid B;
(3) Coating the aramid nano-fiber/carbon nano-tube mixed dispersion liquid B on a substrate, transferring the substrate to a coagulating bath, and forming a hybrid gel film through a sol-gel process;
(4) Drying the hybrid gel film to obtain a hybrid aerogel film;
(5) Performing pressure densification on the hybrid aerogel film to obtain a layered hybrid film;
(6) And under the protection of inert gas, carrying out high-temperature carbonization treatment on the layered hybrid film to obtain the soft layered carbon film.
In a more preferred embodiment, step (1) may specifically include: and uniformly dispersing the carbon nano tubes in a solvent to form a carbon nano tube dispersion liquid.
Further, the solvent includes dimethyl sulfoxide, 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 diameter of the carbon nano tube is 1nm to 50nm, and the length of the carbon nano tube is 500nm to 30 mu m.
Further, the concentration of the carbon nanotubes in the carbon nanotube dispersion is 0.1wt% to 0.5wt%.
In a preferred embodiment, step (2) may specifically include: macroscopic aramid nano-fiber and alkaline substances are mixed according to the mass ratio of 2:1 to 1:1, adding the mixture into the carbon nano tube dispersion liquid A, and magnetically stirring for 4 days at normal temperature until a uniform dispersion liquid is formed to obtain an aramid nano fiber/carbon nano tube mixed dispersion liquid.
Further, the mass ratio of the aramid nano-fiber to the alkaline substance is 2:1 to 1:1.
further, the aramid nanofibers include para-aramid nanofibers.
In some embodiments, the aramid nanofibers have a diameter of 2nm to 50nm and a length of 200nm to 5 μm.
Further, the basic substance includes any one or a combination of two of potassium hydroxide, potassium tert-butoxide, and the like, but is not limited thereto.
Further, the concentration of the aramid nano-fiber in the aramid nano-fiber/carbon nano-tube mixed dispersion liquid is 1wt% -2 wt%.
Further, the mass ratio of the carbon nano tubes to the aramid nano fibers is 2:1 to 10:1.
in a more preferred embodiment, step (3) may comprise: coating the aramid nano-fiber/carbon nano-tube mixed dispersion liquid on a substrate by a scraper coating method, and regulating the thickness of a film by controlling the distance (250-1000 mu m) between a scraper and the substrate; coating can also be carried out by other methods such as casting.
Further, transferring the coated sample into a coagulation bath which is water, and standing to form a gel film; the coagulation bath may be a protic solution such as ethanol or methanol, but is not limited thereto.
In a more preferred embodiment, in step (4), the hybrid gel film is subjected to a drying process, wherein the drying process comprises vacuum freeze drying and supercritical drying, preferably freeze drying. And (3) performing solvent replacement before the vacuum freeze drying, namely performing solvent replacement on the hybrid gel film by using a replacement solvent, and then performing vacuum freeze drying. Wherein the adopted replacement solvent is a mixed solution of tert-butyl alcohol and water. The cold trap temperature of the freeze dryer is set to-50 ℃ and the vacuum degree is not more than 0.1kPa.
Further, the mass ratio of the tert-butyl alcohol to the water is 1:1 to 1:5.
in a more preferred embodiment, in step (5), the compression densification treatment is performed at a pressure of 5 to 10Mpa and a compression temperature of 20 to 50 ℃ for 10 to 30min.
In a more preferred embodiment, in the step (6), the temperature of the high-temperature carbonization treatment is 550 to 950 ℃.
Furthermore, the time of the high-temperature carbonization treatment is 0.5 to 7 hours.
Further, the inert gas includes any one or a combination of two of nitrogen and argon.
The preparation process of the soft layered carbon film provided by the invention is simple and is easy for large-scale growth.
Another reverse side of the embodiment of the present invention also provides a soft layered carbon film prepared by the aforementioned method, which has excellent mechanical, electrical and hydrophobic properties, and excellent electromagnetic shielding properties; meanwhile, the soft layered carbon film can be cut, bent and twisted.
Another aspect of the embodiments of the present invention also provides a potential application of any one of the aforementioned soft layered carbon films, including but not limited to the field of electromagnetic protection.
By the technical scheme, the soft layered carbon film is obtained by pressure densification and carbonization of the aerogel intermediate, is formed by mutually lapping carbonized aramid nano fibers and carbon nano tubes, and has a porous structure of a layered network. The soft layered carbon film has adjustable density and conductivity, and has an electromagnetic shielding function, so that the application prospect is very wide.
