CN112053806B - Preparation method of transparent heating film with nanosheet-nanowire composite structure - Google Patents
Preparation method of transparent heating film with nanosheet-nanowire composite structure Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 8
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- 238000004528 spin coating Methods 0.000 claims description 7
- 239000002042 Silver nanowire Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 6
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052582 BN Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 100
- 238000002834 transmittance Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
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- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The invention discloses a preparation method of a transparent heating film with a nanosheet-nanowire composite structure, which comprises the following steps: processing the transparent heating film substrate; coating the nanosheet dispersion liquid on the surface of one side of the treated substrate, and drying to form a nanosheet transparent film with the thickness of 2-20 nm on the substrate; coating the nano-wire dispersion liquid on the nano-sheet transparent film, and drying to form a nano-sheet-nano-wire composite structure transparent film with the thickness of 50-500 nm on the substrate; carrying out post-treatment on the transparent conductive film with the nanosheet-nanowire composite structure; and respectively sticking an electrode strip and a corresponding polyurethane protective layer at two ends of the treated transparent conductive film with the nano sheet-nano wire composite structure. The transparent heating film with the nanosheet-nanowire composite structure and improved photoelectric performance, heating performance and thermal stability can be obtained by adopting the method.
Description
Technical Field
The invention relates to the field of flexible electronics and thin film devices, in particular to a preparation method of a transparent heating thin film with a nanosheet-nanowire composite structure.
Background
The transparent conductive film has high transmittance and high conductivity in a visible light wave band, has wide application scenes in the fields of photoelectric devices and micro-electronics, and is applied to different devices such as organic light emitting diodes, thin-film solar cells, thin-film heating devices, photon and photoelectronic equipment, electromagnetic shielding equipment, wearable equipment and the like. With the rapid development of flexible electronics in the future, various flexible devices have an urgent need for transparent thin film heating devices. The currently used Indium Tin Oxide (ITO) material is mature as a heating thin film material, but also faces many problems. Indium tin oxide is used as a metal oxide, has relatively low conductivity, cannot further improve the heating performance of the film, has obvious brittleness and is not suitable for the application of flexible electrons; meanwhile, the production of indium tin oxide at present adopts modes such as sputtering and the like, a large amount of vacuum equipment is needed, and the cost is high; in addition, indium resources are relatively scarce, and material cost is becoming high. Therefore, it is of great significance to develop a new generation of flexible heating films with higher photoelectric and heating properties.
Compared with an indium tin oxide film, the flexible transparent heating film prepared from the one-dimensional nanowire material such as a silver nanowire or a carbon nanotube has better photoelectric property and bendability, has wide material sources, can be prepared in a large size and at low cost by adopting a solution method, and has great application potential in future flexible electronic devices. However, in the conductive network formed by the one-dimensional nanowires, the nanowires are mutually overlapped, the resistance of the contact part is large, which is not beneficial to further improvement of photoelectric performance and heating performance, and meanwhile, the heat generated at the overlapping part can only be conducted along the nanowires, so that the nanowires can be damaged when the power of the heating film is too high, and the heating film fails. In CN106131984A, a mode of alternately spin-coating silver nanowires and graphene is adopted to improve the thermal stability and heating performance of the heating film; but the process is complex and the production cost is high. CN104053256B adopts organic conductive polymer to improve the heating performance of the film, but the stability of the organic polymer is not enough, especially the stability is reduced under the heating condition, which is not beneficial to long-term application. Therefore, a method for preparing a transparent heating film, which is simple and convenient, has low cost, is suitable for large-scale solution production, and simultaneously enhances the photoelectric property, the heating property and the thermal stability of the film, is urgently needed.
Disclosure of Invention
The invention aims to provide a nano-sheet-nano wire composite structure transparent heating film for improving the performance of the transparent heating film.
