CN117586539A - Preparation method of high-conductivity self-supporting carbon nano tube composite film - Google Patents
Preparation method of high-conductivity self-supporting carbon nano tube composite film Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 75
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 105
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006221 acetate fiber Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000012465 retentate Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 description 41
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 17
- 239000011970 polystyrene sulfonate Substances 0.000 description 17
- 229960002796 polystyrene sulfonate Drugs 0.000 description 17
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 239000002238 carbon nanotube film Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- -1 sodium alkyl benzene Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Abstract
The application discloses a preparation method of a high-conductivity self-supporting carbon nano tube composite film, and relates to the technical field of carbon nano tubes. The method comprises the following steps: uniformly mixing a single-walled carbon nanotube, a sodium alkylbenzenesulfonate dispersant, a poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and dispersing to obtain a single-walled carbon nanotube dispersion; filtering the single-wall carbon nanotube dispersion liquid to obtain a black trapped substance, and drying the black trapped substance to obtain a black film; and washing and drying the black film to obtain the finished carbon nano tube composite film. The application reduces the use of insulating substances and can improve the poly (3, 4-ethylenedioxygen) which is a high-conductivity substanceThiophene) in water, greatly improves the conductivity of the carbon nano tube composite film, and can reach 5 multiplied by 10 at most 5 The preparation of the large-area high-conductivity self-supporting carbon nano tube composite film can be realized by more than S/m.
Description
Technical Field
The application relates to the technical field of carbon nanotubes, in particular to a preparation method of a high-conductivity self-supporting carbon nanotube composite film.
Background
Single-wall carbon nanotubes are used as carbon nanotube varieties with excellent performance, and have special performance in the aspects of electricity, magnetism, heat and the like. The self-supporting (substrate-free) film prepared from the single-wall carbon nano tube as a main raw material is a new direction of application of the carbon nano tube, and the composite film has the advantages of high carbon nano tube content, high electrical conductivity, good thermal conductivity, low density, high strength, repeated bending and the like, and has wide application prospect in the fields of lightning protection of aircrafts, electromagnetic shielding protection of electronic devices, electrical conduction, thermal conduction and the like. However, when the conventional method is used for preparing the single-walled carbon nanotube composite film, the single-walled carbon nanotubes are difficult to disperse, the contact resistance between the single-walled carbon nanotubes is high, the film forming property of the single-walled carbon nanotubes is poor, other materials are needed to be added for assisting in film forming, but the introduced auxiliary materials are mostly insulators (such as common dispersing agents, polymers and the like), which is very unfavorable for reducing the contact resistance between the carbon nanotubes, so that the conductivity of the carbon nanotube film is difficult to break through 1 multiplied by 10 5 S/m, it is difficult to take advantage of the performance of single-walled carbon nanotubes. Therefore, the application provides a preparation method of the high-conductivity self-supporting carbon nano tube composite film.
Disclosure of Invention
The main purpose of the application is to provide a preparation method of a high-conductivity self-supporting carbon nano tube composite film, which aims to solve the technical problem that the conductivity of the existing self-supporting carbon nano tube composite film is low.
In order to achieve the above purpose, the present application proposes a method for preparing a highly conductive self-supporting carbon nanotube composite film, comprising the following steps:
uniformly mixing a single-walled carbon nanotube, a sodium alkylbenzenesulfonate dispersant, a poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and dispersing to obtain a single-walled carbon nanotube dispersion;
filtering the single-walled carbon nanotube dispersion liquid to obtain a black trapped substance, and drying the black trapped substance to obtain a black film;
and washing and drying the black film to obtain the finished carbon nano tube composite film.
Optionally, the sodium alkylbenzene sulfonate dispersant comprises at least one of sodium dodecylbenzene sulfonate and sodium hexadecylbenzene sulfonate.
Optionally, the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1: (0.5-5); the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1: (0.5-3).
Optionally, the mass concentration of the single-walled carbon nanotubes in the single-walled carbon nanotube dispersion is 0.05% -0.2%.
Optionally, the step of filtering the single-walled carbon nanotube dispersion to obtain a black trapped substance, and drying the black trapped substance to obtain a black film comprises the following steps:
filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance at the temperature of 50-100 ℃ to obtain a black film.
Optionally, the pore diameter of the microporous filter membrane is 0.01 mu m-0.5 mu m, and the microporous filter membrane is made of one of mixed fiber, nitrocellulose, acetate fiber, nylon 6, nylon 66 and polyethersulfone.
