CN117316526B - Method for preparing self-supporting nano carbon-based conductive macroscopic body and application thereof - Google Patents
Method for preparing self-supporting nano carbon-based conductive macroscopic body and application thereof Download PDFInfo
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002904 solvent Substances 0.000 claims abstract description 36
- -1 uniformly dispersing Substances 0.000 claims abstract description 26
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- 238000000576 coating method Methods 0.000 claims abstract description 22
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- 229920005989 resin Polymers 0.000 claims abstract description 21
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- 238000002156 mixing Methods 0.000 claims abstract description 19
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims abstract description 8
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 7
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 6
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- 239000000243 solution Substances 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002041 carbon nanotube Substances 0.000 claims description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 27
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of carbon nano materials, and provides a method for preparing a self-supporting nano carbon-based conductive macroscopic body and application thereof, wherein the method comprises the following steps: s1, mixing a carbon-based material, a sulfonic acid-based compound and a solvent, uniformly dispersing, and coating on a substrate to obtain a nano carbon-based conductive macroscopic body coated on the substrate; s2, separating the nano carbon-based conductive macroscopic body from the substrate by using an acid solution to obtain a self-supporting nano carbon-based conductive macroscopic body; the sulfonic acid group compound comprises one or more of dodecylbenzene sulfonic acid, perfluorinated sulfonic acid resin, polystyrene sulfonic acid and camphorsulfonic acid. By the technical scheme, the problems that a self-supporting structure is difficult to form and the conductivity is low in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a method for preparing a self-supporting nano carbon-based conductive macroscopic body and application thereof.
Background
Carbon-based nanomaterials encompass a variety of low-dimensional nanomaterials, including carbon nanotubes, graphene, carbon black, and the like, in which carbon atoms are bonded mainly by means of sp 2 hybridized carbon-carbon bonds, and a carbon six-membered ring is used as a basic structural unit, and the outermost layer of each carbon atom contains an unpaired electron to form pi bonds. The unique molecular structure gives these materials excellent electrical properties and high chemical stability. As a low-dimensional nanomaterial, the carbon-based nanomaterial has the characteristics of quantum confinement effect, strong phonon-electron coupling, special energy band structure and the like, and shows various novel physical characteristics such as extremely high carrier mobility, light absorption coefficient, near infrared fluorescence emission, adjustable metal semiconductor characteristics and the like. Therefore, the carbon-based nano material has wide application prospect in the aspects of electronics, photoelectricity, biological medicine and the like.
Because the carbon-based nano material has large specific surface area, the carbon nano material is generally agglomerated together due to Van der Waals force, so that the prepared carbon nano tube, graphene and carbon black are in powder form, and large-area continuous nano carbon-based macroscopic body is difficult to directly prepare. At present, a large-area continuous nano carbon-based macroscopic body is prepared by dispersing a carbon-based material in a solvent to prepare a dispersion liquid, and then forming a film on a substrate, wherein the formed film is required to be attached to the substrate and cannot spontaneously form a self-supporting structure. Although it is possible to peel from the substrate by dissolving the substrate, immersing in a specific solution, mechanically peeling, etc., such a substrate-free supporting structure can be developed only in a liquid such as water and maintains the shape and pattern of the structure, and is highly complex in technology, and is liable to cause breakage and breakage during transfer or removal of the substrate.
CN110171815A discloses a preparation method of a low-cost high-purity carbon nanotube film, which prepares the carbon nanotube film by suction filtration, and then heats the filter membrane and the carbon nanotube in boiling ethanol together, so that the carbon nanotube film is separated from the filter membrane under the overflow tension of bubbles; CN107265439B discloses a method for nondestructively separating a macroscopic film of a carbon nanotube, which reduces the surface energy of a substrate by spraying a low surface free energy substance onto the substrate before the film is formed, thereby reducing the interaction force between the carbon nanotube and the substrate and enabling the carbon nanotube film to be peeled off from the substrate more easily. The interaction force between the carbon nanomaterial and the substrate is strong, and the carbon nanomaterial is difficult to separate from the substrate naturally. Although this method provides a viable path for reducing the interaction forces between the carbon nanotubes and the substrate, it still requires mechanical stripping, which tends to disrupt the macroscopic film shape and cause some carbon nanomaterial to remain on the substrate.
