CN114150354B - High-strength high-conductivity carbon nano tube composite film and preparation method thereof - Google Patents
High-strength high-conductivity carbon nano tube composite film and preparation method thereof Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Abstract
The invention discloses a high-strength high-conductivity carbon nano tube composite film and a preparation method thereof. The preparation method comprises the following steps: the carbon nano tube fiber is used as a main body, the hydrogen evolution expansion method is adopted to expand the network volume of the carbon nano tube, then the electrolyte is designed to carry out in-situ doping or compounding in the expansion process of the carbon nano tube aggregate, so that functional nano particles can enter the inside of the carbon nano tube fiber and even gaps among tubes, doping of nano particles with different functions such as gold, chlorine, bromine, iodine and the like can be realized, certain encapsulation can be formed on the functional nano particles with bromine, iodine and the like after winding film forming, sublimation or oxidation of the functional particles can be effectively avoided, winding and collection can be directly carried out after the aggregation doping and compounding of the carbon nano tube, the formed film has higher orientation, the content of the carbon nano tube can be regulated and controlled, and higher mechanical property can be maintained while the functional property is endowed.
Description
Technical Field
The invention relates to a preparation method of a carbon nano tube composite film, in particular to a high-strength high-conductivity carbon nano tube composite film and a preparation method thereof, belonging to the technical field of nano science.
Background
Carbon Nanotubes (CNTs) are the best-found one-dimensional building blocks for electroheating performance, not only with superior tensile strength, but also with excellent electrical, thermal and chemical stability. Fibers and films are common macroscopic forms assembled from carbon nanotubes. The method for preparing the carbon nanotube film is mainly divided into two types: wet and dry preparation (Rinzler a G, liu J, et al applied Physics,1998;Li Y L,Kinloch I A,Windle A H.Science,2004). After the carbon nanotubes are assembled into macroscopic aggregates, a large number of tubes are connected, so that the transmission of loads and electrons among the tubes is limited, and the mechanical and electrical properties of macroscopic fibers and films are greatly different from those of microscopic carbon nanotubes. In order to improve the electrical conductivity of the macroscopic assembly of carbon nanotubes, a great deal of research has been conducted by researchers. The method mainly comprises metal compounding, halogen doping and preparing a carbon nano tube/copper composite conductive fiber on a film by adopting a traditional continuous electroplating method, wherein a copper layer of the composite conductive fiber obtained by the method is mainly distributed outside the carbon nano tube fiber, and the conductivity mainly depends on the thickness of a coating (Xu G, zhao J, li S, et al, nanoscales, 2011,3 (10): 4215-4219; small,2010,6 (16): 1806-1811: carbon,2016,107 (support C): 281-287); the CNT/WPU composite film is prepared by dispersing and solidifying the carbon nano tube in the aqueous polyurethane solution by adopting a physical mixing method, the conductivity can reach 362.6S/cm, the electromagnetic shielding can reach 24.7dB (Hui L, du Y, et al. Composites,2019, 411-417), but the special structure of the carbon nano tube is easy to curl and wind, and the poor dispersibility leads to low mechanical strength; the fiber is thermally doped with metals such as potassium, gold, bromine and the like, so that the conductivity can be effectively improved (Advanced Materials,2013,25:3249-3253.Advanced Materials,2016,28:7941-7947). Gold is deposited in the pore structure of the carbon nanotube fiber by a solution soaking method, so that the mechanical strength and the electrical conductivity (Young-Jin, kim, junbeom, et al, nanoscales, 2019) of the composite fiber can be improved. Some existing patents such as (20110058079. X;200610164717.5;201610421261. X) can improve the conductivity of the carbon nanotube aggregate to a certain extent, but the problems that the doping or the compounding amount is small, the doping phase is mainly on the surface of the aggregate, the doping cannot be continuous and the like are common.
In summary, the prior art mainly has the following disadvantages: 1) The composite of the carbon nano tube and the metal powder has the defects of easy agglomeration, poor dispersity, poor orientation, low addition amount and the like of the carbon nano tube; 2) In the carbon nano tube fiber electroplating technology, the surface of the copper layer carbon nano tube fiber has poor bonding performance between metal and carbon nano tube interface; 3) The doping of iodine, bromine and the like to the carbon nano tube is mainly performed by sublimation of iodine and bromine, and the iodine and the bromine enter the surface or gaps of the carbon nano tube, so that the doping degree is limited.
