CN114988474A - Tantalum disulfide film and preparation method thereof - Google Patents
Tantalum disulfide film and preparation method thereof Download PDFInfo
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- JAAVTMIIEARTKI-UHFFFAOYSA-N [S--].[S--].[Ta+4] Chemical compound [S--].[S--].[Ta+4] JAAVTMIIEARTKI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000000034 method Methods 0.000 claims description 43
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- 238000005119 centrifugation Methods 0.000 claims description 23
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 18
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- 230000010355 oscillation Effects 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000000703 high-speed centrifugation Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
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- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
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- 230000002776 aggregation Effects 0.000 claims description 5
- 238000004220 aggregation Methods 0.000 claims description 5
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- 229920000515 polycarbonate Polymers 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
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- 230000008569 process Effects 0.000 claims description 4
- 239000002055 nanoplate Substances 0.000 claims 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 57
- 239000005016 bacterial cellulose Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The preparation method of the tantalum disulfide film provided by the application comprises the step of mixing 2H-TaS 2 Mixing the nano-sheet dispersion liquid and the pre-acidified BC or ANFs solution to form TaS 2 /BC or TaS 2 /ANFs homodisperse, TaS 2 /BC or TaS 2 Preparing a composite film from the ANFs composite dispersion liquid through vacuum filtration; or will TaS 2 Preparation of Van der Waals-acting self-supporting pure TaS from nanosheet dispersion liquid through vacuum filtration 2 The tantalum disulfide film prepared by the preparation method has ultralow porosity, high tensile strength, Young modulus, toughness, conductivity and electromagnetic shielding efficiency, is simple, green and environment-friendly, and can be prepared on a large scale.
Description
Technical Field
The application relates to the technical field of nano material preparation, in particular to a tantalum disulfide film and a preparation method thereof.
Background
Transition Metal Dichalcogenides (TMDs) are a class of layered two-dimensional materials composed of transition metal elements and chalcogen elements that interact through weak van der waals forces (vdW). (nat. nanotechnol.2012,7,699; chem. Soc. Rev.2015,44,2702; adv. Mater.2021,33,2004557) TMD has a wide range of electrical properties, such as semiconductor (2H-MoS) 2 、1T-TaS 2 ) Semi-metal (1T-MoTe) 2 、1T-WTe 2 、1T-TiSe 2 ) And metal (2H-NbS) 2 、1T-MoS 2 、2H-TaS 2 ). (Science 2011,331,568) the different crystal structures, layer numbers, stacking order, defect control and unique two-dimensional morphology allow the TMD materials to have excellent physical, chemical, electronic and optical properties, which are of great interest in the fields of electrochemistry, sensors, supercapacitors and lithium ion batteries. (J.am.chem.Soc.2017,139, 4623; Joule 2019,3, 338; adv.Mater.2018,30,1705916) tantalum disulfide (TaS) 2 ) Is a popular TMDs material, 2H-TaS 2 Metallic behavior with Charge Density Wave (CDW) phase transition (TCDW 75K) and superconductivity (Tc 0.8K). (npj Quantum. Mater.2017,2, 1; Small 2020,16,1901901) their unique electrical properties make them ideal materials for exploring the effects of electrical conductivity on EMI shielding performance. It is well known that high quality 2D materials must be subjected to a lift-off process to fully develop their potential. 2H-TaS 2 Exfoliation can be performed by high boiling point solvents, (j.phys.chem.c 2016,120,3929) electrochemical, (nat.protoc.2022,17,358) n-butyllithium intercalation, (j.am.chem.soc.2017,139,9019) and mechanical milling, (adv.funct.mater.2020,30,2004139) and the like. However, these methods suffer from low efficiency, poor reproducibility and extreme environmental sensitivity, and more seriously, the stacked nanosheets will have poor electron mobility and significantly reduced macroscopic conductivity due to solvent residues. Due to the lack of surface polar functional groups (e.g. -F, ═ O, -OH), TMDs nanosheets can only be re-stacked by vdW. And a high-performance macroscopic structure can not be obtained by bridging between the nanosheets and the material containing polar groups through hydrogen bonds or covalent bonds. Furthermore, nanoplateletsThe transverse dimensions of (a) also have a significant impact on film production, however, the production of high quality and large scale nanoplatelets is often in low yields and requires a great deal of effort. The development of flexible, high strength, and highly conductive TMDs films remains a challenge, limiting their application in the field of electronic devices.
Therefore, there is a need to develop TaS 2 Novel method for preparing nanosheets, obtaining high quality TaS having a large transverse dimension and a small number of layers 2 Nanosheet and capable of retaining 2H-TaS 2 The electrical property of the metallic state is effectively enhanced by the TaS 2 Interface strength between nanosheets and interlayer pores are eliminated, so that TaS is greatly improved 2 Mechanical and electrical properties of the self-supporting thin film. Furthermore, TaS is produced by electrostatic interaction 2 The nano sheet is compounded with Bacterial Cellulose (BC) or Aramid Nano Fibers (ANFs) to prepare the composite film with high mechanical property and good electrical property. At present, flexible pure TaS with ultralow porosity, ultrahigh mechanical property, electric conductivity and electromagnetic shielding effect is not found 2 Relevant literature and patent reports of self-supporting thin films, TaS of high mechanical strength and conductivity and electromagnetic shielding effectiveness 2 Reports related to the composite film of the nanosheet and Bacterial Cellulose (BC) or Aramid Nanofibers (ANFs) are not found.
