CN114702029A - Efficient preparation method of graphene/carbon nanotube self-assembled conductive film - Google Patents
Efficient preparation method of graphene/carbon nanotube self-assembled conductive film Download PDFInfo
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Abstract
The invention relates to an efficient preparation method of a graphene/carbon nanotube self-assembly conductive film, which comprises the steps of mixing a modified carbon nanotube dispersion solution and a modified graphene dispersion solution, adjusting the pH value to 7, and then filtering and forming by using a 300-500-mesh filter screen to prepare the graphene/carbon nanotube self-assembly conductive film, wherein the modified carbon nanotube is an aminated modified carbon nanotube, and the modified graphene is carboxylated modified graphene; or the modified carbon nanotube is a carboxylated modified carbon nanotube, and the modified graphene is aminated modified graphene; the pH value ranges of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are the same, and are both 9-10 or both 5-6; the method is simple, and the prepared product has low resistance, and is washable and bending-resistant.
Description
Technical Field
The invention belongs to the technical field of self-assembled conductive films, and relates to an efficient preparation method of a graphene/carbon nanotube self-assembled conductive film.
Background
With the development of the fields of artificial intelligence, electronic skin, health monitoring and the like, the attention of the flexible wearable device is high. The carbon nanotubes and graphene are respectively one-dimensional nanofibers and two-dimensional carbon materials with excellent properties, and exhibit one-dimensional and two-dimensional anisotropy, such as electric conductivity, mechanics and heat conductivity. Meanwhile, the graphene and the carbon nano tube are jointly used for preparing the composite fiber membrane, a three-dimensional structure can be constructed, a synergistic effect is generated, and the preparation method has good application prospects in the aspects of super capacitors, solar cells, biological detection, fuel cells and the like, so that the preparation technology of the carbon nano tube and graphene composite fiber membrane material is widely concerned.
The preparation method of the carbon nanotube and graphene composite fiber membrane material comprises the following steps: conventional Chemical Vapor Deposition (CVD), plasma enhanced Chemical Vapor Deposition (CVD), layer-by-layer deposition (LBL), electrophoretic deposition, coating-film method, in-situ chemical reduction, vacuum filtration;
the conventional Chemical Vapor Deposition (CVD) method can prepare a uniform film, the components are easy to control, the repeatability is good, the method is not limited by the surface shape of a matrix, but the operation temperature is higher than 800 ℃, and the base material is required to be stable in a high-temperature environment;
the plasma enhanced Chemical Vapor Deposition (CVD) method can carry out chemical vapor deposition at a lower temperature, has high deposition speed and good film forming quality, but has high cost and high requirement on gas purity, and can generate severe noise, strong light radiation, harmful gas and other influences in the process;
the thickness, the components and the density of an assembled film can be regulated and controlled by adjusting the ionic strength, the pH value and the like in a liquid phase by a layer-by-layer deposition method (LBL), compared with a CVD method, the LBL method is relatively simple, but the used raw materials generally have active functional groups, such as carboxyl, amino and the like, and the preparation efficiency is low;
the electrophoretic deposition method has high deposition rate, good homogeneity, easily controlled film thickness, no need of adding adhesive, low cost and the like, but has high requirement on the surface cleanliness of the substrate;
compared with the suction filtration film-forming technology, the coating film-forming method has the advantages that the area of the film prepared by the method is controlled by the size of the substrate, the thickness can be adjusted by changing the parameters of an instrument, the film-forming process is simple and efficient, but the film prepared by the method has uneven thickness and relatively low utilization rate of raw materials;
the in-situ chemical reduction method has the advantages of simplicity, high preparation speed, large yield, low product quality and difficult removal of oxidized groups;
the vacuum filtration method is applied to the macro preparation of the carbon nano tube and graphene self-assembled film, the film thickness of the film can be accurately controlled by configuring suspensions with different concentrations and volumes, the operation is simple, the film forming is uniform, the raw material utilization rate is high, and the method has application prospect and research value compared with other preparation methods.