Disclosure of Invention
The invention mainly aims to provide a high-strength high-conductivity carbon nano tube composite film and a preparation method thereof, so as to overcome the defects in the prior art.
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 preparation method of a high-strength high-conductivity carbon nano tube composite film, which comprises the following steps:
a carbon nanotube fiber is provided which is substantially free of carbon,
the method comprises the steps of taking carbon nanotube fibers fully infiltrated by water as a cathode, and constructing an electrochemical reaction system together with an anode and electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte and functional nanoparticle precursors;
electrifying the electrochemical reaction system, uniformly expanding the carbon nano tube fiber in the radial direction and/or the length direction under the action of gas generated by electrolysis, simultaneously carrying out in-situ doping and compounding, and fully penetrating functional nano particles generated by the reaction into the surface and/or the inside of the carbon nano tube in the carbon nano tube fiber to prepare the carbon nano tube/functional nano particle composite fiber;
and collecting the carbon nano tube/functional nano particle composite fiber to form a film and carrying out hot pressing treatment to obtain the high-strength high-conductivity carbon nano tube composite film.
In some embodiments, the functional nanoparticle precursor includes, but is not limited to, any one or a combination of two or more of chloroauric acid, chloroplatinic acid, bromine, iodine, and the like.
The embodiment of the invention also provides the high-strength high-conductivity carbon nano tube composite film prepared by the method, wherein the high-strength high-conductivity carbon nano tube composite film comprises carbon nano tube fibers and functional nano particles distributed on the surfaces and/or inside the carbon nano tube fibers.
In some embodiments, the functional nanoparticles include, but are not limited to, any one or a combination of two or more of gold, platinum, bromine, iodine, and the like.
Further, the methodThe mechanical strength of the high-strength high-conductivity carbon nano tube composite film is 380-850 MPa, and the conductivity is 0.7-1.2 x 10 7 S/m, and the shielding performance is 80-101 dB.
Compared with the prior art, the invention has the advantages that:
1) The preparation method of the high-strength high-conductivity carbon nano tube composite film provided by the invention takes carbon nano tube fibers as a main body, adopts a hydrogen evolution expansion method to expand the network volume of the carbon nano tube, and then performs in-situ doping or compounding in the expansion process of the carbon nano tube aggregate by designing the electrolyte, so that functional nano particles can enter the inside of the carbon nano tube fibers and even gaps among the tubes, doping of nano particles with different functions such as gold, chlorine, bromine, iodine and the like can be realized, certain encapsulation can be formed on the functional nano particles such as bromine, iodine and the like after winding into a film, sublimation or oxidation of the functional particles can be effectively avoided, winding and collection can be directly performed after the aggregation doping and compounding of the carbon nano tube, the formed film has higher orientation, the carbon nano tube content can be regulated and controlled, and higher mechanical properties can be maintained while the functional properties are endowed;
2) According to the invention, functional nano particles such as chloroauric acid, chloroplatinic acid, bromine, iodine and the like are added into the electrolyte, so that the conductivity of the composite film can be effectively improved, and in addition, the low-concentration polymer is added into the electrolyte, so that the mechanical strength of the fiber can be effectively maintained, and the high-strength composite film is obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a high-strength and high-conductivity carbon nanotube composite film according to an exemplary embodiment of the invention;
FIG. 2 is a physical diagram of a CNT/Au composite film prepared in example 1 of the present invention;
FIG. 3 is a graph showing the results of the resistance characterization before and after compounding the carbon nanotube fiber in example 1 of the present invention;
FIG. 4 is a graph showing the characterization result of electromagnetic shielding before and after compounding carbon nanotube fiber in example 1 of the present invention;
FIGS. 5a and 5b are electron microscopic views of the CNT/Au composite film prepared in example 1 of the present invention;
FIG. 6 is a graph showing mechanical properties of the CNT/Au composite film prepared in example 1 of the present invention;
FIG. 7 is a graph showing the results of electromagnetic shielding characterization of the CNT/iodine composite film prepared in example 2 of the present invention;
FIG. 8 is a graph showing mechanical properties of the CNT/iodine composite film prepared in example 2 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has provided a technical scheme of the present invention through long-term research and a large number of practices, mainly by adopting electrolysis water to generate hydrogen to generate gas so as to expand carbon nanotube fibers, then carrying out in-situ doping or compounding in the expanding process of carbon nanotube aggregates through the design of electrolyte, and then forming a carbon nanotube composite film by layering and winding the doped or compounded carbon nanotube fibers, wherein the orientation of the carbon nanotube composite film prepared by the method is good, and the carbon nanotube content can be regulated and controlled; functional nano particles such as chloroauric acid, chloroplatinic acid, bromine, iodine and the like are added into the electrolyte, so that the conductivity of the composite film can be effectively improved, and in addition, the mechanical strength of the fiber can be effectively maintained by adding a low-concentration polymer into the electrolyte, so that the high-strength composite film is obtained. The technical scheme, the implementation process, the principle and the like are further explained as follows.