Disclosure of Invention
In view of this, it is necessary to provide a method for preparing a tantalum disulfide thin film having good flexibility, ultra-low porosity, high tensile strength, young's modulus, toughness, electrical conductivity, and electromagnetic shielding effect, aiming at the defects existing in the prior art.
In order to solve the above problems, the following technical solutions are adopted in the present application:
one of the purposes of the application is to provide a preparation method of a tantalum disulfide film, which comprises the following steps:
preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is a few-layer nano-sheet;
protonating the aqueous dispersion of BC or ANFs with inorganic acid, and mixing with TaS with different concentrations 2 Mixing the aqueous dispersions to obtain different mass ratiosTaS of 2 BC or TaS 2 ANFs heterogeneous aggregated dispersions;
the TaS with different mass ratios is added 2 /BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 /ANFs composite films.
In some of these embodiments, different concentrations of TaS are configured 2 The step of dispersing the aqueous dispersion specifically includes the steps of:
adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is mechanically dispersed at room temperature 2 Configured as uniform TaS 2 An aqueous dispersion.
In some of these embodiments, the high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The alkaline solvent comprises n-hexylamine or ammonia water.
In some embodiments, the intercalation time of the intercalation treatment is 6-12 h, the volume of the intercalation agent is 1-2 mL, and inert gas is required to be introduced during intercalation.
In some embodiments, the centrifugation speed of the high-speed centrifugation is 8000-12000 rpm, the centrifugation times are 3-5 times, each time of centrifugation is 10-30 min until the pH of the supernatant is 7, and the TaS after the high-speed centrifugation is finished 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
In some embodiments, the mechanical dispersion method comprises ultrasonic dispersion, vortex oscillation dispersion or ultrasonic and vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the vortex oscillation dispersion gear is 4-7 gears, and the time is 0.5-2 h.
In some of these examples, aqueous dispersions of BC or ANFs are protonated with mineral acids and then treated with varying concentrations of the TaS 2 Mixing the aqueous dispersions to obtain TaS with different mass ratios 2 /BC or TaS 2 ANFs heterogeneous agglomerated dispersionsIn the step (b), the inorganic acid comprises sulfuric acid, hydrochloric acid and nitric acid, and the concentration after protonation is 0.01-1 mol L -1 The protonation time is 0.5-2 h.
In some of these embodiments, the TaS of different mass ratios will be described 2 /BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 The method for preparing the ANFs composite film comprises the following steps:
the TaS with different mass ratios is added 2 /BC or TaS 2 Vacuum-filtering the ANFs heterogeneous aggregation dispersion liquid, adding 10-50 mL of deionized water, and carrying out vacuum drying on a vacuum-filtering membrane to finally obtain the TaS 2 BC or TaS 2 /ANFs composite films.
In some of the embodiments, the vacuum filtration membrane is selected from a mixed cellulose filtration membrane or a polyethersulfone filtration membrane.
In some embodiments, the vacuum drying is performed under a negative pressure of 0.08-0.1 MPa, at a drying temperature of 50-90 ℃ for 9-15 h.
In some of these embodiments, the TaS 2 /BC or TaS 2 the/ANFs composite film is circular and has a thickness of 1-30 μm.
The second object of the present application is to provide a tantalum disulfide film, which is prepared by the preparation method of the tantalum disulfide film, wherein the tantalum disulfide film comprises TaS 2 Nanoplatelets, BC or ANFs.
The third objective of the present application provides a method for preparing a tantalum disulfide thin film, comprising the following steps:
preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is a few-layer nano-sheet;
(ii) bringing different concentrations of said TaS 2 And carrying out vacuum filtration on the aqueous dispersion, and then carrying out vacuum drying to obtain the tantalum disulfide films with different thicknesses.
In some of these embodiments, different concentrations of TaS are provided 2 The step of dispersing the aqueous dispersion specifically includes the steps of:
adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is mechanically dispersed at room temperature 2 Configured as uniform TaS 2 An aqueous dispersion.
In some of these embodiments, the high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The basic solvent comprises n-hexylamine or ammonia water.
In some embodiments, the intercalation time of the intercalation treatment is 6-12 h, the volume of the intercalation agent is 1-2 mL, and inert gas is required to be introduced during intercalation.
In some embodiments, the centrifugation speed of the high-speed centrifugation is 8000-12000 rpm, the centrifugation times are 3-5 times, each centrifugation time is 10-30 min until the pH of the supernatant is-7, and the TaS after the high-speed centrifugation is finished 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
In some embodiments, the mechanical dispersion method comprises ultrasonic dispersion, vortex oscillation dispersion or ultrasonic and vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the vortex oscillation dispersion gear is 4-7 gears, and the time is 0.5-2 h.
In some of these embodiments, the TaS is added at different concentrations 2 In the step of obtaining the tantalum disulfide films with different thicknesses by vacuum drying after vacuum filtration of the aqueous dispersion, a polycarbonate filter membrane or a mixed cellulose filter membrane is selected as a vacuum filtration membrane, the negative pressure range of vacuum drying is 0.08-0.1 MPa, the drying temperature is 50-90 ℃, and the drying time is 9-15 hours.