The high-strength transparent high-conductivity self-supporting carbon nanotube ultrathin film disclosed by CN102110489B, a preparation method thereof and a preparation and transfer method of the unsupported single-orientation carbon nanotube film disclosed by CN107867679B are characterized in that the carbon nanotubes are dispersed by an anionic surfactant, and after film formation, the film finally floats in a solvent in a mode of dissolving the substrate or soaking in an aqueous solvent, and can be transferred to other substrates. The method has higher dependence on the properties of the substrate material and the surfactant used for dispersing the carbon nano material, and meanwhile, when the corrosion resistance of the substrate is stronger, the film cannot be peeled off; on the other hand, in the solvent volatilization process after film formation, a large number of surfactant molecules in the solvent are precipitated and deposited on the surface of the substrate or are coated on the surface of the carbon nanomaterial, and the surfactant molecules prevent the direct contact between the substrate and the carbon nanomaterial to a certain extent. With the flushing of a large amount of aqueous solution, part of the surfactant is redissolved and the film is peeled off. In addition, the method of immersing and falling off in an aqueous solution is generally only applicable to anionic surfactants, and the requirements on the surfactants are high.
WO2016015658A1 discloses a carbon nanotube-polymer layered composite transparent flexible electrode and a preparation method thereof, which uses alkylated quaternary ammonium base and anionic acidic substance as a dispersing agent, PET as a substrate, spin-coating to construct a carbon nanotube composite film, washing with ethanol and deionized water, and even soaking with concentrated nitric acid, wherein the carbon nanotube composite film does not fall off the substrate to form a self-supporting structure (see the patent example 2 in detail), which indicates that when different substances are used as dispersing agents, the soaking with deionized water, acidity, alkalinity and salt solution does not necessarily fall off the film from the substrate. In addition, the method of soaking in aqueous solution has certain requirement on the hydrophilicity of the substrate, and simultaneously, as a large amount of surfactant crystals are adhered to the surface and the substrate of the film in the solvent volatilization process, the uniformity of the film is reduced, the film is easy to crack in the aqueous solution, and the conductivity of the macroscopic film is reduced due to the fact that a large amount of surfactant is coated on the surface of the carbon nanomaterial.
In summary, carbon nanomaterials are insoluble in water and most organic solvents, and therefore, dispersants are critical to adequately disperse these materials and maintain a long-term stable state of the dispersion. At present, the carbon nano material is directly dispersed in organic solvents such as alcohols and N-methyl pyrrolidone by means of strong shearing force, so that high-concentration dispersion is difficult to realize, and full dispersion of the carbon nano material cannot be ensured. The ionic surfactant such as sodium dodecyl sulfate, sodium cholate, sodium deoxycholate and the like can be used for fully dispersing the carbon nanomaterial, but the viscosity and the surface tension of the dispersion liquid are greatly reduced due to the strong lubricating capability of the surfactant molecules. The excessive fluidity of the dispersion liquid makes it difficult to construct macroscopic bodies of specific shapes by large-scale preparation processes such as knife coating, printing, wire drawing and the like, and higher concentration of nano materials are generally required to be added to increase the viscosity, but the nano materials are also difficult to sufficiently disperse. Meanwhile, the ionic surfactants are coated on the surface of the carbon nano material to prevent carrier transport, so that the conductivity of the material is seriously reduced.
Disclosure of Invention
The invention provides a method for preparing a self-supporting nano carbon-based conductive macroscopic body and application thereof, and solves the problems that the nano carbon-based macroscopic body in the related art is difficult to form a self-supporting structure and has low conductivity.
The technical scheme of the invention is as follows:
a method of preparing a self-supporting nanocarbon-based conductive macroscopic body comprising the steps of:
s1, mixing a carbon-based material, a sulfonic acid-based compound and a solvent, uniformly dispersing, and coating on a substrate to obtain a nano carbon-based conductive macroscopic body coated on the substrate;
s2, separating the nano carbon-based conductive macroscopic body from the substrate by using an acid solution to obtain a self-supporting nano carbon-based conductive macroscopic body;
the sulfonic acid group compound comprises one or more of dodecylbenzene sulfonic acid, perfluorinated sulfonic acid resin, polystyrene sulfonic acid and camphorsulfonic acid.
As a further technical scheme, the mass ratio of the carbon-based material to the sulfonic acid group compound is 1:2.5-20.
As a further technical scheme, the sulfonic acid group compound comprises perfluorinated sulfonic acid resin and camphorsulfonic acid with the mass ratio of 2:3-4:1.