Therefore, it is very important to research an efficient preparation method of the graphene/carbon nanotube self-assembled conductive film to solve the above problems.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an efficient preparation method of a graphene/carbon nanotube self-assembled conductive film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-efficiency preparation method of a graphene/carbon nanotube self-assembly conductive film comprises the steps of mixing a modified carbon nanotube dispersion solution and a modified graphene dispersion solution, adjusting the pH value to 7, and filtering and forming by using a 300-500-mesh filter screen to obtain the graphene/carbon nanotube self-assembly conductive film;
the modified carbon nanotube is an aminated modified carbon nanotube, and the modified graphene is carboxylated modified graphene; or the modified carbon nanotube is a carboxylated modified carbon nanotube, and the modified graphene is aminated modified graphene;
the value ranges of the pH values of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are the same, and are both below 7, or both above 7;
the modified carbon nanotube dispersion liquid is prepared by dispersing modified carbon nanotubes in an amphoteric surfactant solution A and then adjusting the pH value; the modified graphene dispersion liquid is prepared by dispersing modified graphene in an amphoteric surfactant solution B and then adjusting the pH value.
The carbon nano tube and graphene self-assembled film prepared by the vacuum filtration method in the prior art can only adopt a filter membrane with a smaller aperture, the filtration speed is too slow, and mass preparation is difficult.
The principle of self-assembly is as follows: after carboxyl or aminated carbon nano materials are mixed with an amphoteric surfactant solution, the surfactant is grafted to the surface of the materials according to electronegativity, repulsion is formed among the carbon nano materials, dispersion is promoted, and stability is kept; after the two dispersions are mixed, the two carbon nano materials are self-assembled and adsorbed together under the electrostatic action, so that the convenient regulation and control of the performance are realized; specifically, the carboxyl group of the carboxylated modified carbon nanomaterial is ionized to be negatively charged under neutral and alkaline conditions; the amino group of the aminated modified carbon nano material can be ionized to be positively charged under neutral and acidic conditions; the two modified carbon nano material dispersions are adjusted to the same acidic or alkaline pH value, only one group is ionized, the groups cannot be mutually adsorbed and can be fully dispersed, the pH value of the mixed solution is adjusted to be neutral, the two modified carbon nano materials are ionized, and at the moment, the two modified carbon nano materials are spontaneously adsorbed together due to electrostatic attraction to generate a self-assembly process.
As a preferred technical scheme:
according to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the value ranges of the pH values of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are both 9-10 or 5-6, and the stability of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid is poorer when the pH value is closer to neutral, so that the value ranges of the pH values of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are set to be 9-10 or 5-6.
According to the efficient preparation method of the graphene/carbon nanotube self-assembly conductive film, the concentration of the modified carbon nanotubes in the modified carbon nanotube dispersion liquid is the same as that of the modified graphene in the modified graphene dispersion liquid, and the concentration of the modified carbon nanotubes in the modified carbon nanotube dispersion liquid is 0.1-0.5 wt%; the preparation of the film requires that the carbon nano tube and the graphene keep large size as much as possible, so that the assembly is facilitated and the forming efficiency is improved; however, the large size is unfavorable for dispersion, and a good dispersion effect can be achieved only under the condition of low concentration; on the contrary, if high concentration is adopted, the sizes of the carbon nano tube and the graphene must be reduced through the process, so that the preparation of the conductive film is not favorable; this concentration range is experimentally verified.
According to the efficient preparation method of the graphene/carbon nanotube self-assembly conductive film, the volume ratio of the modified carbon nanotube dispersion liquid to the modified graphene dispersion liquid is 1: 0.2-1; the modified carbon nanotubes tend to be arranged on the surface of the modified graphene, so the modified carbon nanotubes are used in a little more amount.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the amphoteric surfactant in the amphoteric surfactant solution A is the same as that in the amphoteric surfactant solution B; the same surfactants have the same HLB value, ensuring dispersion stability when mixed.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the amphoteric surfactant is coconut oil amphoteric sodium acetate, betaine amphoteric surfactant or lauryl amphoteric sodium acetate.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the solvents in the amphoteric surfactant solution A and the amphoteric surfactant solution B are the same.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the solvent is water.