Optionally, the step of washing and drying the black film to obtain a finished carbon nanotube composite film includes:
firstly, placing the black film into a dimethyl sulfoxide solution at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, then placing the black film soaked into concentrated nitric acid at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film.
Optionally, the step of performing dispersion includes: one or more of ultrasonic dispersion, sand milling blending and ball milling blending modes are carried out.
Optionally, the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the specific surface area of the single-walled carbon nanotube is less than or equal to 500m 2 /g。
Optionally, the thickness of the carbon nanotube composite film is 1-500 [ mu ] m.
The application introduces poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution into single-wall carbon nanotube dispersion liquid, the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution consists of a mixture of ionomer poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonate, the polymer is a transparent high-conductivity polymer, can assist the single-wall carbon nanotube to form a film, effectively improves the film forming performance of the single-wall carbon nanotube, and poly (3, 4-ethylenedioxythiophene) in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution has good conductivity, but the water solubility of the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution can effectively improve the solubility of the poly (3, 4-ethylenedioxythiophene) in water, but the polystyrene sulfonate is insulating, excessive addition can influence the conductive performance of the composite film of the single-wall carbon nanotube, the application adds sodium alkylbenzenesulfonate dispersant to disperse the single-wall carbon nanotube, and the sodium alkylbenzenesulfonate and the poly (3, 4-ethylenedioxythiophene) has a similar conductive property with the poly (3, 4-ethylenedioxythiophene) sulfonate in the composite film in the aspect of having a water-soluble film in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution, thereby improving the single-wall carbon nanotube dispersion performance in the solvent, the film forming equipment is non-corrosive, the filtered filtrate is transparent water solution, the treatment is easy, and the sodium alkylbenzenesulfonate and polystyrene sulfonate on the carbon nano tube composite film are further removed after the subsequent washing and drying of the black film, so that the film forming equipment is greatly treatedThe conductivity of the carbon nano tube composite film is improved to be up to 5 multiplied by 10 5 Above S/m, the carbon nano tube composite film has no substrate material, can be self-supported, and realizes the preparation of the large-area high-conductivity self-supporting carbon nano tube composite film.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required 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 of the present application, and that other drawings may be obtained from the structures shown in these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a schematic view of a carbon nanotube composite film according to example 1 of the present application;
fig. 2 is a scanning electron microscope image of the carbon nanotube composite film according to example 3 of the present application.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
At present, when the conventional method is used for preparing the single-wall carbon nanotube composite film, the single-wall carbon nanotubes are difficult to disperse, the contact resistance between the single-wall carbon nanotubes is high, the film forming property of the single-wall carbon nanotubes is poor, other materials are needed to be added for assisting in film forming, but the introduced auxiliary materials are mostly insulators (such as common dispersing agents, polymers and the like), which is very unfavorable for reducing the contact resistance between the carbon nanotubes, so that the conductivity of the carbon nanotube film is difficult to break through 1 multiplied by 10 5 S/m, the property of single-walled carbon nanotubes is difficult to be exertedCan be used to advantage.
Aiming at the technical problems of the existing carbon nano tube composite film, the embodiment of the application provides a preparation method of a high-conductivity self-supporting carbon nano tube composite film, which comprises the following steps:
uniformly mixing a single-walled carbon nanotube, a sodium alkylbenzenesulfonate dispersant, a poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and dispersing to obtain a single-walled carbon nanotube dispersion;
filtering the single-walled carbon nanotube dispersion liquid to obtain a black trapped substance, and drying the black trapped substance to obtain a black film;
and washing and drying the black film to obtain the finished carbon nano tube composite film.
The poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is introduced into the single-walled carbon nanotube dispersion liquid, the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution consists of a mixture of ionomer poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonate, the poly-3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is a transparent high-conductivity polymer, film forming of the single-walled carbon nanotubes can be assisted, film forming performance of the single-walled carbon nanotubes can be effectively improved, the poly (3, 4-ethylenedioxythiophene) in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution has good conductivity, but water solubility is poor, polystyrene sulfonate in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution can effectively improve the solubility of the poly (3, 4-ethylenedioxythiophene) in water, but the polystyrene sulfonate is insulating, excessive addition can influence the conductive performance of the composite film of the single-walled carbon nanotubes, sodium alkylbenzenesulfonate dispersant is added to disperse the single-walled carbon nanotubes, and sodium alkylbenzenesulfonate and the poly (3, 4-ethylenedioxythiophene) has the same conductivity as the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate) in the poly-4-ethylenedioxythiophene sulfonate solution, so that the poly (3, 4-ethylenedioxythiophene) has the same water solubility as the polystyrene sulfonate has the water-soluble polystyrene sulfonate, and the two-soluble polystyrene sulfonate in the water-soluble polystyrene sulfonate solution has the water-soluble effect, and the polystyrene sulfonate has the water-soluble conductivity of the water-soluble polystyrene sulfonate, and the polystyrene sulfonate is the water-solubleThe conductive performance of the composite carbon nanotube film is achieved, the dispersion liquid of the single-wall carbon nanotube is free of organic solvent, the dispersion liquid is neutral, the film forming equipment is free of corrosiveness, the filtered filtrate is transparent water solution, the treatment is easy, the sodium alkylbenzenesulfonate and the polystyrene sulfonate on the composite carbon nanotube film are further removed after the black film is washed and dried, the conductivity of the composite carbon nanotube film is greatly improved, and the maximum conductivity of the composite carbon nanotube film can reach 5 multiplied by 10 5 Above S/m, the carbon nano tube composite film has no substrate material, can be self-supported, and realizes the preparation of the large-area high-conductivity self-supporting carbon nano tube composite film.
As one embodiment of the present application, the sodium alkylbenzene sulfonate dispersant includes at least one of sodium dodecylbenzene sulfonate and sodium hexadecylbenzene sulfonate.
Sodium dodecyl benzene sulfonate and sodium hexadecyl benzene sulfonate are both anionic surfactants, have good dispersibility, have good dispersing effect on single-wall carbon nanotubes, have hydrophilic groups in a molecular structure, have strong hydrophilicity, can cooperate with polystyrene sulfonate, strengthen the solubility of poly (3, 4-ethylenedioxythiophene) in water, and further increase the content of conductive substances in the carbon nanotube composite film, thereby improving the conductivity of the carbon nanotube composite film.
As an embodiment of the present application, the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1: (0.5-5); the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1: (0.5-3).
According to the preparation method, the single-wall carbon nano tube, the sodium alkylbenzenesulfonate dispersant and the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution are effectively compounded, so that the content of insulating substances in the carbon nano tube composite film is reduced as much as possible, the content of the high-conductivity substance poly (3, 4-ethylenedioxythiophene) is improved, and the conductivity of the carbon nano tube composite film is further improved.
As an embodiment of the present application, the mass concentration of the single-walled carbon nanotubes in the single-walled carbon nanotube dispersion is 0.05% -0.2%.
As an embodiment of the present application, the step of filtering the single-walled carbon nanotube dispersion to obtain a black trapped material, and drying the black trapped material to obtain a black film includes:
filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance at the temperature of 50-100 ℃ to obtain a black film.
According to the method, the single-walled carbon nanotube dispersion liquid is filtered through the microporous filter membrane, the microporous filter membrane is high in porosity, precise filtration can be achieved, after the single-walled carbon nanotube dispersion liquid is filtered through the microporous filter membrane, the filtrate is a transparent aqueous solution, the treatment is easy, the surface of the microporous filter membrane is a black trapped object, and the black membrane obtained after the black trapped object is dried has conductivity.
As an implementation manner of the present application, the pore diameter of the microporous filter membrane is 0.01 μm-0.5 μm, and the microporous filter membrane is made of one of mixed fiber, nitrocellulose, acetate fiber, nylon 6, nylon 66 and polyethersulfone. Through the microporous filter membrane with the aperture of 0.01 mu m-0.5 mu m, particles in the single-walled carbon nanotube dispersion liquid can be filtered out as much as possible, and more black trapped matters are obtained.
As an embodiment of the present application, the step of washing and drying the black film to obtain a finished carbon nanotube composite film includes:
firstly, placing the black film into a dimethyl sulfoxide solution at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, then placing the black film soaked into concentrated nitric acid at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film.
The black film is soaked in dimethyl sulfoxide solution, so that a large amount of sodium alkylbenzenesulfonate dispersant and polystyrene sulfonate in the black film can be removed, and then concentrated nitric acid is used for soaking, so that the sodium alkylbenzenesulfonate dispersant and polystyrene sulfonate attached to the black film can be further removed, and insulating substances in the carbon nano tube composite film are reduced, and the conductivity of the carbon nano tube composite film is improved.
As an embodiment of the present application, the step of performing dispersion includes: one or more of ultrasonic dispersion, sand milling blending and ball milling blending modes are carried out. Through ultrasonic dispersion, sand grinding blending or ball milling blending, the uniform mixing of the single-walled carbon nanotube, the sodium alkyl benzene sulfonate dispersant and the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate can be promoted, so that the single-walled carbon nanotube is dispersed in the solution as much as possible.