As a further technical scheme, the sulfonic acid group compound comprises perfluorosulfonic acid resin and camphorsulfonic acid with a mass ratio of 3:2.
As a further technical scheme, the carbon-based material comprises one or more of carbon nanotubes, carbon black, graphene and graphite.
As a further technical scheme, the solvent comprises one or more of water, ethanol, isopropanol, methanol and propanol.
As a further technical scheme, the mass-volume ratio of the carbon-based material to the solvent is 1 mg/0.5-3 mL.
As a further technical solution, the dispersing includes ultrasonic dispersing or shearing dispersing.
As a further technical scheme, the coating comprises one of knife coating, spin coating and spray coating.
As a further technical scheme, the acidic solution comprises one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, chloroauric acid solution, ferric chloride solution and chlorosulfonic acid solution;
the mass concentration of the acidic solution is 4% -99%.
As a further technical scheme, the using amount of the acidic solution is 30-100 mu L/cm 2 based on the area of the substrate.
As a further technical scheme, the acidic solution is a nitric acid solution with a mass concentration of 40%.
As a further technical scheme, the action time of the acid solution is 10 s-2 h.
As a further technical scheme, after the substrate is separated from the substrate, one or more of water, ethanol, isopropanol and methanol are used for washing to remove the residual acid solution on the surface of the macroscopic body.
The working principle and the beneficial effects of the invention are as follows:
1. The self-supporting nano carbon-based conductive macroscopic body is prepared by using the aqueous solution of the carbon-based material and the sulfonic acid-based compound and the solvent, the mixed dispersion of one or more carbon nano materials can be directly realized in the solution, and the mixed dispersion liquid of different carbon nano materials can be prepared according to practical requirements and the properties of various carbon nano materials, so that the self-supporting nano carbon-based conductive macroscopic body of different carbon nano material hybrids can be prepared.
2. The self-supporting nano carbon-based conductive macroscopic body is prepared by using the sulfonic acid group compound, the construction of the macroscopic body with a specific shape is easy to realize on the substrate, the self-supporting nano carbon-based conductive macroscopic body can be completely separated from the substrate, and good flexibility is shown. Because the sulfonic acid group in the sulfonic acid group compound is a hydrophilic end, the free H ＋ in the solution can be promoted to transfer to the surface of the carbon-based material at one side far away from the carbon-based material, and the protonation of the carbon-based material is initiated under the acidic condition, so that the surface of the carbon-based material is positively charged, the coulomb force among molecules of the carbon-based material is changed, the dispersibility of the carbon-based material is improved, the adhesion between the nano carbon-based conductive macroscopic body and the substrate is reduced, and the self-supporting nano carbon-based conductive macroscopic body can be formed while the shape and the pattern of the nano carbon-based conductive macroscopic body are maintained. In addition, the carbon-based material is doped with p-type while protonating, so that the conductivity and work function are improved, the contact resistance among molecules of the carbon-based material is reduced, and the self-supporting nano carbon-based conductive macroscopic body shows good conductivity.
3. The method for preparing the self-supporting nano carbon-based conductive macroscopic body provided by the invention can be suitable for the processes of blade coating, printing and the like, has high fitting degree with the existing production process, can construct the macroscopic body with a specific shape or pattern with the assistance of a mask or a mould, and provides a feasible path for preparing the large-area self-supporting nano carbon-based conductive macroscopic body. In addition, the method for preparing the self-supporting nano carbon-based conductive macroscopic body provided by the invention can be rapidly completed, is short in time consumption, does not influence the overall structure and shape of the macroscopic body, is suitable for preparing the macroscopic body with large area, and the self-supporting structure still keeps a self-supporting state in the atmosphere.