According to the efficient preparation method of the graphene/carbon nanotube self-assembly conductive film, the concentrations of the amphoteric surfactant solution A and the amphoteric surfactant solution B are the same and are 0.001-0.003 mol/L, and when the concentrations exceed the concentration range, the dispersion effect is not obviously improved, but more residues are left in the film, so that the conductivity is influenced.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, X is marked as graphene or a carbon nanotube, and the preparation process of the carboxylation modified X is as follows: adding X into mixed acid, performing ultrasonic dispersion for 0.5-1 h to obtain a dispersion liquid with the concentration of 1-3 wt%, performing reflux reaction at the temperature of 130-160 ℃ for 1.5-2 h, and performing post-treatment (washing, filtering and drying) to obtain the carboxylated modified X, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1-3: 1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the preparation process of the amination modified X is as follows: firstly, adding carboxylation modified X into DMF or DMAc, performing ultrasonic dispersion for 30-50 min to obtain a dispersion liquid with the concentration of 0.1-0.5 wt%, then adding polyethylene polyamine with the mass 2-4 times that of the carboxylation modified X into the dispersion liquid, reacting for 10-12 h at 20-25 ℃ in an inert atmosphere, and finally performing post-treatment (washing, filtering and drying) to obtain the amination modified X.
According to the efficient preparation method of the graphene/carbon nanotube self-assembly conductive film, when the modified carbon nanotube dispersion liquid is prepared, the modified carbon nanotube is dispersed in the amphoteric surfactant solution A, mixed and stirred for 1-1.5 hours at the rotating speed of 500-1000 rpm, and then the pH value is adjusted; when preparing the modified graphene dispersion liquid, firstly dispersing the modified graphene in the amphoteric surfactant solution B, mixing and stirring at the rotating speed of 500-1000 rpm for 1-1.5 h, and then adjusting the pH value.
According to the efficient preparation method of the graphene/carbon nanotube self-assembly conductive film, the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are mixed, and then stirred for 30-40 min, the pH value is adjusted to 7, and then stirred for 30-40 min.
According to the efficient preparation method of the graphene/carbon nanotube self-assembled conductive film, the resistivity of the graphene/carbon nanotube self-assembled conductive film is 30-60 m omega cm, the thickness of the graphene/carbon nanotube self-assembled conductive film is 30-70 μm, the resistance change rate after 20000 times of bending is less than or equal to 10%, and the resistance change rate after 50 times of standard water washing is less than or equal to 10%; the existing films are of the following types: 1. films with base materials prepared by a CVD method, a spin coating method and the like have poor flexibility, and the base materials are always high in rigidity; the resistance is higher and is one order of magnitude larger than that of the method; 2. the film assembled layer by layer has complex process and durability such as water washing resistance, bending resistance and the like.
Has the advantages that:
(1) according to the method, the carbon nano tube and the graphene can be fully and uniformly combined and assembled in a liquid phase through the surface functional group modification and the double surfactant lap joint to form a multi-dimensional structure;
(2) in the method, the surface functional group modification and the amphoteric surfactant are overlapped to form a pre-assembly body under the drive of pH, so that the requirement on the aperture of a suction filtration hole is reduced, the rapid suction filtration is realized, and the preparation is efficient;
(4) the product of the invention is washable, bending resistant and has small resistance change rate.
Drawings
Fig. 1 is a surface topography of a graphene/carbon nanotube self-assembled conductive film;
FIG. 2 is a partially enlarged view of the surface topography of the graphene/carbon nanotube self-assembled conductive film;
FIG. 3 shows the self-assembled morphology of two nanomaterials.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified graphene:
adding graphene into mixed acid, performing ultrasonic dispersion for 0.5h to obtain a dispersion liquid with the concentration of 1wt%, performing reflux reaction for 2h at the temperature of 130 ℃, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of the modified carbon nanotube:
(a) adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 0.5h to obtain a dispersion liquid with the concentration of 1wt%, performing reflux reaction for 2h at the temperature of 130 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified carbon nano tube in the step (a) into DMF, performing ultrasonic dispersion for 30min to obtain a dispersion liquid with the concentration of 0.1wt%, then adding polyethylene polyamine with the mass 2 times that of the carboxylated modified carbon nano tube into the dispersion liquid, reacting for 12h at the temperature of 20 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified carbon nano tube;
amphoteric surfactant solution a and amphoteric surfactant solution B: both are coconut oil amphoteric sodium acetate water solution with the concentration of 0.001 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nano tubes in an amphoteric surfactant solution A, mixing and stirring for 1.5h at the rotating speed of 500rpm, and then adjusting the pH value to 9 to prepare a modified carbon nano tube dispersion liquid with the concentration of the modified carbon nano tubes being 0.1 wt%;
preparing a modified graphene dispersion liquid: firstly, dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring at the rotating speed of 500rpm for 1.5h, and then adjusting the pH value to 9 to prepare a modified graphene dispersion liquid with the concentration of 0.1wt% of the modified graphene;
(3) mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:0.2, stirring for 30min after mixing, adjusting the pH value to 7, stirring for 30min, and finally filtering and forming by using a 300-mesh filter screen to prepare the graphene/carbon nanotube self-assembled conductive film, carrying out SEM observation on the mixed liquid before filtering and forming, and observing the self-assembled forms of the two nano materials, wherein the result is shown in figure 3.