In order to solve the technical problem, the invention provides a preparation method of a transparent heating film with a nanosheet-nanowire composite structure, which comprises the following steps:
1) and processing the transparent heating film substrate:
respectively carrying out ultrasonic cleaning treatment on the substrate in deionized water, ethanol and acetone, drying and then carrying out hydrophilic treatment to obtain a treated substrate;
2) and preparing the nanosheet transparent film:
coating a nanosheet dispersion solution with the concentration of 0.1-5 mg/mL on one side surface of the treated substrate obtained in the step 1), and drying to form a nanosheet transparent film with the thickness of 2-20 nm on the substrate;
3) and preparing the transparent conductive film with the nanosheet-nanowire composite structure:
coating the nano-wire dispersion liquid with the concentration of 1-10 mg/mL on the nano-sheet transparent film obtained in the step 2), and drying to form a nano-sheet-nano-wire composite structure transparent film with the thickness of 50-500 nm on the substrate;
4) and post-processing the transparent conductive film with the nanosheet-nanowire composite structure:
carrying out post-treatment on the product (without removing the substrate) obtained in the step 3) and drying to obtain a treated nano-sheet-nano-wire composite structure transparent conductive film;
5) and preparing the transparent heating film with the nanosheet-nanowire composite structure:
respectively sticking an electrode strip at two ends of the processed transparent conductive film with the nano sheet-nano wire composite structure obtained in the step 4), thereby realizing the conduction between the electrode and the transparent conductive film with the nano sheet-nano wire composite structure;
then arranging a polyurethane protective layer which can coat the electrode strips and the transparent conductive film with the nanosheet-nanowire composite structure; obtaining the transparent heating film with the nano-sheet-nano wire composite structure.
The improvement of the preparation method of the transparent heating film with the nano-sheet-nano wire composite structure comprises the following steps: in the step 2), the number of the layers of the nano sheets is less than or equal to 5 (a single layer or a few layers), and the sheet diameter is 0.5-50 μm;
the nano sheet is a two-dimensional nano material;
the solvent of the nano-sheet dispersion liquid is at least one (one or a mixture of several) of deionized water, ethanol, isopropanol, propylene glycol methyl ether, acetone, benzene, toluene, xylene, ethylene glycol, glycerol, DMF and NMP.
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows: the two-dimensional nano material is graphene, graphene oxide, reduced graphene oxide, Boron Nitride (BN) or molybdenum disulfide (MoS)2) Tungsten disulfide (WS)2) MXene materials (Ti)3C2、Ti2C、Nb2C、V2C、Mo2C)。
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows: in the step 3), the diameter of the nanowire is 5-200 nm, and the length of the nanowire is 0.5-100 mu m;
the nano wire is a one-dimensional nano material, a modified product of the one-dimensional nano material and a composite product of the one-dimensional nano material;
the solvent of the nanowire dispersion liquid is at least one (one or a mixture of several) of deionized water, ethanol, isopropanol, propylene glycol methyl ether, acetone, benzene, toluene, xylene, ethylene glycol, glycerol, DMF and NMP.
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows: the one-dimensional nano-wires are copper nano-wires, silver nano-wires, gold nano-wires and carbon nano-tubes.
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows: the post-treatment mode of the step 4) is at least one (one or a combination of several) of the following:
heat treatment (treatment in an oven at 120 ℃ for 10min), hot pressing (pressure 30MPa, temperature 50 ℃), hydrochloric acid treatment (concentration 0.5%, treatment for 30s), hydrazine hydrate solution treatment (concentration 30%, treatment for 100s), and silver ammonia solution treatment (concentration 0.05mol/L, treatment for 60 s).
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows: the thickness of the polyurethane protective layer is 100 +/-10 nm.
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows:
in the step 2), the coating mode is as follows: spin coating, blade coating, spray coating, ink jet printing or dip-draw methods.
In the step 3), the coating mode is as follows: spin coating, spray coating, ink jet printing or dip-draw methods.