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 intended to limit the scope of the invention, which may be modified by those skilled in the art in view of the circumstances.
Example 1
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-50 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature (25 ℃) to perform lamellar densification for 20min, and finally carbonizing at 550 ℃ for 1h under the protection of argon to obtain the soft lamellar carbon film. Fig. 2 shows SEM photographs of the soft layered carbon film obtained in the present example, and fig. 4 shows a density histogram of the soft layered carbon film obtained in the present example. Fig. 5 shows a conductivity histogram of the soft layered carbon film obtained in the present example, fig. 7 shows an electromagnetic shielding characteristic diagram of the soft layered carbon film obtained in the present example, fig. 8 shows a specific electromagnetic shielding efficiency diagram of the soft layered carbon film obtained in the present example, and other parameters are shown in table 1.
Example 2
Adding a multi-wall carbon nanotube into dimethyl sulfoxide to prepare a multi-wall carbon nanotube dispersion liquid, adding para-aramid nano-fibers and potassium tert-butoxide into the multi-wall carbon nanotube dispersion liquid according to a mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-80 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 10min, and finally carbonizing at 650 ℃ for 1h under the protection of argon to obtain the soft layered carbon film. Fig. 3 shows a stress-strain curve in a tensile mode of the soft layered carbon film obtained in the present example, and fig. 4 shows a density histogram of the soft layered carbon film obtained in the present example. Fig. 5 shows a bar graph of the conductivity of the soft layered carbon film obtained in the present example, fig. 7 shows a graph of the electromagnetic shielding characteristics of the soft layered carbon film obtained in the present example, fig. 8 shows a graph of the specific electromagnetic shielding efficiency of the soft layered carbon film obtained in the present example, and other parameters are shown in table 1.
Example 3
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the water solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-60 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 30min, and finally carbonizing at 750 ℃ for 1h under the protection of argon to obtain the soft layered carbon film. Fig. 4 shows a density histogram of the soft layered carbon film obtained in the present example, fig. 5 shows a conductivity histogram of the soft layered carbon film obtained in the present example, fig. 7 shows an electromagnetic shielding characteristic diagram of the soft layered carbon film obtained in the present example, fig. 8 shows a specific electromagnetic shielding efficiency diagram of the soft layered carbon film obtained in the present example, and other parameters are shown in table 1.
Example 4
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-70 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 20min, and finally carbonizing for 1h at 850 ℃ under the protection of argon to obtain the soft layered carbon film. Fig. 4 shows a density histogram of the soft layered carbon film obtained in the present example, fig. 5 shows a conductivity histogram of the soft layered carbon film obtained in the present example, fig. 7 shows an electromagnetic shielding characteristic diagram of the soft layered carbon film obtained in the present example, fig. 8 shows a specific electromagnetic shielding efficiency diagram of the soft layered carbon film obtained in the present example, and other parameters are shown in table 1.
Example 5
Adding a multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion liquid, adding para-aramid nano-fibers and potassium tert-butoxide into the multi-walled carbon nanotube dispersion liquid according to a mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-50 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 10min, and finally carbonizing for 1h at 950 ℃ under the protection of argon to obtain the soft layered carbon film. Fig. 4 shows a density histogram of the light and soft layered carbon film obtained in the present example, fig. 5 shows a conductivity histogram of the light and soft layered carbon film obtained in the present example, fig. 6 shows a water-repellent angle characteristic of the light and soft layered carbon film obtained in the present example, fig. 7 shows an electromagnetic shielding characteristic diagram of the light and soft layered carbon film obtained in the present example, fig. 8 shows a specific electromagnetic shielding efficiency diagram of the light and soft layered carbon film obtained in the present example, and other parameters are shown in table 1.
Example 6
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared from the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-50 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 10min, and finally carbonizing at 750 ℃ for 1h under the protection of argon to obtain the soft layered carbon film.
Example 7
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding para-aramid and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared from the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-60 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at normal temperature to perform layered densification for 10min, and finally carbonizing at 750 ℃ for 1h under the protection of nitrogen to obtain the soft layered carbon film.