The preparation method of the high-strength high-conductivity carbon nano tube composite film provided by one aspect of the embodiment of the invention comprises the following steps:
a carbon nanotube fiber is provided which is substantially free of carbon,
the method comprises the steps of taking carbon nanotube fibers fully infiltrated by water as a cathode, and constructing an electrochemical reaction system together with an anode and electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte and functional nanoparticle precursors;
electrifying the electrochemical reaction system, uniformly expanding the carbon nano tube fiber in the radial direction and/or the length direction under the action of gas generated by electrolysis, simultaneously carrying out in-situ doping and compounding, and fully penetrating functional nano particles generated by the reaction into the surface and/or the inside of the carbon nano tube in the carbon nano tube fiber to prepare the carbon nano tube/functional nano particle composite fiber;
and collecting the carbon nano tube/functional nano particle composite fiber to form a film and carrying out hot pressing treatment to obtain the high-strength high-conductivity carbon nano tube composite film.
In some embodiments, the functional nanoparticle precursor includes any one or a combination of two or more of chloroauric acid, chloroplatinic acid, bromine, iodine, and the like, but is not limited thereto.
Further, the concentration of the functional nanoparticle precursor in the electrolyte is 0.5-2 wt%.
Further, the electrolyte includes chloroauric acid (chloroauric acid solution).
In some embodiments, the electrolyte provided by the invention can be selectively enriched and diversified, and all water-soluble polymers and small molecule solvents can be rapidly expanded, so that the method provided by the invention has universality.
Wherein the water-soluble polymer includes, but is not limited to, polyvinyl alcohol and/or polyacrylic acid, etc.
In some embodiments, the electrolyte further includes an auxiliary agent including any one or a combination of two or more of ethanol, ethylene glycol, glycerol, and the like, but is not limited thereto. According to the invention, the addition of the assistants such as ethanol, glycol, glycerol and the like in the electrolyte can effectively reduce the surface tension between the carbon nanotubes and the solution, improve the wettability of the solution to the carbon nanotubes, promote the solution to carry functional nano particles into gaps among the tubes, and enhance the doping or compounding effect.
Further, the concentration of the auxiliary agent in the electrolyte is 0.05-1 wt%.
Furthermore, the invention takes the carbon nano tube aggregate as a main body, and the defects of low dispersion, agglomeration, orientation degree, low content and the like of the carbon nano tube in the traditional mixing method are overcome.
Further, the gas generated by the electrolysis comprises hydrogen and/or chlorine, preferably hydrogen.
In some exemplary embodiments, the preparation method specifically includes: and applying voltage between two selected stations on the carbon nano tube fiber or passing current through the carbon nano tube fiber so as to generate gas, and then uniformly expanding the carbon nano tube fiber to 400-2000 times of the original carbon nano tube fiber in the radial direction and/or the length direction, wherein the two selected stations are distributed at different positions on the carbon nano tube fiber in the length direction.
The principle of the invention for using hydrogen generated by hydrogen evolution of electrolytic water to lead the carbon nano tube fiber to expand nondestructively is that: the electrolytic water hydrogen evolution adopted by the invention can realize the instantaneous expansion of the carbon nano tube fiber from inside to outside, the carbon nano tube fiber is uniformly expanded and has high efficiency, and compared with the simple mechanical draft, the expanded carbon nano tube fiber has higher draft rate.