In some embodiments, the tantalum disulfide film is circular and has a thickness in the range of 1-40 μm.
The fourth objective of the application is to provide a tantalum disulfide film prepared by the preparation method of the tantalum disulfide film, wherein the tantalum disulfide film comprises TaS 2 Nanosheets.
This application adopts above-mentioned technical scheme, its beneficial effect as follows:
the preparation method of the tantalum disulfide film provided by the application comprises the step of adding 2H-TaS 2 Mixing the nano-sheet dispersion liquid with a Bacterial Cellulose (BC) or aramid nano-fiber (ANFs) solution which is pre-acidified to obtain TaS 2 /BC or TaS 2 /ANFs homodisperse, TaS 2 /BC or TaS 2 Preparing TaS with electrostatic interaction by using ANFs composite dispersion liquid through vacuum filtration 2 Cellulose composite film or TaS 2 Preparation of Van der Waals-acting self-supporting pure TaS from nanosheet dispersion liquid through vacuum filtration 2 A film; the preparation method is simple, green and environment-friendly, can be used for large-scale preparation, and the prepared TaS 2 /BC or TaS 2 the/ANFs composite film has enhanced tensile strength and good conductivity, and shows good shielding effectiveness in the frequency band of 8.2-12.4 GHz; the prepared self-supporting pure TaS 2 The internal porosity of the film is 6.01 percent, the tensile strength is 23.3 +/-4.8 MPa, the Young modulus is 14.9 +/-6.2 GPa, and the toughness is 0.033 +/-0.018 MJ m -3 The conductivity is 2666S cm -1 The shielding effectiveness for electromagnetic wave with frequency of 8.2-12.4 GHz is 41.8dB (thickness is 3.1 μm), and the absolute shielding effectiveness SSE/t is 27,859dB cm 2 g -1 。
The application provides a tantalum disulfide film, is applicable to emerging electronic equipment fields that rely on two-dimensional nano-material performance such as electromagnetic shield, flexible electron, super capacitor.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments of the present application or the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Figure 1 is a flow chart illustrating the steps of a method for forming a tantalum disulfide film according to one embodiment of the present disclosure.
Figure 2 is a flow chart illustrating the steps of a method for forming a tantalum disulfide film according to another embodiment of the present invention.
FIG. 3 shows TaS prepared in example 1 of the present application 2 A nanosheet aqueous dispersion. In the figure, A represents a concentration of 1.25mg mL - 1 TaS 2 A nanosheet aqueous dispersion; in the figure, B represents 0.1mg mL -1 TaS 2 Obvious Tyndall phenomenon can be observed in the nano sheet water dispersion.
FIG. 4 shows TaS prepared in example 1 of the present application 2 Nanosheet scanning electron microscopy (TEM) morphology (A), atomic microscopy (AFM) thickness analysis (B), selected area electron diffraction (SEAD) images (C) and X-ray diffraction (XRD) curves (D). In the figure, A shows TaS 2 The nanoplatelets have a large lateral dimension; in the figure, TaS obtained by AFM test 2 The thickness of the nanosheet is 1.75 nm; in the figure C shows TaS 2 The nano sheet has good crystallinity, and a defect structure is formed on the surface of the nano sheet; in the figure, D TaS 2 Half-peak width ratio 2H-TaS of 002 peak of nano sheet 2 The half-peak width of the 002 peak of the crystal is large, and TaS 2 The 2 theta value ratio of 002 peaks of the nanosheets is 2H-TaS 2 The crystals are small, indicating successful exfoliation of the nanoplatelets.
FIG. 5 shows pure TaS having a thickness of 3.1 μm prepared in examples 1, 2 and 3 of the present application 2 Self-supporting film (A, B, C), TaS 2 (ii) BC (10:5) (D, E, F) and TaS 2 Scanning Electron Microscope (SEM) pictures and three-dimensional reconstruction models of/ANFs (10:5) (G, H, I) composite thin film Focused Ion Beam (FIB) cut sections. In the figure, A represents TaS having a thickness of 3.1 2 Cross-sectional view of the self-supporting film, B represents three-dimensionally reconstituted pores wherein the porosity is 6.01%, and C represents three-dimensionally reconstituted TaS 2 (ii) a In the figure, D represents TaS 2 Cross-sectional view of the/BC (10:5) composite film, showing that the BC and TaS are randomly distributed in the laminate 2 E denotes BC (volume ratio of 30.78%) for three-dimensional reconstruction, and F denotes TaS for three-dimensional reconstruction 2 (ii) a In the figure, G represents TaS 2 Section view of/ANFs (10:5) composite film, and randomly distributed ANFs and TaS can be seen in stacking 2 E represents three-dimensional reconstructed ANFs (volume fraction of 39.81%), and F represents three-dimensional reconstructed TaS 2 。
FIG. 6 shows that pure TaS was obtained in examples 1, 2 and 3 of the present application 2 Self-supportingSupporting film (A) and TaS with different content ratios 2 /BC (B-F)) and TaS 2 ANFs (G-K)) composite film tensile stress-strain curve. In the figure, A to K each include the test results of 3 groups of samples.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present application and should not be construed as limiting the present application.