The preparation method of the transparent heating film with the nano-sheet-nano wire composite structure is further improved as follows:
the transparent heating film substrate in the step 1) is a flexible or non-flexible substrate,
the flexible substrate is a PET substrate, a PEN substrate, a PI substrate, a PVA film, a PDMS film or other commercial transparent films;
the non-flexible substrate is a glass substrate.
In the present invention:
step 1): ultrasonic cleaning in deionized water, ethanol and acetone for 10-20 min (preferably 15 min); the hydrophilic treatment time is about 10-20 min.
The drying in the steps 2) and 3) of the invention comprises the following steps: naturally drying in the air, and then placing in a 120 ℃ oven for processing for 1.5-2.5 min.
The electrode strips are generally copper electrode strips with the width of 5 mm.
According to the invention, the two-dimensional nano sheet and the one-dimensional nano wire material are compounded, and the two-dimensional nano sheet material can improve the hydrophilic property of the substrate, thereby being beneficial to the uniform distribution of the nano wire material and improving the uniformity; meanwhile, the conductive two-dimensional nanowires can provide additional conductive paths, reduce the contact resistance among the nanowires, and improve the photoelectric property and the heating property; the two-dimensional nanosheets with good thermal conductivity can lead out heat generated at the overlapping positions of the nanowires in time and disperse the heat on the whole film, and the thermal stability of the composite heating film can be obviously improved. The transparent heating film with the nanosheet-nanowire composite structure is prepared by an all-solution method, and the method is simple and convenient and is easy to realize large-scale low-cost production.
Therefore, the transparent heating film with the nanosheet-nanowire composite structure and improved photoelectric performance, heating performance and thermal stability is obtained by constructing the nanosheet-nanowire composite structure.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Embodiment 1, a method for preparing a transparent heating film with a nanosheet-nanowire composite structure, sequentially performing the following steps:
1) treatment of transparent heating film substrates (conventional technique):
respectively carrying out ultrasonic treatment on a 10cm x 13cm PDMS substrate in deionized water, ethanol and acetone for 10-20 min (preferably 15min), drying (conventionally drying), and then carrying out hydrophilic treatment by using oxygen plasma for 15min (the flow is about 120mL/min) to obtain a treated PDMS substrate;
2) and preparing the nanosheet transparent film:
taking Ti3C2TxMXene (MXene) nanosheets, the diameter of each nanosheet is 5 microns, the solvent is isopropanol, MXene dispersion liquid with the concentration of 0.5mg/mL is prepared, the MXene dispersion liquid is sprayed on one side surface of a PDMS substrate after treatment, the surface is naturally dried in the air, and then the substrate is placed in an oven at 120 ℃ for treatment for 2min, so that a nanosheet transparent film with the thickness of 6nm is formed on the substrate;
3) and preparing the transparent conductive film with the nanosheet-nanowire composite structure:
taking silver nanowires (the diameter is 20nm, the length is 25 microns), using ethanol as a solvent, preparing silver nanowire dispersion liquid with the concentration of 2mg/mL, blade-coating the silver nanowire dispersion liquid on the nanosheet transparent film obtained in the step 2), naturally drying the nanosheet transparent film in the air, and then placing the nanosheet transparent film in an oven at 120 ℃ for 2min to form a nanosheet-nanowire composite structure transparent film with the thickness of 200nm on the substrate;
4) and post-processing the transparent conductive film with the nanosheet-nanowire composite structure:
immersing the whole obtained substance in the step 3) (i.e. the substrate is not removed) into a silver ammonia solution with the concentration of 0.05mol/L for treatment for 60s, naturally airing, and then carrying out hot pressing treatment at the pressure of 30MPa and the temperature of 50 ℃ to obtain the treated nano-sheet-nano wire composite structure transparent conductive film;
5) and preparing the transparent heating film with the nanosheet-nanowire composite structure:
respectively sticking a copper electrode strip with the width of 5mm at two ends of the treated nano sheet-nano wire composite structure transparent conductive film obtained in the step 4), so as to realize the conduction of the copper electrode and the nano sheet-nano wire composite structure transparent conductive film, and coating a polyurethane protective layer with the thickness of 100nm on the surfaces of the copper electrode strip and the nano sheet-nano wire composite structure transparent conductive film, namely the polyurethane protective layer can coat the electrode strip and the nano sheet-nano wire composite structure transparent conductive film; thereby obtaining the transparent heating film with the nano-sheet-nano wire composite structure.