Compared with the method for expanding chlorosulfonic acid with strong corrosiveness, the method for expanding chlorosulfonic acid by using the gas by using the electrolytic water method has the advantages of higher efficiency, safety and continuity.
The invention utilizes electrolytic water to hydrogen out and expand the carbon nano tube fiber, which is a nondestructive expansion, can maintain the mechanical property of the fiber and has a certain purification effect on the carbon nano tube.
Further, the voltages applied to the different carbon nanotube fibers are different and are not limited herein.
Further, the current is generally fixed between 30 mA and 90mA, and the voltage is changed along with the change of the current.
Further, the carbon nanotube fiber of the present invention can be rapidly expanded within several seconds, and can be maintained in an expanded state all the time, so that there is no specific requirement for the energization time.
The invention mainly utilizes electrolytic water to release hydrogen to lead the carbon nano tube fiber to expand nondestructively, and the narrow band of the carbon nano tube expanded by high volume ratio is beneficial to doping of functional nano particles and increase of the loading capacity of the functional nano particles.
The hydrogen evolution expansion method adopted by the invention realizes that functional nano particles enter the inside of the carbon nano tube aggregate and even gaps among tubes by expanding the network volume of the carbon nano tube, not only adheres to the surface, but also can form certain encapsulation on the functional nano particles such as bromine, iodine and the like after being wound into a film, and can effectively avoid sublimation or oxidation of the functional nano particles.
In some exemplary embodiments, the preparation method specifically includes: and performing layering, winding and collecting on the carbon nano tube/functional nano particle composite fiber to form a carbon nano tube composite film. The invention directly carries out winding collection after the aggregation of the carbon nano tubes is doped and compounded, and the formed film has higher orientation, and can maintain higher mechanical property while being endowed with functional characteristics.
Further, the preparation method further comprises the following steps: and packaging the carbon nano tube composite film, namely, coating functional particles by using a polymer to prevent oxidization, so that the packaging-like effect is achieved.
Further, the temperature of the hot pressing treatment is 90-130 ℃ and the pressure is 8-12 MPa.
Another aspect of the embodiments of the present invention provides a high-strength and high-conductivity carbon nanotube composite film prepared by the foregoing method, wherein the high-strength and high-conductivity carbon nanotube composite film includes carbon nanotube fibers and functional nanoparticles distributed on the surfaces and/or inside of the carbon nanotube fibers.
In some exemplary embodiments, the functional nanoparticles include any one or a combination of two or more of gold, platinum, bromine, iodine, etc., but are not limited thereto.
Further, the content of the functional nano particles in the high-strength high-conductivity carbon nano tube composite film is 25-40 wt%.
Further, the surface and/or the inside of the carbon nano tube fiber is/are also distributed with a polymer.
Further, the thickness of the high-strength high-conductivity carbon nano tube composite film is 40-60 mu m.
Further, the mechanical strength of the high-strength high-conductivity carbon nano tube composite film is 380-850 MPa, and the conductivity is 0.7-1.2 x 10 7 S/m, and the shielding performance is 80-101 dB.
Specifically, a schematic diagram of the method for continuously preparing the high-strength high-conductivity carbon nano tube composite film is shown in fig. 1, and the whole process is divided into four processes of water impregnation, functional nano particle doping/polymer impregnation, layering winding collection and hot pressing. After fully soaking the original carbon nanotube fibers, introducing the carbon nanotube fibers into an electrolytic tank, electrifying in a mixed electrolyte to enable the carbon nanotube fibers to be expanded in a hydrogen evolution and lossless manner, presenting a fluffy state so that functional nano particles are fully doped into the carbon nanotube fibers, adding a low-concentration polymer infiltration process, finally carrying out hot pressing treatment on the film obtained by layering, winding and collecting, and improving the compactness of the composite film through the applied pressure and the surface tension effect of the infiltration liquid.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
The specific preparation steps of the high-strength high-conductivity carbon nano tube composite film in the embodiment are as follows (chloroauric acid is taken as an electrolyte for example):
1) Carbon nanotube fiber: carbon nanotube fibers prepared by chemical deposition (CVD) using a floating catalyst.