4. The self-supporting nano carbon-based conductive macroscopic body provided by the invention has a plurality of potential application values. For example, in the aspect of new energy devices, the method can be used for cathode materials of lithium ion batteries to prepare flexible electrodes; the silicon heterojunction solar cell can be used for a photovoltaic device and used as an emission area to form a heterojunction solar cell with silicon; can be laid on a novel perovskite solar cell to be used as a back electrode, an electron transport layer or a hole transport layer. In the aspect of the semiconductor device, p-doping and n-doping can be further carried out to construct a flexible thermoelectric module, a flexible thin film transistor, a light detecting device, a flexible thermoelectric device and the like.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in example 1 of the present invention;
FIG. 2 is an SEM test chart of a self-supporting nanocarbon-based conductive macroscopic body prepared in example 1 of the present invention;
FIG. 3 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in example 2 of the present invention;
FIG. 4 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in example 5 of the present invention;
FIG. 5 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in example 14 of the present invention;
FIG. 6 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in comparative example 1 of the present invention;
FIG. 7 is an SEM test chart of a self-supporting nanocarbon-based conductive macroscopic body prepared in comparative example 1 of the present invention;
FIG. 8 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body prepared in comparative example 2 of the present invention;
FIG. 9 is a photograph of a self-supporting nanocarbon-based conductive macroscopic body obtained in example 16 of the present invention;
Fig. 10 is a graph showing the transmittance test of the self-supporting nanocarbon-based conductive macroscopic body obtained in example 16 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill 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 carbon nanotubes in the following examples and comparative examples were of the type CoMoCAT (6, 5) with an average diameter of 0.78nm and were manufactured under the brand name Sigma-Aldrich; the particle size of the carbon black is 5nm, and the brand is Xianfeng nanometer; CAS number of perfluorosulfonic acid resin: 31175-20-9, the brand being microphone; polystyrene sulfonic acid has a weight average molecular weight of 7 ten thousand and is branded as sigma-Aldrich; dodecyl benzene sulfonic acid, camphorsulfonic acid, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate are brands sigma-Aldrich.
Example 1
S1, mixing 4mL of perfluorosulfonic acid resin aqueous solution with concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1 mu m (shown in figures 1-2).
Example 2
S1, mixing 6mg of carbon nano tube, 4mL of polystyrene sulfonic acid aqueous solution with the concentration of 0.03g/mL and 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
s3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1 mu m (shown in figure 3).
Example 3
S1, mixing 4mL of dodecylbenzene sulfonic acid aqueous solution with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 4
S1, mixing 4mL of camphorsulfonic acid aqueous solution with concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 5
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1 mu m (shown in figure 4).
Example 6
S1, mixing 4mL of aqueous solution of 6mg of carbon nano tube and 0.03g/mL of sulfonic compound with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic compound consists of perfluorosulfonic resin and dodecylbenzenesulfonic acid in a mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 7
S1, mixing 4mL of aqueous solution of 6mg of carbon nano tube and 0.03g/mL of sulfonic compound with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic compound consists of perfluorosulfonic resin and camphorsulfonic acid in a mass ratio of 4:1;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 8
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 2:3;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 9
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 30wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 10
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 50wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 11
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 20wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 12
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and camphorsulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 60wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 13
S1, mixing 4mL of aqueous solution of a sulfonic acid group compound with the concentration of 0.03g/mL and 6mg of carbon nano tube with 14mL of ethanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use, wherein the sulfonic acid group compound consists of perfluorosulfonic acid resin and polystyrene sulfonic acid with the mass ratio of 3:2;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm glass substrate, placing a mask plate with a square hollow center above the glass substrate, scraping the dispersion liquid on the glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
S3, dripping 5mL of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1mu m.
Example 14
S1, mixing 6mg of carbon nano tube, 4mg of carbon black and 5mL of polystyrene sulfonic acid aqueous solution with the concentration of 0.05g/mL with 10mL of isopropanol, and shearing and dispersing in a shearing and dispersing machine for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm adhesive tape substrate, placing a mask plate with a square hollow center above the adhesive tape substrate, scraping the dispersion liquid on a glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing the mask plate after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain the nano carbon-based conductive macroscopic body covered on the substrate;
s3, dripping 6.5mL of sulfuric acid solution with the concentration of 4wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1 mu m (shown in figure 5).
Example 15
S1, mixing 6mg of carbon nano tube, 4mg of carbon black, 2mg of graphene, 0.5mL of polystyrene sulfonic acid aqueous solution with the concentration of 0.1g/mL and 5.5mL of methanol, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 5mL of dispersion liquid, dripping the dispersion liquid on a clean 8cm multiplied by 8cm polyimide substrate, scraping the dispersion liquid on a glass substrate by using a scraping coater, setting the speed of the scraping coater to be 17.5mm/S and the height to be 0.9mm, removing a mask after the scraping coating is finished, and waiting for the solvent to volatilize completely to obtain a nano carbon-based conductive macroscopic body covered on the substrate;
S3, 2mL of chloroauric acid solution with the concentration of 99wt% is dripped on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, the solution is kept stand for 30min, then the solution is washed by deionized water, the nano carbon-based conductive macroscopic body naturally falls off from the substrate, and the self-supporting nano carbon-based conductive macroscopic body with the thickness of 1 μm is obtained by drying by using nitrogen.