As one implementation mode of the application, the diameter of the single-wall carbon nano tube is less than or equal to 3nm, and the specific surface area of the single-wall carbon nano tube is less than or equal to 500m 2 And/g. The specific surface area of the single-walled carbon nanotubes is determined by a nitrogen adsorption method, and the single-walled carbon nanotubes with the diameter of not more than 3nm are more easily dispersed by a dispersing agent, preferably, the diameter of the single-walled carbon nanotubes is 2nm.
As an implementation manner of the method, the thickness of the carbon nanotube composite film is 1-500 μm. The carbon nanotube composite film obtained through the preparation method is a self-supporting (i.e. substrate-free) black opaque flexible film, and the thickness of the film is between 1 mu m and 500 mu m.
The above technical solutions of the present application are described in detail below with reference to specific embodiments.
Example 1
The preparation method of the high-conductivity self-supporting carbon nano tube composite film comprises the following steps:
uniformly mixing a single-wall carbon nanotube, sodium dodecyl benzene sulfonate, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and performing ultrasonic dispersion to obtain a single-wall carbon nanotube dispersion liquid, wherein the mass concentration of the single-wall carbon nanotube in the single-wall carbon nanotube dispersion liquid is 0.1%; the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1:2; the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1:1.5;
wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the specific surface area of the single-walled carbon nanotube is less than or equal to 500m 2 /g；
Filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance within a temperature range of 75 ℃ to obtain a black film;
the pore diameter of the microporous filter membrane is 0.2 mu m, and the microporous filter membrane is made of nitrocellulose;
firstly, placing the black film into a dimethyl sulfoxide solution at 55 ℃ to be soaked for 1.2 hours, washing the black film by deionized water, then placing the black film soaked in the dimethyl sulfoxide solution into concentrated nitric acid at 55 ℃ to be soaked for 1.2 hours, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film, wherein the thickness of the carbon nano tube composite film is 100 mu m.
The physical diagram of the carbon nano tube composite film is shown in figure 1, and the conductivity of the carbon nano tube composite film can reach 5 multiplied by 10 after detection 5 S/m。
Example 2
The preparation method of the high-conductivity self-supporting carbon nano tube composite film comprises the following steps:
uniformly mixing a single-walled carbon nanotube, sodium hexadecyl benzenesulfonate, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and performing sanding and blending to obtain a single-walled carbon nanotube dispersion liquid, wherein the mass concentration of the single-walled carbon nanotube in the single-walled carbon nanotube dispersion liquid is 0.05%; the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1:0.5; the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1:0.5;
wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the specific surface area of the single-walled carbon nanotube is less than or equal to 500m 2 /g；
Filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance within a temperature range of 50 ℃ to obtain a black film;
the pore diameter of the microporous filter membrane is 0.01 mu m, and the microporous filter membrane is made of acetate fibers;
firstly, placing the black film into a dimethyl sulfoxide solution at 40 ℃ to be soaked for 2 hours, washing the black film by deionized water, then placing the black film soaked in the dimethyl sulfoxide solution into concentrated nitric acid at 40 ℃ to be soaked for 2 hours, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film, wherein the thickness of the carbon nano tube composite film is 300 mu m.
Through detection, the conductivity of the carbon nano tube composite film can reach 4.85 multiplied by 10 5 S/m。
Example 3
The preparation method of the high-conductivity self-supporting carbon nano tube composite film comprises the following steps:
uniformly mixing a single-wall carbon nanotube, sodium dodecyl benzene sulfonate, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and performing ball milling and blending to obtain a single-wall carbon nanotube dispersion liquid, wherein the mass concentration of the single-wall carbon nanotube in the single-wall carbon nanotube dispersion liquid is 0.2%; the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1:5, a step of; the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1:3, a step of;
wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the specific surface area of the single-walled carbon nanotube is less than or equal to 500m 2 /g；
Filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped object, and drying the black trapped object at the temperature of 100 ℃ to obtain a black film;
the pore diameter of the microporous filter membrane is 0.5 mu m, and the microporous filter membrane is made of polyether sulfone;
firstly, placing the black film into a dimethyl sulfoxide solution at 70 ℃ to be soaked for 0.5h, washing the black film by deionized water, then placing the black film soaked in the dimethyl sulfoxide solution into concentrated nitric acid at 70 ℃ to be soaked for 0.5h, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film, wherein the thickness of the carbon nano tube composite film is 50 mu m.