In the description of the present application, it is to be understood that the terms "upper", "lower", "horizontal", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments.
Referring to fig. 1, a flow chart of steps of a method for preparing a tantalum disulfide film according to an embodiment of the present application includes the following steps S110 to S130, and implementation of the steps is described in detail below.
Step S110: preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is a few-layer nano-sheet.
In some of these embodiments, different concentrations of TaS are provided 2 The step of dispersing the aqueous dispersion specifically includes the steps of: adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is dispersed mechanically at room temperature 2 Configured as uniform TaS 2 An aqueous dispersion.
In some of these embodiments, the high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The basic solvent comprises n-hexylamine or ammonia water.
It can be understood that 2H-TaS is due to the two-dimensional material 2 Shows a metallization behavior and has good electrical conductivity. The high-quality 2D material can fully exert the potential thereof only through stripping treatment, the stripping method and the quality of the stripped nano sheets can seriously influence the macroscopic mechanical property and the electrical property of the nano sheets after being re-stacked, and TaS with different concentrations is prepared by the method 2 The aqueous dispersion step adopts a high-concentration alkali metal ion aqueous solution, so that the reduction of the conductivity caused by the residue of a high-boiling point solvent is avoided, and the high-concentration alkali metal ion can be converted into TaS 2 A large amount of electrons are injected into the nano-sheets, so that TaS is obtained 2 Maintaining the 2H phase with high conductivity while causing TaS 2 Nanosheet defects enhance out-of-plane electron and ion transport.
In some embodiments, the intercalation time of the intercalation treatment is 6-12 h, the volume of the intercalation agent is 1-2 mL, and inert gas is required to be introduced during intercalation.
It can be understood that the application adopts a mild and feasible intercalation strategy to prepare the 2H-TaS with the surface defect structure in the environment-friendly alkali metal ion aqueous solution 2 The efficiency and safety of the nano-sheet are higher than those of the common methods (such as mechanical grinding, n-butyl lithium intercalation and electrochemistry) to obtain TaS 2 The lateral dimension of the nano-sheet is between 0.5 and 11 mu m, and the thickness of the nano-sheet is about 1.74 nm.
In some of these embodiments, the high speed centrifugal separationThe heart speed is 8000-12000 rpm, the centrifugation times are 3-5 times, the centrifugation time is 10-30 min each time until the pH of the supernatant is about 7, and the TaS after high-speed centrifugation 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
In some embodiments, the mechanical dispersion method comprises ultrasonic dispersion, vortex oscillation dispersion or ultrasonic and vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the vortex oscillation dispersion gear is 4-7 gears, and the time is 0.5-2 h.
Step S120: protonating the aqueous dispersion of Bacterial Cellulose (BC) or aramid nano-fibers (ANFs) by using inorganic acid, and then mixing the aqueous dispersion with the TaS with different concentrations 2 Mixing the aqueous dispersions to obtain TaS with different mass ratios 2 /BC or TaS 2 ANFs heterogeneous aggregated dispersions.
For example: according to TaS 2 Corresponding to the content ratio of the nano fibers (BC or ANFs) to prepare TaS 2 the/BC composite films are respectively marked as TaS 2 /BC(10:1)、TaS 2 /BC(10:2)、TaS 2 /BC(10:3)、TaS 2 /BC(10:4)、TaS 2 BC (10:5), corresponding to TaS 2 the/ANFs composite films are respectively marked as TaS 2 /ANFs(10:1)、TaS 2 /ANFs(10:2)、TaS 2 /ANFs(10:3)、TaS 2 /ANFs(10:4)、TaS 2 /ANFs(10:5)。
In some of these examples, aqueous dispersions of BC or ANFs are protonated with mineral acids and then treated with varying concentrations of the TaS 2 Mixing the aqueous dispersions to obtain TaS with different mass ratios 2 BC or TaS 2 In the step of ANFs heterogeneous aggregation dispersion liquid, the inorganic acid comprises sulfuric acid, hydrochloric acid and nitric acid, and the concentration after protonation treatment is 0.01-1 mol L -1 The protonation time is 0.5-2 h.
It will be appreciated that aqueous dispersions of BC or ANFs are protonated with mineral acids for a period of time and then contacted with varying concentrations of TaS 2 Mixing the aqueous dispersion, dispersing sufficiently, and subjecting the TaS to electrostatic force 2 Nano-sheetCan be gathered and adsorbed on bacterial cellulose or aramid nano-fiber to obtain TaS 2 /BC or TaS 2 Heterogeneous aggregated dispersions of ANFs.
In some of the examples, the inorganic acid is selected from the group consisting of sulfuric acid, hydrochloric acid and nitric acid, preferably hydrochloric acid, and the final concentration after protonation is 0.01 to 1mol L -1 Wherein the preferred concentration is 0.01mol L -1 . The range of protonation treatment is 0.5-2 h, and 0.5h is preferred.
It can be understood that TaS 2 The nanoplatelets are further combined with polymer fibers of BC and ANFs to significantly improve the tensile strength and flexibility of the film while still having high electrical conductivity and EMI SE.
Step S130: the TaS with different mass ratios is added 2 /BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 /ANFs composite films.