Example 8
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding para-aramid and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 1000 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, performing solvent replacement on the tertiary butanol and the aqueous solution, performing vacuum freeze drying after full replacement, wherein the temperature of a cold trap is-80 ℃, and the vacuum degree is less than 0.1kPa to obtain a hybrid aerogel film, applying 8MPa to the hybrid aerogel film at normal temperature to perform lamellar densification for 30min, and finally carbonizing at 750 ℃ for 0.5h under the protection of argon to obtain the soft lamellar carbon film.
Example 9
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding para-aramid and potassium hydroxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 2 to 1, stirring for 7 days at 25 ℃, and preparing a mixed solution of which the mass fractions of the multi-walled carbon nanotube and the para-aramid are 0.2% and 1%, respectively. Controlling the distance between a scraper and a substrate to be 550 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:2, carrying out solvent replacement on the tertiary butanol and the aqueous solution, fully replacing, carrying out supercritical drying to obtain a hybrid aerogel film, applying 5MPa to the hybrid aerogel film at 70 ℃ to carry out lamellar densification for 10min, and finally carbonizing at 750 ℃ for 5h under the protection of argon to obtain the soft lamellar carbon film.
Example 10
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding para-aramid and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 250 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared from the following components in a mass ratio of 1: and 5, carrying out solvent replacement on the tertiary butanol and the water solution, after full replacement, carrying out vacuum freeze drying at the cold trap temperature of-50 ℃ and the vacuum degree of less than 0.1kPa to obtain a hybrid aerogel film, applying 10MPa to the hybrid aerogel film at the temperature of 20 ℃ to carry out lamellar densification for 30min, and finally carbonizing at the temperature of 750 ℃ for 7h under the protection of argon to obtain the soft lamellar carbon film.
Comparative example 1
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1: and (2) carrying out solvent replacement on the tertiary butanol of the step (1) and an aqueous solution, and after full replacement, carrying out vacuum freeze drying to obtain the hybrid aerogel film.
Comparative example 2
Adding the multi-walled carbon nanotube into dimethyl sulfoxide to prepare a multi-walled carbon nanotube dispersion solution, adding the para-aramid nano-fiber and potassium tert-butoxide into the multi-walled carbon nanotube dispersion solution according to the mass ratio of 1. Controlling the distance between a scraper and a substrate to be 750 mu m, carrying out blade coating to form a film, transferring the film into an aqueous solution coagulating bath to carry out sol-gel to form a hybrid gel film, wherein the hybrid gel film is prepared by mixing the following components in a mass ratio of 1:1, carrying out solvent replacement on the tertiary butanol and the aqueous solution, fully replacing, carrying out vacuum freeze drying to obtain a hybrid aerogel film, and applying 5MPa to the hybrid aerogel film at normal temperature (25 ℃) to carry out lamellar densification to obtain the soft lamellar carbon film.
TABLE 1 Structure and Performance parameters of the soft layered carbon films obtained in examples 1-10 and comparative examples 1-2
Comparative example 3
The inventor also refers to the method of CN108794790A to prepare an aramid fiber electromagnetic shielding paper, but the thickness of the electromagnetic shielding paper is 300 μm, while the thickness of the carbon film in the invention is only 15 μm.
Comparative example 4
The inventor also refers to a method for preparing the aramid fiber/carbon nano tube hybrid aerogel film by using CN110982114A, but the specific electromagnetic shielding efficiency of the aramid fiber/carbon nano tube hybrid aerogel film is 10 3 ～10 5 dB·cm 2 The carbon film of the invention has the highest specific electromagnetic shielding efficiency of 200647.9dB cm 2 /g。
Through the embodiments 1-10, it can be found that the soft layered carbon film obtained by the technical scheme of the invention has good mechanical properties, excellent self-cleaning function, excellent electromagnetic shielding function, simple preparation process and easy large-scale production.
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, for example, experiments with single-walled carbon nanotubes, double-walled carbon nanotubes, etc. instead of multi-walled carbon nanotubes have all obtained desirable results.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A soft layered carbon film, characterized in that the soft layered carbon film has a layered network porous structure formed by a nanofiber network through lamination densification and mutual lap joint, the thickness of the soft layered carbon film is 15-101 μm, and the density is 0.06-0.5 g/cm 3 The tensile strength is 5-26 MPa, the hydrophobic angle is 54.8-115.9 degrees, the conductivity is 14-289S/cm, the electromagnetic shielding efficiency is 25-42 dB, and the specific electromagnetic shielding efficiency is 53697.3-200647.9 dB cm 2 The pore diameter distribution of pores contained in the porous structure is 10-100 nm.