The scanning electron microscope image of the carbon nano tube composite film under the condition of 1 mu m is shown as figure 2, and the conductivity of the carbon nano tube composite film can reach 4.9x10 after detection 5 S/m。
Example 4
The preparation method of the high-conductivity self-supporting carbon nano tube composite film comprises the following steps:
uniformly mixing a single-walled carbon nanotube, sodium hexadecyl benzenesulfonate, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and performing ultrasonic dispersion to obtain a single-walled carbon nanotube dispersion liquid, wherein the mass concentration of the single-walled carbon nanotube in the single-walled carbon nanotube dispersion liquid is 0.15%; the mass ratio of the single-walled carbon nanotubes to the sodium alkylbenzenesulfonate dispersant is 1:1.5; the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1:2.5;
wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, and the specific surface area of the single-walled carbon nanotube is less than or equal to 500m 2 /g；
Filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance within a temperature range of 60 ℃ to obtain a black film;
the pore diameter of the microporous filter membrane is 0.09 mu m, and the microporous filter membrane is made of mixed fibers;
firstly, placing the black film into a dimethyl sulfoxide solution at 50 ℃ to be soaked for 0.7h, washing the black film by deionized water, then placing the black film soaked in the dimethyl sulfoxide solution into concentrated nitric acid at 50 ℃ to be soaked for 0.7h, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film, wherein the thickness of the carbon nano tube composite film is 87 mu m.
The foregoing description is only of the optional embodiments of the present application, and is not intended to limit the scope of the patent application, and all equivalent structural changes made by the specification and drawings of the present application or direct/indirect application in other related technical fields are included in the scope of the patent protection of the present application.
Claims (10)
1. The preparation method of the high-conductivity self-supporting carbon nano tube composite film is characterized by comprising the following steps of:
uniformly mixing a single-walled carbon nanotube, a sodium alkylbenzenesulfonate dispersant, a poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution and deionized water, and dispersing to obtain a single-walled carbon nanotube dispersion;
filtering the single-walled carbon nanotube dispersion liquid to obtain a black trapped substance, and drying the black trapped substance to obtain a black film;
and washing and drying the black film to obtain the finished carbon nano tube composite film.
2. The method for preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the sodium alkylbenzenesulfonate dispersant comprises at least one of sodium dodecylbenzenesulfonate and sodium hexadecylbenzenesulfonate.
3. The method for preparing the high-conductivity self-supporting carbon nano tube composite film according to claim 1, wherein the mass ratio of the single-wall carbon nano tube to the sodium alkylbenzenesulfonate dispersant is 1: (0.5-5); the mass ratio of the single-walled carbon nanotubes to the solid components in the poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution is 1: (0.5-3).
4. The method for preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the mass concentration of the single-walled carbon nanotubes in the single-walled carbon nanotube dispersion is 0.05% -0.2%.
5. The method for preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the step of filtering the single-walled carbon nanotube dispersion to obtain a black retentate, and drying the black retentate to obtain a black film comprises:
filtering the single-walled carbon nanotube dispersion liquid through a microporous filter membrane to obtain a black trapped substance, and drying the black trapped substance at the temperature of 50-100 ℃ to obtain a black film.
6. The method for preparing the high-conductivity self-supporting carbon nanotube composite film according to claim 5, wherein the pore diameter of the microporous filter membrane is 0.01-0.5 mu m, and the microporous filter membrane is made of one of mixed fiber, nitrocellulose, acetate fiber, nylon 6, nylon 66 and polyethersulfone.
7. The method for preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the step of washing and drying the black film to obtain a finished carbon nanotube composite film comprises:
firstly, placing the black film into a dimethyl sulfoxide solution at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, then placing the black film soaked into concentrated nitric acid at 40-70 ℃ to be soaked for 0.5-2 hours, washing the black film by deionized water, and drying the black film to obtain the finished carbon nano tube composite film.
8. The method of preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the dispersing step comprises: one or more of ultrasonic dispersion, sand milling blending and ball milling blending modes are carried out.
9. The method for preparing a highly conductive self-supporting carbon nanotube composite film according to claim 1, wherein the diameter of the single-walled carbon nanotube is less than or equal to 3nm, the singleThe specific surface area of the wall carbon nano tube is less than or equal to 500m 2 /g。
10. The method for preparing the high-conductivity self-supporting carbon nanotube composite film according to claim 1, wherein the thickness of the carbon nanotube composite film is 1 [ mu ] m to 500 [ mu ] m.
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