In some of these embodiments, the TaS of different mass ratios will be described 2 /BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 The method for preparing the ANFs composite film comprises the following steps: the TaS with different mass ratios is added 2 /BC or TaS 2 Vacuum-filtering the ANFs heterogeneous aggregation dispersion liquid, adding 10-50 mL of deionized water, and carrying out vacuum drying on a vacuum-filtering membrane to finally obtain the TaS 2 BC or TaS 2 /ANFs composite films.
In some of the examples, the vacuum filtration membrane is selected from a mixed cellulose filter (Brand of Jinteng or Shanghai Xinya, pore size of 0.22 μm) or a polyethersulfone filter (Brand of Labfilter, pore size of 0.22 μm).
In some embodiments, the vacuum drying is performed under a negative pressure of 0.08-0.1 MPa, preferably under a negative pressure of 0.1MPa, at a drying temperature of 50-90 ℃, preferably at a drying temperature of 50 ℃, for 9-15 h, preferably for 10 h.
In some of these embodiments, the TaS 2 /BC or TaS 2 the/ANFs composite film is circular and has a thickness of 1-30 μm.
The preparation method of the tantalum disulfide film provided by the embodiment of the application is simple, green and environment-friendly, can be used for large-scale preparation, and the prepared TaS 2 /BC or TaS 2 the/ANFs composite film has enhanced tensile strength and good conductivity, shows good shielding effectiveness in the frequency band of 8.2-12.4 GHz, and is suitable for the fields of emerging electronic equipment which depend on the performance of two-dimensional nano materials, such as electromagnetic shielding, flexible electronics, super capacitors and the like.
Referring to fig. 2, a flow chart of steps of a method for preparing a tantalum disulfide film according to another embodiment of the present application includes the following steps S210 to S220, and the implementation of each step is described in detail below.
Step S210: preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is a few-layer nano-sheet.
In some of these embodiments, different concentrations of TaS are provided 2 The step of dispersing the aqueous dispersion specifically includes the steps of: adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is dispersed mechanically at room temperature 2 Configured as a uniform TaS 2 An aqueous dispersion.
In some of these embodiments, the high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The basic solvent comprises n-hexylamine or ammonia water.
It is understood that the present application is directed to the formulation of TaS at various concentrations 2 In the step of the aqueous dispersion, a high-concentration alkali metal ion aqueous solution is adopted as a solvent, so that the problem of reduced conductivity caused by the residue of a high-boiling-point solvent is avoided, and the high-concentration alkali metal ion can be converted into TaS 2 A large amount of electrons are injected into the nano-sheets, so that TaS is obtained 2 Maintaining the 2H phase with high conductivity while causing TaS 2 Nanosheet defects enhance out-of-plane electron and ion transport.
In some embodiments, the intercalation time of the intercalation treatment is 6-12 h, the volume of the intercalation agent is 1-2 mL, and inert gas is required to be introduced during intercalation.
It can be understood that the application adopts a mild and feasible intercalation strategy to prepare the 2H-TaS with the surface defect structure in the environment-friendly alkali metal ion aqueous solution 2 The efficiency and safety of the nano-sheet are higher than those of the common methods (such as mechanical grinding, n-butyl lithium intercalation and electrochemistry) to obtain TaS 2 The lateral dimension of the nano-sheet is between 0.5 and 11 mu m, and the thickness of the nano-sheet is about 1.74 nm.
In some embodiments, the centrifugation speed of the high-speed centrifugation is 8000-12000 rpm, the centrifugation times are 3-5 times, each time of centrifugation is 10-30 min until the pH of a supernatant is about 7, and TaS after the high-speed centrifugation is performed 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
In some embodiments, the mechanical dispersion method comprises ultrasonic dispersion, vortex oscillation dispersion or ultrasonic and vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the vortex oscillation dispersion gear is 4-7 gears, and the time is 0.5-2 h.
Step S220: (ii) bringing different concentrations of said TaS 2 And carrying out vacuum filtration on the aqueous dispersion, and then carrying out vacuum drying to obtain the tantalum disulfide films with different thicknesses.
In some of these embodiments, the TaS is added at different concentrations 2 In the step of obtaining the tantalum disulfide films with different thicknesses by vacuum drying after vacuum filtration of the aqueous dispersion, a polycarbonate filter membrane (brand: Whatman or GVS, aperture of 0.2 μm) or a mixed cellulose filter membrane (brand: Jinteng or Shanghai Xinya, aperture of 0.22 μm) is selected as the vacuum filtration membrane, wherein the polycarbonate filter membrane is preferred.
The negative pressure range of the vacuum drying is 0.08-0.1 MPa, wherein the preferable negative pressure is 0.09MPa, the drying temperature is 50-90 ℃, the preferable drying temperature is 50 ℃, the drying time is 9-15 h, and the preferable drying time is 10 h.
In some embodiments, the tantalum disulfide film is circular and has a thickness in the range of 1-40 μm.
It will be appreciated that different concentrations of the TaS will be used 2 Vacuum filtration of the aqueous dispersion, with the filtration proceeding, TaS 2 And re-stacking the nanosheets under the action of Van der Waals force, and then drying in vacuum to obtain the tantalum disulfide thin films with different thicknesses. TaS 2 The film has good flexibility, high tensile rate and high conductivity through van der waals force interaction, the suction filtration time of the over-thick film is greatly prolonged due to the increase of the content of the nanosheets, and more pores are formed between layers, so that the density and the performance are not improved; the thin film is not easy to peel off from the filter membrane.