The transparent heating film with the nano-sheet-nano-wire composite structure has the square resistance of 11 omega/sq, the transmittance of 83 percent and the heating power of 0.7W/cm2The heating temperature was 105 ℃.
Embodiment 2, a method for preparing a transparent heating film with a nanosheet-nanowire composite structure, which sequentially comprises the following steps:
1) and processing the transparent heating film substrate:
respectively carrying out ultrasonic treatment on a 5cm × 5cm glass substrate in deionized water, ethanol and acetone for 10-20 min (preferably 15min), drying, and then carrying out ultraviolet-ozone hydrophilic treatment for 15min (power 300W) to obtain a treated glass substrate;
2) and preparing the nanosheet transparent film:
taking graphene oxide, the sheet diameter of which is 20 microns, and a solvent of which is NMP (N-methyl pyrrolidone), preparing graphene oxide dispersion liquid with the concentration of 3mg/mL, taking about 2mL of the graphene oxide dispersion liquid, and spin-coating the graphene oxide dispersion liquid on a treated glass substrate at the rotation speed of 4000rpm for 60 s. Naturally airing in the air, and then placing in an oven at 120 ℃ for processing for 2min, thereby forming a nano-sheet transparent film with the thickness of 4nm on the substrate;
3) and preparing the transparent conductive film with the nanosheet-nanowire composite structure:
taking a carbon nano tube (the diameter is 10nm, the length is 20 mu m), using DMF as a solvent, preparing about 2mL of carbon nano tube dispersion liquid with the concentration of 8mg/mL, spin-coating the carbon nano tube dispersion liquid on the nano sheet transparent film obtained in the step 2), rotating at 2000rpm for 60s, naturally drying in the air, and then placing in an oven at 120 ℃ for processing for 2min, so that a nano sheet-nanowire composite structure transparent film with the thickness of 60nm is formed on the substrate;
4) and post-processing the transparent conductive film with the nanosheet-nanowire composite structure:
performing post-treatment on the nanosheet-nanowire composite structure transparent conductive film obtained in the step 3) by adopting a hydrazine hydrate solution, namely soaking the whole obtained material (without removing the substrate) in the step 3) into a hydrazine hydrate solution with the concentration of 30% for 100s, and then treating in an oven at 120 ℃ for 10min to obtain the treated nanosheet-nanowire composite structure transparent conductive film;
5) and preparing the transparent heating film with the nanosheet-nanowire composite structure:
respectively sticking a copper electrode strip with the width of 5mm at two ends of the processed transparent conductive film with the nanosheet-nanowire composite structure obtained in the step 4), so as to realize the conduction of the electrode and the transparent conductive film with the nanosheet-nanowire composite structure, and coating a polyurethane protective layer with the thickness of 100nm on the surfaces of the copper electrode strip and the transparent conductive film with the nanosheet-nanowire composite structure, so as to obtain the transparent heating film with the nanosheet-nanowire composite structure.
The transparent heating film with the nano-sheet-nano-wire composite structure has the square resistance of 50 omega/sq, the transmittance of 85 percent and the heating power of 0.3W/cm2The heating temperature was 55 ℃.