As shown in fig. 1-2, which are surface topography diagrams of the graphene/carbon nanotube self-assembled conductive film of the present invention, the carbon nanotubes and the graphene are uniformly arranged and fully overlapped, and the prepared graphene/carbon nanotube self-assembled conductive film has a resistivity of 60m Ω · cm, a thickness of 31 μm, a resistance change rate of 4% after 20000 bending, and a resistance change rate of 5% after 50 standard water washing.
Comparative example 1
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
graphene (same as example 1):
carbon nanotubes (same as example 1):
amphoteric surfactant solution a and amphoteric surfactant solution B: both are coconut oil amphoteric sodium acetate water solution with the concentration of 0.001 mol/L;
(2) preparing a carbon nano tube dispersion liquid and a graphene dispersion liquid;
preparing a carbon nano tube dispersion liquid: dispersing carbon nano tubes in an amphoteric surfactant solution A, mixing and stirring at the rotating speed of 500rpm for 1.5h to prepare a carbon nano tube dispersion liquid with the concentration of the carbon nano tubes being 0.1 wt%;
preparing a graphene dispersion liquid: dispersing graphene in an amphoteric surfactant solution B, mixing and stirring at a rotating speed of 500rpm for 1.5h to prepare a graphene dispersion liquid with the concentration of 0.1wt% of graphene;
(3) mixing the carbon nanotube dispersion liquid and the graphene dispersion liquid in a volume ratio of 1:0.2, stirring for 60min after mixing, and then filtering and forming by using a filter screen to obtain the graphene/carbon nanotube self-assembled conductive film, wherein multiple experiments show that the mesh number of the filter screen cannot be higher than 600 meshes to the maximum extent, so that the dehydration efficiency is affected, otherwise, the graphene/carbon nanotube self-assembled conductive film cannot be successfully prepared.
When the volume of the mixed liquid of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid of example 1 is 600mL, which is the same as the volume of the mixed liquid of the carbon nanotube dispersion liquid and the graphene dispersion liquid of comparative example 1, the time required for filtering and molding of example 1 by using a 300-mesh filter screen is 0.5min, and the time required for filtering and molding of comparative example 1 by using a 600-mesh filter screen is 5min, it can be seen that the filtering time of example 1 is significantly shorter than that of comparative example 1.
Example 2
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified graphene:
adding graphene into mixed acid, performing ultrasonic dispersion for 0.6h to obtain a dispersion liquid with the concentration of 1wt%, performing reflux reaction for 1.9h at the temperature of 135 ℃, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of the modified carbon nanotube:
(a) adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 0.6h to obtain a dispersion liquid with the concentration of 1wt%, performing reflux reaction for 1.9h at the temperature of 135 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified carbon nano tube in the step (a) into DMF, performing ultrasonic dispersion for 35min to obtain a dispersion liquid with the concentration of 0.1wt%, then adding polyethylene polyamine with the mass 2 times that of the carboxylated modified carbon nano tube into the dispersion liquid, reacting for 12h at 21 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified carbon nano tube;
amphoteric surfactant solution a and amphoteric surfactant solution B: both are coconut oil amphoteric sodium acetate water solution with the concentration of 0.001 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nanotubes in an amphoteric surfactant solution A, mixing and stirring at the rotating speed of 600rpm for 1.4h, and then adjusting the pH value to 9 to prepare a modified carbon nanotube dispersion liquid with the concentration of the modified carbon nanotubes of 0.1 wt%;
preparing a modified graphene dispersion liquid: firstly, dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring at the rotating speed of 600rpm for 1.4h, and then adjusting the pH value to 9 to prepare a modified graphene dispersion liquid with the concentration of 0.1wt% of the modified graphene;
(3) and mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:0.3, stirring for 33min after mixing, adjusting the pH value to 7, stirring for 33min, and finally filtering and molding by using a 300-mesh filter screen to obtain the graphene/carbon nanotube self-assembled conductive film.