2. A soft, layered carbon film according to claim 1, characterized in that: the nano-fibers comprise aramid nano-fibers and carbon nano-tubes; preferably, the aramid nano-fiber comprises para-aramid nano-fiber, the diameter of the para-aramid nano-fiber is 2nm to 50nm, and the length of the para-aramid nano-fiber is 200nm to 5 mu m; preferably, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes; preferably, the diameter of the carbon nano tube is 1nm to 50nm, and the length of the carbon nano tube is 500nm to 30 mu m; preferably, the mass ratio of the aramid nanofibers to the carbon nanotubes is 2:1 to 10:1.
3. a method for preparing a soft layered carbon film, comprising:
uniformly dispersing aramid nano-fibers in a carbon nano-tube dispersion liquid to form an aramid nano-fiber/carbon nano-tube mixed dispersion liquid;
applying the aramid nano-fiber/carbon nano-tube mixed dispersion liquid on a substrate, performing film formation treatment, transferring the solution 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;
carrying out compression densification treatment on the hybrid aerogel film to obtain a layered hybrid film;
and under the protection of inert gas, carrying out high-temperature carbonization treatment on the layered hybrid film to obtain the soft layered carbon film.
4. The method according to claim 3, characterized by comprising: uniformly dispersing carbon nanotubes in a solvent to form a carbon nanotube dispersion liquid; preferably, the solvent comprises dimethyl sulfoxide; preferably, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes; preferably, the diameter of the carbon nano tube is 1nm to 50nm, and the length of the carbon nano tube is 500nm to 30 mu m; and/or the concentration of the carbon nano tubes in the carbon nano tube dispersion liquid is 0.1-0.5 wt%.
5. The production method according to claim 3, characterized by comprising: adding macroscopic aramid nano-fiber and alkaline substances into the carbon nano-tube dispersion liquid, and stirring for 3-7 days at normal temperature to form uniform aramid nano-fiber/carbon nano-tube mixed dispersion liquid; preferably, the mass ratio of the aramid nanofibers to the alkaline substances is 2:1 to 1:1; preferably, the aramid nanofibers comprise para-aramid nanofibers; preferably, the diameter of the aramid nanofiber is 2nm to 50nm, and the length of the aramid nanofiber is 200nm to 5 mu m; preferably, the alkaline substance comprises any one or a combination of two of potassium hydroxide and potassium tert-butoxide; preferably, the concentration of the aramid nano-fiber in the aramid nano-fiber/carbon nano-tube mixed dispersion liquid is 1wt% -2 wt%; preferably, the mass ratio of the carbon nanotubes to the aramid nanofibers is 2:1 to 10:1.
6. the production method according to claim 3, characterized by comprising: coating the aramid nano-fiber/carbon nano-tube mixed dispersion liquid on a substrate by adopting at least one of a tape casting method and a scraper coating method; preferably, the distance between the doctor blade and the substrate in the doctor blade coating method is 250 to 1000 μm.
7. The production method according to claim 3, characterized in that: the coagulating bath comprises any one or combination of more than two of water, ethanol and methanol; and/or the drying treatment comprises any one of a supercritical drying method and a vacuum freeze-drying method, preferably a freeze-drying method;
preferably, the preparation method specifically comprises the following steps: firstly, carrying out solvent replacement on the hybrid aerogel film by using tert-butyl alcohol and water, and then carrying out vacuum freeze drying; preferably, the mass ratio of the tertiary butanol to the water is 1:1 to 1:5; preferably, the cold trap temperature of the vacuum freeze drying method is-80 to-50 ℃, and the vacuum degree is less than 0.1kPa.
8. The production method according to claim 3, characterized in that: the pressure adopted by the compression densification treatment is 5-10 Mpa, the compression temperature is 20-50 ℃, and the time is 10-30 min; and/or the temperature of the high-temperature carbonization treatment is 550-950 ℃, and the time of the high-temperature carbonization treatment is 0.5-7 h; and/or the inert gas comprises any one or combination of two of nitrogen and argon.
9. A soft layered carbon film produced by the method of any one of claims 3 to 8.
10. Use of a soft, layered carbon film according to any of claims 1-2, 9 in the field of electromagnetic protection.
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