Embodiment 3, a method for preparing a transparent heating film with a nanosheet-nanowire composite structure, which sequentially comprises the following steps:
1) and processing the transparent heating film substrate:
respectively carrying out ultrasonic treatment on a PI substrate of 6cm multiplied by 10cm in deionized water, ethanol and acetone for 10-20 min (preferably 15min), drying (drying), and then carrying out ultraviolet-ozone hydrophilic treatment for 15min to obtain a treated PI substrate;
2) and preparing the nanosheet transparent film:
taking molybdenum disulfide (MoS) with the diameter of 0.8 mu m2) The solvent is ethanol, and the molybdenum disulfide (MoS) with the concentration of 12mg/mL is prepared2) The dispersion liquid is coated with molybdenum disulfide nanosheets on the treated PI substrate by a dip-coating method; drying (naturally drying in air), and then placing in a 120 ℃ oven for 2min, so as to form a nano-sheet transparent film with the thickness of 10nm on the substrate;
3) and preparing the transparent conductive film with the nanosheet-nanowire composite structure:
taking copper nanowires with the diameter of 40nm and the length of 50 microns, preparing copper nanowire dispersion liquid with the concentration of 1mg/mL by using toluene as a solvent, spraying the copper nanowire dispersion liquid on the nanosheet transparent film obtained in the step 2), drying (naturally drying in the air), and then placing the nanosheet transparent film in an oven at 120 ℃ for 2min to form a nanosheet-nanowire composite structure transparent film with the thickness of 450nm on the substrate;
4) and post-processing the transparent conductive film with the nanosheet-nanowire composite structure:
treating the nanosheet-nanowire composite structure transparent conductive film obtained in the step 3) in a drying oven at 120 ℃ for 10min to obtain a treated nanosheet-nanowire composite structure transparent conductive film;
5) and preparing the transparent heating film with the nanosheet-nanowire composite structure:
and (3) attaching copper electrode strips with the width of 5mm to two ends of the processed transparent conductive film with the nanosheet-nanowire composite structure obtained in the step 4), so as to realize the conduction of the electrodes and the transparent conductive film with the nanosheet-nanowire composite structure, and coating a polyurethane protective layer with the thickness of 100nm on the surfaces of the copper electrode strips and the transparent conductive film with the nanosheet-nanowire composite structure, so as to obtain the transparent heating film with the nanosheet-nanowire composite structure.
The transparent heating film with the nano-sheet-nano-wire composite structure has the square resistance of 8 omega/sq, the transmittance of 72 percent and the heating power of 0.8W/cm2And the heating temperature was 115 ℃.
Comparative example 1, step 2) was omitted, i.e., the silver nanowire dispersion was blade coated on the treated PDMS substrate; the rest is equivalent to embodiment 1.
The results obtained were: the transparent heating film had a sheet resistance of 33. omega./sq, a transmittance of 84% and a heating power of 0.4W/cm2The heating temperature was 70 ℃.
Comparative example 2, step 3) was eliminated, that is, the nanosheet transparent film obtained in step 2) was subjected to post-treatment, and the rest was identical to example 1.
The results obtained were: the transparent heating film has square resistance greater than 100 omega/sq, transmittance of 88% and no heating effect.
Comparative example 3, the sequence of step 2) and step 3) was interchanged, and the rest was identical to example 1.
The results obtained were: the transparent heating film has uneven silver nanowire distribution, square resistance of 21 omega/sq, transmittance of 84 percent and heating power of 0.5W/cm2The heating temperature was 85 ℃.
Comparative example 4 Ti of step 2) of example 13C2TxMXene (MXene) nanoplatelets modified to PEDOT: PSS, otherwise identical to example 1.