The resistivity of the prepared graphene/carbon nano tube self-assembled conductive film is 52m omega cm, the thickness is 36 mu m, the resistance change rate after 20000 times of bending is 5%, and the resistance change rate after 50 times of standard water washing is 6%.
Example 3
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified graphene:
adding graphene into mixed acid, performing ultrasonic dispersion for 0.7h to obtain a dispersion liquid with the concentration of 2wt%, performing reflux reaction at the temperature of 140 ℃ for 1.8h, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of modified carbon nanotubes:
(a) adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 0.7h to obtain a dispersion liquid with the concentration of 2wt%, performing reflux reaction for 1.8h at the temperature of 140 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified carbon nano tube in the step (a) into DMF, performing ultrasonic dispersion for 40min to obtain a dispersion liquid with the concentration of 0.2wt%, then adding polyethylene polyamine with the mass 2 times that of the carboxylated modified carbon nano tube into the dispersion liquid, reacting for 11h at the temperature of 22 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified carbon nano tube;
amphoteric surfactant solution a and amphoteric surfactant solution B: both are betaine type amphoteric surfactant (concretely CAB-35) water solution with the concentration of 0.002 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing a modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nanotubes in an amphoteric surfactant solution A, mixing and stirring at the rotating speed of 700rpm for 1.3h, and then adjusting the pH value to 10 to prepare a modified carbon nanotube dispersion liquid with the concentration of the modified carbon nanotubes of 0.2 wt%;
preparing a modified graphene dispersion liquid: firstly, dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring at the rotating speed of 700rpm for 1.3h, and then adjusting the pH value to 10 to prepare a modified graphene dispersion liquid with the concentration of 0.2wt% of the modified graphene;
(3) and mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:0.4, stirring for 36min after mixing, adjusting the pH value to 7, stirring for 36min, and finally filtering and molding by using a 400-mesh filter screen to obtain the graphene/carbon nanotube self-assembled conductive film.
The resistivity of the prepared graphene/carbon nano tube self-assembled conductive film is 48m omega cm, the thickness is 40 mu m, the resistance change rate after 20000 times of bending is 5%, and the resistance change rate after 50 times of standard water washing is 7%.
Example 4
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified carbon nanotubes:
adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 0.8h to obtain a dispersion liquid with the concentration of 2wt%, performing reflux reaction for 1.7h at the temperature of 150 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of modified graphene:
(a) adding graphene into mixed acid, performing ultrasonic dispersion for 0.8h to obtain a dispersion liquid with the concentration of 2wt%, performing reflux reaction for 1.7h at the temperature of 150 ℃, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified graphene in the step (a) into DMAc, performing ultrasonic dispersion for 45min to obtain a dispersion liquid with the concentration of 0.3wt%, then adding polyethylene polyamine with the mass being 3 times that of the carboxylated modified graphene into the dispersion liquid, reacting for 11h at 23 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified graphene;
amphoteric surfactant solution a and amphoteric surfactant solution B: both are betaine type amphoteric surfactant (concretely CAB-35) water solution with the concentration of 0.002 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nano tubes in an amphoteric surfactant solution A, mixing and stirring at the rotating speed of 800rpm for 1.2h, and then adjusting the pH value to 5 to prepare a modified carbon nano tube dispersion liquid with the concentration of the modified carbon nano tubes being 0.3 wt%;
preparing a modified graphene dispersion liquid: firstly dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring for 1.2h at the rotating speed of 800rpm, and then adjusting the pH value to 5 to prepare a modified graphene dispersion liquid with the concentration of the modified graphene being 0.3 wt%;
(3) and mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:0.7, stirring for 39min after mixing, adjusting the pH value to 7, stirring for 39min, and finally filtering and molding by using a 400-mesh filter screen to obtain the graphene/carbon nanotube self-assembled conductive film.