Example 16
S1, mixing 4mL of perfluorosulfonic acid resin aqueous solution with concentration of 0.03g/mL and 6.5 mL of ethanol with 6mg of carbon nano tube, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid for later use;
S2, taking 800 mu L of dispersion liquid to be coated on a clean 2cm multiplied by 5cm glass substrate, setting the rotating speed of a spin coater to be 3000r/min and the time to be 10S, spin coating to obtain a uniform carbon nano tube film, and waiting for the solvent to volatilize completely to obtain a nano carbon-based conductive macroscopic body coated on the substrate;
S3, dripping 500 mu L of nitric acid solution with the concentration of 40wt% on the surface of the nano carbon-based conductive macroscopic body covered on the substrate, standing for 30min, flushing with deionized water, naturally falling off the nano carbon-based conductive macroscopic body from the substrate, and drying with nitrogen to obtain the self-supporting nano carbon-based conductive macroscopic body with the thickness of 200 nm.
Comparative example 1
The difference from example 1 is only that the aqueous perfluorosulfonic acid resin solution was replaced with an aqueous sodium dodecylsulfonate solution; the glass substrate area was 4cm. Times.4 cm.
In the process of preparing the nano carbon-based conductive macroscopic body coated on the substrate, a large amount of white crystals are precipitated on the surface along with the volatilization of the solvent, and the crystals are sodium dodecyl sulfonate serving as a surfactant. Meanwhile, although the dispersion liquid uniformly covers the whole substrate after blade coating, in the solvent volatilizing process, the solvent contracts inwards from the edge to generate stronger capillary force, and the carbon-based material contracts with the solvent under the action of the capillary force to destroy the original film shape and make the film quite uneven (as shown in fig. 6-7).
Comparative example 2
The difference from example 1 is only that the aqueous perfluorosulfonic acid resin solution was replaced with an aqueous sodium dodecylbenzenesulfonate solution; the glass substrate area was 4cm. Times.4 cm.
During the preparation of the nanocarbon-based conductive macroscopic body coated on the substrate, as the solvent volatilizes, a part of white crystals were precipitated on the surface, similar to the result of comparative example 1. Meanwhile, in the process of volatilizing the solvent, the carbon-based material contracts towards the center of the nano carbon-based conductive macroscopic body along with the volatilization of the solvent, and finally an obvious coffee ring is formed, which means that the surface of the film is uneven, and the shape of the macroscopic body is changed difficultly (as shown in figure 8).
Comparative example 3
The difference from example 1 is only that the nitric acid solution with a concentration of 40wt% in S3 is replaced with water, and it was found that the nanocarbon-based conductive macroscopic body cannot be detached from the substrate to form a self-supporting nanocarbon-based conductive macroscopic body.
Performance test:
(1) Conductivity: the self-supporting nanocarbon-based conductive macrostructures obtained in examples 1 to 15 and comparative examples 1 to 2 were subjected to sheet resistance test using a four-probe tester, film thickness was tested using a step tester, and conductivity was calculated according to the following formula from sheet resistance and film thickness:
conductivity=1/(sheet resistance×film thickness)
The calculation results are recorded in table 1.
TABLE 1 conductivity
As can be seen from Table 1, the self-supporting nano carbon-based conductive macroscopic body obtained by the method for preparing the self-supporting nano carbon-based conductive macroscopic body has the conductivity of more than 875S/cm and good conductive performance.
Example 1 the aqueous perfluorosulfonic acid resin solution used in example 1, the aqueous sodium dodecyl sulfate solution used in comparative example 1, the aqueous sodium dodecyl benzene sulfonate solution used in comparative example 2, and the self-supporting nanocarbon-based conductive macroscopic body obtained in example 1 had higher conductivity than comparative examples 1 to 2, indicating that the self-supporting nanocarbon-based conductive macroscopic body prepared using the sulfonic acid-based compound of the present invention had better conductivity than the surfactant using the sulfonic acid group.
In example 5, compared with examples 9 to 12, the nitric acid solution having a concentration of 40wt% was used in example 5, the nitric acid solution having a concentration of 30wt% was used in example 9, the nitric acid solution having a concentration of 50wt% was used in example 10, the nitric acid solution having a concentration of 20wt% was used in example 11, the nitric acid solution having a concentration of 60wt% was used in example 12, and the conductivity of the self-supporting nanocarbon-based conductive macroscopic body obtained in examples 9 to 12 was lower than that of example 5, indicating that the conductivity of the self-supporting nanocarbon-based conductive macroscopic body could be further improved when the nitric acid solution having a concentration of 40wt% was used.