The self-supporting pure TaS prepared by the above embodiments of the present application 2 The internal porosity of the film is 6.01 percent, the tensile strength is 23.3 +/-4.8 MPa, the Young modulus is 14.9 +/-6.2 GPa, and the toughness is 0.033 +/-0.018 MJ m -3 The conductivity is 2666S cm -1 The shielding effectiveness for electromagnetic wave with frequency of 8.2-12.4 GHz is 41.8dB (thickness is 3.1 μm), and the absolute shielding effectiveness SSE/t is 27,859dB cm 2 g -1 The method is suitable for the fields of emerging electronic equipment which depend on the performance of two-dimensional nano materials, such as electromagnetic shielding, flexible electronics, super capacitors and the like.
The above technical solutions of the present application will be described in detail with reference to specific examples.
Example 1
Prepare 1.25mg mL -1 TaS 2 Nanosheet aqueous dispersion: tantalum disulfide (2H-TaS) is reacted at room temperature 2 ) The powder (0.1g) was mixed with lithium hydroxide solution (1mL, 2M) in a centrifuge tube, and intercalated for 9h with nitrogen. The final mixture was then washed 3 times with deionized water by centrifugation at 12000rpm for 15 minutes until the supernatant had a pH of about 7. Subsequently, the resulting precipitate was diluted with 80mL of deionized water and sonicated in an ice bath for 1 hour. Finally, TaS is obtained without centrifugation 2 Aqueous nanosheet dispersion (1.25mg mL) -1 ) As shown in fig. 3 (a).
20mL of the solution is taken, and the concentration is 1.25mg mL -1 TaS 2 Dropwise adding the nanosheet aqueous dispersion into a vacuum filtration bottle, starting a vacuum pump to perform vacuum filtration, wherein the filter membrane is a polycarbonate filter membrane,make TaS 2 The layer under the condition of negative pressure is assembled to form TaS 2 Stacking the nano sheets to form a film, transferring the film after suction filtration and the filter membrane together into a vacuum drying oven with the negative pressure of 0.09MPa and the temperature of 50 ℃ for drying for 10h to finally obtain pure TaS with the van der Waals force action 2 A free-standing film of said pure TaS 2 The self-supporting film had a diameter of about 4cm and a thickness of about 3.1 μm.
Please refer to fig. 3, which shows TaS prepared in example 1 of the present application 2 Nanosheet scanning electron microscopy (TEM) morphology, atomic microscope (AFM) thickness analysis, selected area electron diffraction (SEAD) images and X-ray diffraction (XRD) curves.
Referring to FIG. 5 and FIG. 6, the pure TaS with a thickness of 3.1 μm 2 The self-supporting film has the porosity of only 6.01 percent, the tensile strength of 23.3 +/-4.8 MPa, the Young modulus of 14.9 +/-6.2 GPa and the toughness of 0.033 +/-0.018 MJ m -3 The electrical conductivity was 2666S cm -1 (ii) a The electromagnetic shielding effectiveness is 41.8dB and the absolute electromagnetic shielding effectiveness is 27,859dB cm in the frequency range of 8.2-12.4 GHz in the X wave band 2 g -1 。
The following table, flexible pure TaS prepared as described in this example 2 The self-supporting film conductivity is superior to the TaS reported in the literature at present 2 A base film.
Example 2
1.25mg mL of a solution was prepared -1 TaS 2 Nanosheet aqueous dispersion: at room temperature, tantalum disulfide (2H-TaS) 2 ) The powder (0.1g) was mixed with lithium hydroxide solution (1mL, 2M) in a centrifuge tube and intercalated for 9h with nitrogen. The final mixture was then washed 3 times with deionized water by centrifugation at 12000rpm for 15 minutes until the supernatant had a pH of about 7. Subsequently, the resulting deposit was diluted with 80mL of deionized water and sonicated in an ice bath for 1 hour. Finally, TaS is obtained without centrifugation 2 Aqueous nanosheet dispersion (1.25mg mL) -1 ) As shown in fig. 3 (a).
Bacterial Cellulose (BC) dispersion (0.5g,1 wt%) was taken and HCl solution (0.5mL,1mol L) was added -1 ) Protonation for 30 min. Followed by mixing with freshly prepared 40mL 1.25mg mL -1 TaS 2 Mixing the nano-sheet water dispersion, and fixing the volume to 50mL by using deionized water, wherein the final HCl concentration is 0.01mol L -1 And sonicated for 1min prior to use. Using a polyethersulfone membrane as a filtration membrane, after shaking by hand for 1 minute, the TaS was removed 2 the/BC mixed dispersion was subjected to vacuum filtration and washed with 10mL of deionized water to prepare TaS 2 the/BC composite film is dried in a vacuum drying oven (50 ℃, negative pressure of 0.1MPa) for 10 hours to form independent TaS 2 the/BC (10:1) composite film. The TaS 2 the/BC (10:1) composite film had a diameter of about 4cm and a thickness of about 9.9 μm.