The resistivity of the prepared graphene/carbon nano tube self-assembled conductive film is 45m omega cm, the thickness is 48 mu m, the resistance change rate after 20000 times of bending is 6%, and the resistance change rate after 50 times of standard water washing is 8%.
Example 5
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified carbon nanotubes:
adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 0.9h to obtain a dispersion liquid with the concentration of 3wt%, performing reflux reaction for 1.6h at the temperature of 155 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of modified graphene:
(a) firstly, adding graphene into mixed acid, performing ultrasonic dispersion for 0.9h to obtain a dispersion liquid with the concentration of 3wt%, performing reflux reaction for 1.6h at the temperature of 155 ℃, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified graphene in the step (a) into DMAc, performing ultrasonic dispersion for 45min to obtain a dispersion liquid with the concentration of 0.4wt%, then adding polyethylene polyamine with the mass being 3 times that of the carboxylated modified graphene into the dispersion liquid, reacting for 10h at 24 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified graphene;
amphoteric surfactant solution a and amphoteric surfactant solution B: the sodium lauryl amphoacetate solution with the concentration of 0.003 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing a modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nano tubes in an amphoteric surfactant solution A, mixing and stirring for 1.1h at the rotating speed of 900rpm, and then adjusting the pH value to be 5 to prepare a modified carbon nano tube dispersion liquid with the concentration of the modified carbon nano tubes being 0.4 wt%;
preparing a modified graphene dispersion liquid: firstly, dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring at the rotating speed of 900rpm for 1.1h, and then adjusting the pH value to 5 to prepare a modified graphene dispersion liquid with the concentration of 0.4wt% of the modified graphene;
(3) and mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:0.9, stirring for 40min after mixing, adjusting the pH value to 7, stirring for 40min, and finally filtering and molding by using a 500-mesh filter screen to obtain the graphene/carbon nanotube self-assembled conductive film.
The resistivity of the prepared graphene/carbon nano tube self-assembled conductive film is 40m omega cm, the thickness is 55 mu m, the resistance change rate after 20000 times of bending is 6%, and the resistance change rate after 50 times of standard water washing is 8%.
Example 6
A high-efficiency preparation method of a graphene/carbon nanotube self-assembled conductive film comprises the following specific steps:
(1) preparing raw materials;
carboxylated modified carbon nanotubes:
adding a carbon nano tube into mixed acid, performing ultrasonic dispersion for 1h to obtain a dispersion liquid with the concentration of 3wt%, performing reflux reaction for 1.5h at the temperature of 160 ℃, and performing post-treatment (washing, filtering and drying) to obtain a carboxylated modified carbon nano tube, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
amination of modified graphene:
(a) adding graphene into mixed acid, performing ultrasonic dispersion for 1h to obtain a dispersion liquid with the concentration of 3wt%, performing reflux reaction for 1.5h at the temperature of 160 ℃, and performing post-treatment (washing, filtering and drying) to obtain carboxylated modified graphene, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%;
(b) adding the carboxylated modified graphene in the step (a) into DMAc, performing ultrasonic dispersion for 50min to obtain a dispersion liquid with the concentration of 0.5wt%, then adding polyethylene polyamine with the mass being 4 times that of the carboxylated modified graphene into the dispersion liquid, reacting for 10h at 25 ℃ in argon, and finally performing post-treatment (washing, filtering and drying) to obtain the aminated modified graphene;
amphoteric surfactant solution a and amphoteric surfactant solution B: the sodium lauryl amphoacetate solution with the concentration of 0.003 mol/L;
(2) preparing a modified carbon nanotube dispersion liquid and a modified graphene dispersion liquid;
preparing modified carbon nanotube dispersion liquid: firstly, dispersing modified carbon nanotubes in an amphoteric surfactant solution A, mixing and stirring for 1h at the rotating speed of 1000rpm, and then adjusting the pH value to 6 to prepare a modified carbon nanotube dispersion liquid with the concentration of the modified carbon nanotubes of 0.5 wt%;
preparing a modified graphene dispersion liquid: firstly, dispersing modified graphene in an amphoteric surfactant solution B, mixing and stirring at the rotating speed of 1000rpm for 1h, and then adjusting the pH value to 6 to prepare a modified graphene dispersion liquid with the concentration of the modified graphene being 0.5 wt%;
(3) and mixing the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid in a volume ratio of 1:1, stirring for 40min after mixing, adjusting the pH value to 7, stirring for 40min, and finally filtering and molding by using a 500-mesh filter screen to obtain the graphene/carbon nanotube self-assembled conductive film.