(2) SEM test: SEM tests were performed on the self-supporting nanocarbon-based conductive macrostructures obtained in example 1 and comparative example 1.
The self-supporting nano carbon-based conductive macroscopic body prepared in the embodiment 1 is shown in fig. 1-2, and as can be seen from fig. 1-2, the self-supporting nano carbon-based conductive macroscopic body provided in the embodiment 1 of the invention has the advantages of flat surface, good appearance, even distribution of carbon nanotubes in a single state, smooth surface and no wrapping of other substances.
The self-supporting nano carbon-based conductive macroscopic body prepared in comparative example 1 is shown in fig. 6 to 7, and it can be seen from fig. 6 to 7 that the carbon nanotubes form a network-shaped film in the form of a tube bundle, the surface of the tube bundle is wrapped with a large amount of surfactant, and the boundary is broken, so that the shape is changed.
(3) Light transmittance test: the self-supporting nanocarbon-based conductive macroscopic body obtained in example 16 was subjected to a light transmittance test.
The self-supporting nanocarbon-based conductive macroscopic body obtained in example 16 is shown in fig. 9, and the transmittance test is shown in fig. 10, so that the self-supporting nanocarbon-based conductive macroscopic body provided by the invention has good transmittance, and the transmittance at 550nm is 65%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A method of preparing a self-supporting nanocarbon-based conductive macroscopic body, comprising the steps of:
s1, mixing a carbon-based material, a sulfonic acid-based compound and a solvent, uniformly dispersing, and coating on a substrate to obtain a nano carbon-based conductive macroscopic body coated on the substrate;
s2, separating the nano carbon-based conductive macroscopic body from the substrate by using an acid solution to obtain a self-supporting nano carbon-based conductive macroscopic body;
The sulfonic acid group compound comprises one or more of dodecylbenzene sulfonic acid, perfluorinated sulfonic acid resin, polystyrene sulfonic acid and camphorsulfonic acid;
the acidic solution comprises one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, chloroauric acid solution, ferric chloride solution and chlorosulfonic acid solution.
2. The method for preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 1, wherein the mass ratio of the carbon-based material to the sulfonic acid-based compound is 1:2.5-20.
3. The method for preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 2, wherein the sulfonic acid-based compound comprises a perfluorosulfonic acid resin and camphorsulfonic acid in a mass ratio of 2:3-4:1.
4. The method of preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 1, wherein the carbon-based material comprises one or more of carbon nanotubes, carbon black, graphene, graphite;
the solvent comprises one or more of water, ethanol, isopropanol, methanol and propanol.
5. The method for preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 4, wherein the mass-to-volume ratio of the carbon-based material to the solvent is 1 mg/0.5-3 ml.
6. A method of preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 1, wherein the dispersion comprises ultrasonic dispersion or shear dispersion.
7. The method of preparing a self-supporting nanocarbon-based conductive macroscopic body of claim 1, wherein said coating comprises one of knife coating, spin coating, spray coating.
8. The method for preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 1, wherein the mass concentration of the acidic solution is 4% -99%.
9. The method for preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 8, wherein the amount of the acidic solution is 30-100 μl/cm 2 based on the area of the substrate.
10. The method of preparing a self-supporting nanocarbon-based conductive macroscopic body according to claim 9, wherein the acidic solution is a nitric acid solution with a mass concentration of 40%.
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| CN111293035A (en) * | 2018-12-07 | 2020-06-16 | 中国科学院物理研究所 | Preparation method of carbon nanotube film |
| CN111925697A (en) * | 2019-05-13 | 2020-11-13 | 中国科学院化学研究所 | Graphene/water-soluble polymer composite material and preparation method thereof |
| CN111748241A (en) * | 2020-06-19 | 2020-10-09 | 河北大学 | Ink for solar cell, and preparation method and application thereof |
| CN115767907A (en) * | 2022-11-22 | 2023-03-07 | 桂林电子科技大学 | Preparation process of flexible temperature-stress sensor and flexible sensor |
| CN116253918A (en) * | 2023-01-17 | 2023-06-13 | 中国科学院宁波材料技术与工程研究所 | Self-supporting polyaniline-based film and preparation method thereof |
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