2) Preparing an electrolyte solution: 1g of chloroauric acid and 99g of deionized water are accurately weighed into a beaker and stirred until completely dissolved.
3) The preparation process of the carbon nano tube composite film comprises the following steps: 30mL of electrolyte is added into an electrolytic tank, an anode is an inert electrode, and a cathode is carbon nanotube fiber. The carbon nano tube fibers are respectively controlled by a current method (working current is 50 mA), electrolyzed water expands the carbon nano tube fibers, gold separated out by chloroauric acid is changed into gold nano particles to enter the expanded carbon nano tube, then the narrow band of the carbon nano tube with the gold nano particles is paved and wound on a round shaft through a winding device, finally the paved and wound film is taken down and subjected to hot pressing treatment under the condition of 130 ℃ and 12MPa, and the CNT/Au composite film with the thickness of 52 mu m is prepared, and an example diagram is shown in figure 2.
The characterization results of the CNT/Au composite film obtained in this example are as follows:
the resistance change before and after the carbon nanotube fiber and the gold nanoparticle are compounded is shown in fig. 3, and as can be seen from fig. 3, after the original carbon nanotube fiber is doped with the gold nanoparticle, the resistance is obviously reduced by 6 times. The electromagnetic shielding characterization results of the carbon nanotube fiber composite film before and after being compounded with gold are shown in fig. 4. As can be seen from fig. 4, the electromagnetic shielding of the composite film with gold nanoparticles is significantly better than that of the uncomplexed film, and the shielding benefit can be as high as 97dB, which is 3 times that before compounding.
As shown in fig. 5a and 5b, which are electron microscope images of the carbon nanotube film after being compounded with gold nanoparticles, it can be seen from fig. 5a and 5b that gold nanoparticles are not only distributed on the surface of carbon nanotubes, but also doped into the inside of carbon nanotube fibers, and are uniformly distributed. FIG. 6 is a graph showing the mechanical properties of a carbon nanotube composite film after being compounded with gold nanoparticles, wherein the strength of the film after being compounded can be stabilized at about 450 MPa.
Example 2
1) Carbon nanotube fiber: carbon nanotube fibers prepared by chemical deposition (CVD) using a floating catalyst.
2) Preparing an electrolyte solution: 6.5g of analytically pure iodine tablets are weighed and placed in a small beaker, 18.5g of solid KI is weighed, the iodine tablets are firstly dissolved in a small amount of alcohol, then water is added to 100 ml, stirring is carried out until the iodine tablets are completely dissolved, and dilute sulfuric acid is added dropwise into the solution to adjust the pH value of the solution to 1.
3) The preparation process of the carbon nano tube composite film comprises the following steps: 600mL of electrolyte is added into an electrolytic tank, the anode is an inert electrode, and the cathode is carbon nanotube fiber. Electrolyzing water to expand the carbon nano tube fiber, enabling iodine particles to enter the expanded carbon nano tube, enabling the carbon nano tube narrow band compounded with iodine to infiltrate from polyvinyl alcohol (PVA) solution, winding the carbon nano tube narrow band coated with PVA and provided with the iodine particles onto a circular shaft by a winding device, taking down the film wound by the winding device, and carrying out hot pressing treatment under the conditions of 90 ℃ and 8MPa to obtain the CNT/I composite film.
The characterization results of the CNT/I composite films obtained in this example are as follows:
as shown in fig. 7, the electromagnetic shielding benefit of the CNT/I composite film can reach 49dB, which is slightly higher than that of the carbon nanotube film, because the outer wrapping effect of the PVA polymer results in a decrease in the conductivity of the composite film, so that the electromagnetic shielding benefit is reduced, but still higher than that of the pure carbon nanotube film; in addition, as shown in FIG. 8, the mechanical properties of the carbon nanotube/iodine composite film are improved by adding the polymer PVA, the highest mechanical properties of the composite film can reach 826MPa, and the average strength is 642MPa.
Example 3
The present embodiment differs from the embodiment in that: the chloroauric acid in example 1 was replaced with chloroplatinic acid. The concentration of chloroplatinic acid in the electrolyte solution was 0.5wt%. Finally, the film coiled by the layer is taken down and hot pressed at 120 ℃ and 10 MPa.