The resistivity of the prepared graphene/carbon nanotube self-assembled conductive film is 31m omega cm, the thickness is 60 mu m, the resistance change rate after 20000 times of bending is 8%, and the resistance change rate after 50 times of standard water washing is 7%.
Claims (10)
1. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film is characterized by mixing a modified carbon nanotube dispersion solution and a modified graphene dispersion solution, adjusting the pH value to 7, and filtering and forming by using a 300-500-mesh filter screen to prepare the graphene/carbon nanotube self-assembled conductive film;
the modified carbon nanotube is an aminated modified carbon nanotube, and the modified graphene is carboxylated modified graphene; or the modified carbon nanotube is a carboxylated modified carbon nanotube, and the modified graphene is aminated modified graphene;
the value ranges of the pH values of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are the same, and are both below 7, or both above 7;
the modified carbon nanotube dispersion liquid is prepared by dispersing modified carbon nanotubes in an amphoteric surfactant solution A and then adjusting the pH value; the modified graphene dispersion liquid is prepared by dispersing modified graphene in an amphoteric surfactant solution B and then adjusting the pH value.
2. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film according to claim 1, wherein the pH values of the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are both 9-10 or both 5-6.
3. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film according to claim 1, wherein the concentration of the modified carbon nanotubes in the modified carbon nanotube dispersion liquid is 0.1-0.5 wt% as the concentration of the modified graphene in the modified graphene dispersion liquid.
4. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film according to claim 3, wherein the volume ratio of the modified carbon nanotube dispersion liquid to the modified graphene dispersion liquid is 1: 0.2-1.
5. The method according to claim 1, wherein the amphoteric surfactant solution A and the amphoteric surfactant solution B have the same concentration, and are both 0.001-0.003 mol/L.
6. The method for efficiently preparing the graphene/carbon nanotube self-assembled conductive film according to claim 1, wherein X is graphene or a carbon nanotube, and the preparation process of the carboxylation modification X is as follows: adding X into mixed acid, performing ultrasonic dispersion for 0.5-1 h to obtain a dispersion liquid with the concentration of 1-3 wt%, performing reflux reaction at the temperature of 130-160 ℃ for 1.5-2 h, and performing post-treatment to obtain the carboxylated modified X, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1-3: 1, the concentration of the concentrated sulfuric acid is 98wt%, and the concentration of the concentrated nitric acid is 65 wt%.
7. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film according to claim 6, wherein the preparation process of the amination modified X comprises the following steps: firstly, adding carboxylation modified X into DMF or DMAc, performing ultrasonic dispersion for 30-50 min to obtain a dispersion liquid with the concentration of 0.1-0.5 wt%, then adding polyethylene polyamine with the mass 2-4 times of that of the carboxylation modified X into the dispersion liquid, reacting for 10-12 h at 20-25 ℃ in an inert atmosphere, and finally performing post-treatment to obtain the amination modified X.
8. The efficient preparation method of the graphene/carbon nanotube self-assembled conductive film according to claim 1, wherein when the modified carbon nanotube dispersion liquid is prepared, the modified carbon nanotube is dispersed in the amphoteric surfactant solution A, mixed and stirred at a rotation speed of 500-1000 rpm for 1-1.5 h, and then the pH value is adjusted; when preparing the modified graphene dispersion liquid, firstly dispersing the modified graphene in the amphoteric surfactant solution B, mixing and stirring at the rotating speed of 500-1000 rpm for 1-1.5 h, and then adjusting the pH value.
9. The method for efficiently preparing the graphene/carbon nanotube self-assembled conductive film according to claim 1, wherein the modified carbon nanotube dispersion liquid and the modified graphene dispersion liquid are mixed, and then stirred for 30-40 min, and then the pH value is adjusted to 7, and then stirred for 30-40 min.
10. The method as claimed in claim 1, wherein the graphene/carbon nanotube self-assembled conductive film has a resistivity of 30-60 m Ω -cm, a thickness of 30-70 μm, a resistance change rate of 10% or less after 20000 bending, and a resistance change rate of 10% or less after 50 standard water washing.
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