Referring to FIG. 5 and FIG. 6, the TaS 2 The tensile strength of the/BC (10:1) composite film is 31.7 +/-2.8 MPa, the Young modulus is 8.7 +/-0.9 GPa, and the toughness is 0.066 +/-0.017 MJ m -3 The conductivity is 1435S cm -1 (ii) a The electromagnetic shielding effectiveness is 48.0dB and the absolute electromagnetic shielding effectiveness is 13,774dB cm in the frequency range of 8.2-12.4 GHz in the X wave band 2 g -1 。
Example 3
1.25mg mL of a solution was prepared -1 TaS 2 Nanosheet aqueous dispersion: tantalum disulfide (2H-TaS) is reacted at room temperature 2 ) The powder (0.1g) was mixed with lithium hydroxide solution (1mL, 2M) in a centrifuge tube and intercalated for 9h with nitrogen. The final mixture was then washed 3 times with deionized water by centrifugation at 12000rpm for 15 minutes until the supernatant had a pH of about 7. Subsequently, the resulting precipitate was diluted with 80mL of deionized water and sonicated in an ice bath for 1 hour. Finally, TaS is obtained without centrifugation 2 Aqueous nanosheet dispersion (1.25mg mL) -1 ) As shown in fig. 3 (a).
Taking aramid Nano-fiber (ANFs) dispersion liquid (preparation method according to reference ACS Nano 2019,13, 7886; 1.1g,0.455 wt%), and adding HCl solution (0.5mL,1mol L) -1 ) Protonation for 30 min. Followed by mixing with freshly prepared 40mL 1.25mg mL -1 TaS 2 Mixing the nano-sheet aqueous dispersion, and using deionized waterThe water volume is fixed to 50mL, namely the final HCl concentration is 0.01mol L -1 And sonicated for 1min prior to use. Using a polyethersulfone membrane as a filtration membrane, after shaking by hand for 1 minute, the TaS was removed 2 the/ANFs Mixed Dispersion supernatant was vacuum filtered and the pre-prepared TaS was rinsed with 10mL deionized water 2 the/ANFs composite film is dried in a vacuum drying oven (50 ℃, negative pressure of 0.1MPa) for 10 hours in vacuum to form independent TaS 2 Composite films of/ANFs (10: 1). The TaS 2 the/ANFs (10:1) composite film had a diameter of about 4cm and a thickness of about 10 μm.
Referring to FIG. 5 and FIG. 6, the TaS 2 The composite film of/ANFs (10:1) has tensile strength of 40.7 +/-0.8 MPa, Young's modulus of 8.09 +/-0.31 GPa and toughness of 0.134 +/-0.009 MJ m -3 The conductivity was 1517S cm -1 (ii) a The electromagnetic shielding effectiveness is 46.8dB and the absolute electromagnetic shielding effectiveness is 14,182dB cm in the frequency range of 8.2-12.4 GHz in the X wave band 2 g -1 。
It is to be understood that various features of the above-described embodiments may be combined in any combination, and for the sake of brevity, all possible combinations of features in the above-described embodiments may not be described in detail, but rather, all combinations of features may be considered to fall within the scope of the present disclosure unless there is a conflict between such combinations.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented only for the purpose of illustrating the principles of the invention and not in any way to limit its scope. Any modifications, equivalents and improvements made within the spirit and principles of the present application and other embodiments of the present application without the exercise of inventive faculty will occur to those skilled in the art and are intended to be included within the scope of the present application.
Claims (21)
1. A preparation method of a tantalum disulfide film is characterized by comprising the following steps:
preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is to be lessA layer of nanoplates;
protonating the aqueous dispersion of BC or ANFs by using inorganic acid, and mixing with the TaS with different concentrations 2 Mixing the aqueous dispersions to obtain TaS with different mass ratios 2 /BC or TaS 2 Heterogeneous aggregated dispersions of ANFs;
the TaS with different mass ratios is added 2 BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 /ANFs composite films.
2. The method of claim 1, wherein different concentrations of TaS are provided 2 The step of dispersing the aqueous dispersion specifically includes the steps of:
adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is mechanically dispersed at room temperature 2 Configured as uniform TaS 2 An aqueous dispersion.
3. The method of claim 2, wherein said high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The alkaline solvent comprises n-hexylamine or ammonia water.
4. The method for preparing a tantalum disulfide film according to claim 2, wherein the intercalation time of the intercalation process is 6-12 h, the volume of the intercalation agent is 1-2 mL, and an inert gas is introduced during intercalation.
5. The method for preparing the tantalum disulfide film according to claim 2, wherein the centrifugation speed of the high-speed centrifugation is 8000-12000 rpm, the centrifugation times are 3-5 times, the centrifugation time is 10-30 min each time until the pH of the supernatant is 7, and the TaS after the high-speed centrifugation is performed 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
6. The method of claim 2, wherein the mechanical dispersion comprises ultrasonic dispersion, vortex oscillation dispersion or ultrasonic and vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the vortex oscillation dispersion gear is 4-7 gears, and the time is 0.5-2 h.