The results obtained were: the transparent heating film with the nano-sheet-nano-wire composite structure has the square resistance of 18 omega/sq, the transmittance of 82 percent and the heating power of 0.6W/cm2The heating temperature was 90 ℃.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. The preparation method of the transparent heating film with the nanosheet-nanowire composite structure is characterized by comprising the following steps of:
1) and processing the transparent heating film substrate:
respectively carrying out ultrasonic cleaning treatment on the substrate in deionized water, ethanol and acetone, drying and then carrying out hydrophilic treatment to obtain a treated substrate;
2) and preparing the nanosheet transparent film:
coating a nanosheet dispersion solution with the concentration of 0.1-5 mg/mL on one side surface of the treated substrate obtained in the step 1), and drying to form a nanosheet transparent film with the thickness of 2-20 nm on the substrate;
the number of the layers of the nano sheets is less than or equal to 5, and the sheet diameter is 0.5-50 mu m;
the nano sheet is a two-dimensional nano material;
the two-dimensional nano material is graphene, graphene oxide, reduced graphene oxide, boron nitride, molybdenum disulfide, tungsten disulfide or MXene material;
the solvent of the nano-sheet dispersion liquid is at least one of deionized water, ethanol, isopropanol, propylene glycol methyl ether, acetone, benzene, toluene, xylene, ethylene glycol, glycerol, DMF and NMP;
3) and preparing the transparent conductive film with the nanosheet-nanowire composite structure:
coating the nano-wire dispersion liquid with the concentration of 1-10 mg/mL on the nano-sheet transparent film obtained in the step 2), and drying to form a nano-sheet-nano-wire composite structure transparent film with the thickness of 50-500 nm on the substrate;
the diameter of the nanowire is 5-200 nm, and the length of the nanowire is 0.5-100 mu m;
the nano wire is a one-dimensional nano material, a modified product of the one-dimensional nano material or a composite product of the one-dimensional nano material;
the one-dimensional nano material is a copper nanowire, a silver nanowire, a gold nanowire or a carbon nanotube;
the solvent of the nanowire dispersion liquid is at least one of deionized water, ethanol, isopropanol, propylene glycol methyl ether, acetone, benzene, toluene, xylene, ethylene glycol, glycerol, DMF and NMP;
4) and post-processing the transparent conductive film with the nanosheet-nanowire composite structure:
carrying out post-treatment and drying on the product obtained in the step 3) to obtain a treated nano sheet-nano wire composite structure transparent conductive film;
5) and preparing the transparent heating film with the nanosheet-nanowire composite structure:
respectively sticking an electrode strip at two ends of the processed transparent conductive film with the nano sheet-nano wire composite structure obtained in the step 4), thereby realizing the conduction between the electrode and the transparent conductive film with the nano sheet-nano wire composite structure;
and then arranging a polyurethane protective layer capable of coating the electrode strips and the transparent conductive film with the nanosheet-nanowire composite structure to obtain the transparent heating film with the nanosheet-nanowire composite structure.
2. The preparation method of the nanosheet-nanowire composite structure transparent heating film according to claim 1, characterized in that: the post-treatment mode of the step 4) is at least one of the following modes: heating treatment, hot pressing treatment, hydrochloric acid treatment, hydrazine hydrate solution treatment and silver ammonia solution treatment.
3. The preparation method of the nanosheet-nanowire composite structure transparent heating film according to claim 2, wherein: the thickness of the polyurethane protective layer is 100 +/-10 nm.
4. The preparation method of the nanosheet-nanowire composite structure transparent heating film according to claim 3, wherein:
in the step 2), the coating mode is as follows: spin coating, blade coating, spray coating, ink-jet printing or dip-draw methods;
in the step 3), the coating mode is as follows: spin coating, spray coating, ink jet printing or dip-draw methods.
5. The preparation method of the nanosheet-nanowire composite structure transparent heating film according to claim 4, wherein: the transparent heating film substrate in the step 1) is a flexible or non-flexible substrate;
the flexible substrate is a PET substrate, a PEN substrate, a PI substrate, a PVA film or a PDMS film;
the non-flexible substrate is a glass substrate.
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| CN113411923B (en) * | 2021-06-16 | 2023-04-11 | 浙江希维纳米科技有限公司 | Method for protecting silver nanowire heating film |
| CN113976412A (en) * | 2021-10-26 | 2022-01-28 | 哈尔滨工业大学 | Ultrathin MXene film preparation method based on spin coating process |
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