The mechanical strength of the CNT/Pt composite film obtained in the embodiment can reach 600MPa, and the conductivity is 1.1 x 10 7 S/m, the electromagnetic shielding benefit can reach 101dB.
Example 4
The present embodiment differs from the embodiment in that: the electrolyte in example 2 was changed to a 1% concentration bromine aqueous solution, and the concentration of bromine in the electrolyte solution was 2wt%. And infiltrating the narrow band of carbon nanotubes compounded with bromine from the polyacrylic acid solution. Finally, the film coiled by the layer is taken down and hot-pressed at 110 ℃ and 11 MPa.
The mechanical strength of the CNT/Br composite film obtained by the embodiment can reach 382-415 MPa, and the conductivity is 0.78-0.91 x 10 7 S/m, the electromagnetic shielding benefit can reach 81-87 dB.
Comparative example 1
This comparative example is different from example 1 in that: instead of using a blanket-wound method to prepare a thin film, a carbon nanotube thin film is prepared by Chemical Vapor Deposition (CVD). The mechanical strength of the obtained carbon nano tube film is about 30MPa, and the shielding performance is 25dB.
Comparative example 2
This comparative example is different from example 1 in that: the mechanical strength of the obtained carbon nano tube composite film is about 200MPa, and the shielding performance is 30dB without chloroauric acid.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, 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 the scope thereof. 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. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (6)
1. The preparation method of the high-strength high-conductivity carbon nano tube composite film is characterized by comprising the following steps:
a carbon nanotube fiber is provided which is substantially free of carbon,
the method comprises the steps of taking carbon nanotube fibers fully infiltrated by water as a cathode, constructing an electrochemical reaction system together with an anode and an electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte and functional nanoparticle precursors, the functional nanoparticle precursors are selected from any one or more than two of chloroauric acid, chloroplatinic acid, bromine and iodine, and the concentration of the functional nanoparticle precursors in the electrolyte is 0.5-2wt%;
electrifying the electrochemical reaction system, uniformly expanding the carbon nano tube fiber in the radial direction and/or the length direction under the action of gas generated by electrolysis, simultaneously carrying out in-situ doping and compounding, and fully penetrating functional nano particles generated by the reaction into the surface and/or the inside of the carbon nano tube in the carbon nano tube fiber to prepare the carbon nano tube/functional nano particle composite fiber; the gas generated by the electrolysis is selected from hydrogen;
performing layering, winding and collecting on the carbon nano tube/functional nano particle composite fiber to form a carbon nano tube composite film;
carrying out hot-pressing treatment on the carbon nano tube composite film to obtain a high-strength high-conductivity carbon nano tube composite film, wherein the temperature of the hot-pressing treatment is 90-130 ℃ and the pressure is 8-12 MPa;
the high-strength high-conductivity carbon nano tube composite film comprises carbon nano tube fibers and functional nano particles distributed on the surfaces and inside the carbon nano tube fibers, wherein the functional nano particles are selected from any one or more than two of gold, platinum, bromine and iodine, and the content of the functional nano particles in the high-strength high-conductivity carbon nano tube composite film is 25-40 wt%.
2. The method of manufacturing according to claim 1, characterized in that: the electrolyte further comprises a water-soluble polymer selected from polyvinyl alcohol and/or polyacrylic acid; and/or the concentration of the polymer in the electrolyte is 0.05-1 wt%.
3. The method of manufacturing according to claim 1, characterized in that: the electrolyte also comprises an auxiliary agent, wherein the auxiliary agent is selected from any one or more than two of ethanol, glycol and glycerol; and/or the concentration of the auxiliary agent in the electrolyte is 0.05-1 wt%.
4. The method of manufacturing according to claim 1, characterized in that the method of manufacturing further comprises: and packaging the carbon nano tube composite film.
5. The method of manufacturing according to claim 1, characterized in that: and the surface and/or the inside of the carbon nano tube fiber is/are also distributed with a polymer.
6. The method of manufacturing according to claim 1, characterized in that: the thickness of the high-strength high-conductivity carbon nano tube composite film is 40-60 mu m.
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