7. The method of claim 1 wherein aqueous dispersions of BC or ANFs are protonated with mineral acids and then reacted with different concentrations of said TaS 2 Mixing the aqueous dispersions to obtain TaS with different mass ratios 2 /BC or TaS 2 In the step of ANFs heterogeneous aggregation dispersion liquid, the inorganic acid comprises sulfuric acid, hydrochloric acid and nitric acid, and the concentration after protonation treatment is 0.01-1 mol L -1 The protonation time is 0.5-2 h.
8. The method of claim 1, wherein said different mass ratios of TaS are used to form said tantalum disulfide film 2 /BC or TaS 2 Assembly of ANFs heterogeneous aggregated dispersions into TaS 2 /BC or TaS 2 The method for preparing the ANFs composite film comprises the following steps:
mixing the TaS with different mass ratios 2 /BC or TaS 2 Vacuum-filtering the ANFs heterogeneous aggregation dispersion liquid, adding 10-50 mL of deionized water, and carrying out vacuum drying on a vacuum-filtering membrane to finally obtain the TaS 2 /BC or TaS 2 /ANFs composite films.
9. The method for preparing a tantalum disulfide thin film according to claim 8, wherein the vacuum filtration membrane is a mixed cellulose filtration membrane or a polyethersulfone filtration membrane.
10. The method for preparing a tantalum disulfide film according to claim 8, wherein the vacuum drying is performed at a negative pressure of 0.08 to 0.1MPa, a drying temperature of 50 to 90 ℃ and a drying time of 9 to 15 hours.
11. The method of claim 8 wherein said TaS is formed by a process comprising forming a tantalum disulfide film from said tantalum disulfide 2 /BC or TaS 2 the/ANFs composite film is circular and has a thickness of 1-30 μm.
12. A tantalum disulfide film prepared by the method of any one of claims 1 to 11, said tantalum disulfide film comprising TaS 2 Nanoplatelets, BC or ANFs.
13. A preparation method of a tantalum disulfide film is characterized by comprising the following steps:
preparing TaS with different concentrations 2 An aqueous dispersion of said TaS 2 TaS in aqueous dispersions 2 Is a few-layer nano-sheet;
(ii) bringing different concentrations of said TaS 2 And carrying out vacuum filtration on the aqueous dispersion, and then carrying out vacuum drying to obtain the tantalum disulfide films with different thicknesses.
14. The method of claim 13, wherein different concentrations of TaS are provided 2 The step of preparing the aqueous dispersion comprises the following steps:
adopting alkali metal ion or alkaline solvent to react with 2H-TaS 2 Intercalation treatment is carried out, then high-speed centrifugation is carried out to remove redundant intercalation agent, and then the TaS is mechanically dispersed at room temperature 2 Configured as uniform TaS 2 An aqueous dispersion.
15. The method of claim 14, wherein said high concentration of alkali metal ions comprises Li + 、Na + 、K + Ions, the solution is deionized water, and the concentration range is 1-2 mol L -1 (ii) a The basic solvent comprises n-hexylamine or ammonia water.
16. The method for preparing tantalum disulfide film according to claim 14, wherein the intercalation time of the intercalation process is 6-12 h, the volume of the intercalation agent is 1-2 mL, and an inert gas is introduced during intercalation.
17. The method for preparing the tantalum disulfide film according to claim 14, wherein the centrifugation speed of the high-speed centrifugation is 8000-12000 rpm, the centrifugation times are 3-5 times, each time of the centrifugation is 10-30 min until the pH of the supernatant is 7, and the TaS after the high-speed centrifugation is finished 2 The concentration of the aqueous dispersion was 1.25mg mL -1 。
18. The method of claim 14, wherein the mechanical dispersion comprises ultrasonic dispersion, vortex oscillation dispersion, or ultrasonic plus vortex oscillation composite dispersion; wherein the ultrasonic dispersion is ultrasonic in an ice-water bath, the power is 500W, and the time is 0.5-2 h; the gear of vortex oscillation dispersion is 4-7, and the time is 0.5-2 h.
19. The method of claim 13 wherein different concentrations of said TaS are added to said tantalum disulfide film 2 In the step of obtaining the tantalum disulfide films with different thicknesses by vacuum drying after vacuum filtration of the aqueous dispersion, a polycarbonate filter membrane or a mixed cellulose filter membrane is selected as a vacuum filtration membrane, the negative pressure range of vacuum drying is 0.08-0.1 MPa, the drying temperature is 50-90 ℃, and the drying time is 9-15 hours.
20. The method of claim 13, wherein the tantalum disulfide film is circular and has a thickness in the range of 1 to 40 μm.
21. A tantalum disulfide film produced by the method of any of claims 13 through 19, said tantalum disulfide film comprising TaS 2 Nanosheets.
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| CN111470536A (en) * | 2020-05-29 | 2020-07-31 | 合肥工业大学 | High-performance tantalum disulfide two-dimensional layered film and preparation method and application thereof |
| CN112646236A (en) * | 2020-12-22 | 2021-04-13 | 武汉理工大学 | Preparation method of nanocellulose/molybdenum disulfide piezoelectric composite film |
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| CN103956470A (en) * | 2014-04-28 | 2014-07-30 | 浙江大学 | Two-dimensional layered composite film and preparation method and application thereof |
| CN108529676A (en) * | 2017-03-06 | 2018-09-14 | 中国科学技术大学 | A kind of preparation method of ultra-thin TMD two-dimensional nano pieces |
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